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Rationale: Unravelling the biogeochemical cycle of the potent greenhouse gas nitrous oxide (N2O) is an underdetermined problem in environmental sciences due to the multiple source and sink processes involved, which complicate mitigation of its emissions. Measuring the doubly isotopically substituted molecules (isotopocules) of N2O can add new opportunities to fingerprint and constrain its cycle. Methods: We present a laser spectroscopic technique to selectively and simultaneously measure the eight most abundant isotopocules of N2O, including three doubly substituted species – so called “clumped isotopes”. For the absolute quantification of individual isotopocule abundances, we propose a new calibration scheme that combines thermal equilibration of a working standard gas with a direct mole fraction‐based approach. Results: The method is validated for a large range of isotopic composition values by comparison with other established methods (laser spectroscopy using conventional isotopic scale and isotope ratio mass spectrometry). Direct intercomparison with recently developed ultrahigh‐resolution mass spectrometry shows clearly the advantages of the new laser technique, especially with respect to site specificity of isotopic substitution in the N2O molecule. Conclusions: Our study represents a new methodological basis for the measurements of both singly substituted and clumped N2O isotopes. It has a high potential to stimulate future research in the N2O community by establishing a new class of reservoir‐insensitive tracers and molecular‐scale insights. [ABSTRACT FROM AUTHOR]

RATIONALE: Clumped isotope analyses (Δ47) of carbonates by dual inlet (DI) mass spectrometry require long integration times to reach the necessary high precision due to the low abundance of the rare isotopologue 13C18O16O. Traditional DI protocols reach this only with large amounts of sample and/or a large number of replicates as a large portion of the analyte gas is wasted. We tested an improved analytical workflow that significantly reduces the sample sizes and total analysis time per sample while preserving precision and accuracy. METHODS: We implemented the LIDI (long-integration dual-inlet) protocol to measure carbonates in micro-volume mode using a Kiel IV carbonate device coupled to a Thermo Scientific 253 Plus isotope ratio mass spectrometer without the new 1013 ohm amplifier technology. The LIDI protocol includes a single measurement of the sample gas (600 s integration) followed by a single measurement of the working gas (WG) with the same integration time. RESULTS: The Δ47 measurements of four calcite standards over a period of 5 weeks demonstrate excellent long-term stability with a standard deviation of ±0.021 to ±0.025 ‰ for the final values of the individual aliquots. The Δ47 analyses of a coral, four foraminifera and a calcite precipitated in the laboratory demonstrate that 14 replicates of 90 to 120 μg are sufficient to achieve an external precision of ±0.007 ‰ (1SE) or of ±0.013 ‰ at the 95% confidence level. CONCLUSIONS: This study demonstrates that by using a Kiel IV–253 Plus system with LIDI it is possible to achieve the same analytical precision as conventional DI measurements with at least a factor of 40 less sample material. With the new 1013 ohm resistor technology there is the potential to reduce the required sample material even more. This opens new avenues of research in paleoceanography, paleoclimatology, low-temperature diagenesis and other currently sample size limited applications. [ABSTRACT FROM AUTHOR]

RATIONALE Carbonate clumped isotope thermometry is a powerful new technique increasingly used in many fields in earth science. Recently, it has been shown that clumped isotope measurements can be performed with a Kiel carbonate preparation device and micro-volume analyses, allowing measurements of small (1.5-2 mg) carbonate samples. However, common data correction schemes rely on measurements of gases prepared offline, potentially leading to unrecognized biases in the results. METHODS We propose a new correction scheme for the Kiel device method including: (1) A pressure-sensitive baseline correction (PBL) of the raw beam signals; (2) Transfer of data to the absolute reference frame; (3) Correction for acid fractionation; (4) Correction for average standard offsets; (5) When necessary, correction for Δ47 scale compression based on offsets among standards with different ordering state. The long-term performance of the new scheme was tested with a large set of standard measurements (N = 432) obtained over the course of 15 months. RESULTS The PBL correction reliably removes composition-dependent artifacts, which are commonly corrected for with gas measurements, and offsets observed in micro-volume measurements when ion beams are imbalanced. We show that the shape of the PBL can vary strongly and needs to be properly characterized. Combined PBL and standard correction resulted in long-term stability with standard deviations in Δ47 of 0.012-0.016 ‰ for the five standards over the whole period, close to the average error of 0.011 ‰ observed for individual measurements consisting of 10 replicate analyses. CONCLUSIONS Our correction scheme eliminates the need for routine gas measurements, allowing for equal treatment of samples and standards with the Kiel device setup. While the PBL and standard data obtained over 15 months reveal variable mass spectrometer behavior, they provide a robust means of correction, yielding reproducible results from small carbonate samples in the long term. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

RATIONALE High-precision stable isotope measurements in gas-source isotope ratio mass spectrometry are generally carried out by repeated comparison of the composition of an unknown sample with that of a working gas (WG) through a dual-inlet (DI). Due to the established DI protocols, however, most of the sample gas is wasted rather than measured, which is a major problem when sample size is limited. Here we propose a new methodology allowing the measurement of a much larger portion of the available sample. METHODS We tested a new measurement protocol, the long-integration dual-inlet (LIDI) method, which consists of a single measurement of the sample for 200 to 600 seconds followed by a single measurement of the WG. The isotope ratios of the sample are calculated by comparison of the beam ratios of the WG and sample at equivalent intensities of the major ion beam. RESULTS Three isotopically very different CO2 samples were analyzed. The LIDI measurements of large samples (50 to 100 µmol of CO2) measured at quasi-constant beam sizes, and of small samples (1.5 to 2 µmol of CO2) measured in micro-volume mode, generated results that are indistinguishable from the standard DI measurements for carbon, oxygen and clumped isotope compositions. The external precision of Δ47 using the LIDI protocol (~±0.007 ‰) is similar to that of the state of the art DI measurements. CONCLUSIONS For traditional and clumped isotope measurements of CO2, the LIDI protocol allows the measurement of a much larger portion of the sample gas rather than only ~20 % of it. In addition, the sample can be measured at higher signal intensity and for longer time, allowing the measurement of smaller samples while preserving precision. We suggest that other gases commonly used for stable isotope measurements with gas-source mass spectrometry would also benefit from this new protocol. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

RATIONALE The measurement of the abundances of minor isotopologues by mass spectrometry requires correction of subtle non-linearities in the mass spectrometer that cause deviations in the relationship between actual and measured isotope ratios. Here we show that negative backgrounds on the Faraday cups recording the minor ion beams are the cause of the observed non-linearities in the measurement of CO2 isotopologues, and propose a new correction procedure for clumped isotope measurements. METHODS We carefully investigated the cause of non-linearity effects in the measurement of the abundance of 13C18O16O, a minor isotopologue of CO2 with m/z 47, on two different mass spectrometers. By using gases of different composition with close to stochastic and with non-random distribution of isotopes we demonstrate that the apparent dependence of the excess abundance of the isotopologue of m/z 47 on the bulk isotopic composition of CO2 is due to a background interference that is linearly dependent on the partial pressure of the gas in the source of the mass spectrometer. CONCLUSIONS Background determination with gas flowing into the source of the mass spectrometer is necessary for accurate clumped isotope measurements of CO2. Background corrections can be performed accurately if the slit width of the m/z 44 Faraday cup significantly exceeds that of the one for m/z 47, using a correlation between m/z 44 signal intensity and the corresponding minimum in m/z 47 background. We propose two new correction schemes that reduce the time-consuming measurement of gases of different bulk isotopic compositions. These findings may also be relevant for the measurement of other rare isotopologues by mass spectrometry. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]