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The present paper describes a compact and cryogen-free, quantum cascade laser based absorption spectrometer (QCLAS) designed for in situ, continuous and high precision isotope ratio measurements of atmospheric CO2. The mobile instrument incorporates several new features including a novel astigmatic multi-pass cell assembly, a quasi-room temperature quantum cascade laser, thermoelectrically cooled detectors as well as a new retrieval approach. The combination of these features now makes it possible to measure isotope ratios of ambient CO2 with a precision of 0.03 and 0.05‰ for δ13C and δ18O, respectively, using a 100s integration time. A robust and optimized calibration procedure was developed to bring the retrieved isotope ratios on an absolute scale. This assures an accuracy better than 0.1‰ under laboratory conditions. The instrument performance was also assessed in a field campaign in which the spectrometer operated autonomously and provided mixing ratio values for the main three CO2 isotopologues at one second time resolution. An accuracy of 0.2‰ was routinely obtained for both isotope ratios during the entire period. The results were in excellent agreement with the standard laboratory-based isotope ratio mass spectrometer measurements made on field-collected flask samples. A few illustrative examples are used to depict the potential of this optical method in atmosphere-biosphere research

A quantum cascade laser based absorption spectrometer for continuous and direct measurements of NO and NO2 was employed at the high-altitude monitoring site Jungfraujoch (3580 m a.s.l., Switzerland) during a three-month campaign in spring/summer 2012. The total reactive nitrogen, NOy, was also measured in the form of NO after conversion on a gold catalyst. The aim was to assess the suitability of the instrument for long-term monitoring of the main reactive nitrogen species under predominantly free tropospheric air conditions. A precision (1σ) of 10 and 3 ppt for NO and NO2 was achieved under field conditions after 180 s averaging time. The linear dynamic range of the instrument has been verified for both species from the detection limit up to 45 ppb. The spectrometer shared a common sampling inlet with a chemiluminescence-based analyzer. The comparison of the time series shows excellent agreement between the two techniques and demonstrates the adequacy of the laser spectroscopic approach for this kind of demanding environmental applications.

High-precision analyses of the isotopic composition of methane in ambient air can potentially be used to discriminate between different source categories. Due to the complexity of isotope ratio measurements, such analyses have generally been performed in the laboratory on air samples collected in the field. This poses a limitation on the temporal resolution at which the isotopic composition can be monitored with reasonable logistical effort. Here we present the performance of a dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique for in situ analysis of the isotopic composition of methane under field conditions. Both systems were deployed at the Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months. The IRMS and QCLAS instruments were in excellent agreement with a slight systematic offset of (+0.25 ± 0.04) ‰ for δ13C and (−4.3 ± 0.4) ‰ for δD. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high-precision and high-temporal-resolution dataset not only reveals the overwhelming contribution of isotopically depleted agricultural CH4 emissions from ruminants at the Cabauw site but also allows the identification of specific events with elevated contributions from more enriched sources such as natural gas and landfills. The final dataset was compared to model calculations using the global model TM5 and the mesoscale model FLEXPART-COSMO. The results of both models agree better with the measurements when the TNO-MACC emission inventory is used in the models than when the EDGAR inventory is used. This suggests that high-resolution isotope measurements have the potential to further constrain the methane budget when they are performed at multiple sites that are representative for the entire European domain.

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called TRace gas EXtractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, μmole/mole) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on replicate measurements of compressed air during a two-week intercomparison campaign, the repeatability of the TREX-QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass-spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. Thus, the intercomparison also reveals the need for reference air samples with accurately determined isotopic composition of CH4 to further improve the interlaboratory compatibility.

We describe the first high precision real-time analysis of the N2O site-specific isotopic composition at ambient mixing ratios. Our technique is based on mid-infrared quantum cascade laser absorption spectroscopy (QCLAS) combined with an automated preconcentration unit. The QCLAS allows for simultaneous and specific analysis of the three main stable N2O isotopic species, 14N15N16O, 15N14N16O, 14N14N16O, and the respective site-specific relative isotope ratio differences δ15Nα and δ 15Nβ. Continuous, stand-alone operation is achieved by using liquid nitrogen free N2O preconcentration, a quasi-room-temperature quantum cascade laser (QCL), quantitative sample transfer to the QCLAS and an optimized calibration algorithm. The N2O site-specific isotopic composition (δ15Nα and δ15Nβ) can be analysed with a long-term precision of 0.2‰. The potential of this analytical tool is illustrated by continuous N2O isotopomer measurements above a grassland plot over a three week period, which allowed identification of microbial source and sink processes.

RATIONALE Nitrous oxide (N2O), a highly climate‐relevant trace gas, is mainly derived from microbial denitrification and nitrification processes in soils. Apportioning N2O to these source processes is a challenging task, but better understanding of the processes is required to improve mitigation strategies. The N2O site‐specific 15N signatures from denitrification and nitrification have been shown to be clearly different, making this signature a potential tool for N2O source identification. We have applied for the first time quantum cascade laser absorption spectroscopy (QCLAS) for the continuous analysis of the intramolecular 15N distribution of soil‐derived N2O and compared this with state‐of‐the‐art isotope ratio mass spectrometry (IRMS).METHODSSoil was amended with nitrate and sucrose and incubated in a laboratory setup. The N2O release was quantified by FTIR spectroscopy, while the N2O intramolecular 15N distribution was continuously analyzed by online QCLAS at 1 Hz resolution. The QCLAS results on time‐integrating flask samples were compared with those from the IRMS analysis.RESULTSThe analytical precision (2σ) of QCLAS was around 0.3 ‰ for the δ15Nbulk and the 15N site preference (SP) for 1‐min average values. Comparing the two techniques on flask samples, excellent agreement (R2 = 0.99; offset of 1.2 ‰) was observed for the δ15Nbulk values while for the SP values the correlation was less good (R2 = 0.76; offset of 0.9 ‰), presumably due to the lower precision of the IRMS SP measurements.CONCLUSIONSThese findings validate QCLAS as a viable alternative technique with even higher precision than state‐of‐the‐art IRMS. Thus, laser spectroscopy has the potential to contribute significantly to a better understanding of N turnover in soils, which is crucial for advancing strategies to mitigate emissions of this efficient greenhouse gas.

We present the continuous data record of atmospheric CO2 isotopes measured by laser absorption spectroscopy for an almost four year period at the High Altitude Research Station Jungfraujoch (3580 m a.s.l.), Switzerland. The mean annual cycles derived from data of December 2008 to September 2012 exhibit peak-to-peak amplitudes of 11.0 μmol mol−1 for CO2, 0.60‰ for δ13C and 0.81‰ for δ18O. The high temporal resolution of the measurements also allow us to capture variations on hourly and diurnal timescales. For CO2 the mean diurnal peak-to-peak amplitude is about 1 μmol mol−1 in spring, autumn and winter and about 2 μmol mol−1 in summer. The mean diurnal variability in the isotope ratios is largest during the summer months too, with an amplitude of about 0.1‰ both in the δ13C and δ18O, and a smaller or no discernible diurnal cycle during the other seasons. The day-to-day variability, however, is much larger and depends on the origin of the air masses arriving at Jungfraujoch. Backward Lagrangian particle dispersion model simulations revealed a close link between air composition and prevailing transport regimes and could be used to explain part of the observed variability in terms of transport history and influence region. A footprint clustering showed significantly different wintertime CO2, δ13C and δ18O values depending on the origin and surface residence times of the air masses. Several major updates on the instrument and the calibration procedures were performed in order to further improve the data quality. We describe the new measurement and calibration setup in detail and demonstrate the enhanced performance of the analyzer. A measurement precision of about 0.02‰ for both isotope ratios has been obtained for an averaging time of 10 min, while the accuracy was estimated to be 0.1‰, including the uncertainty of the calibration gases., Atmospheric Measurement Techniques, 6 (7), ISSN:1867-1381, ISSN:1867-8548

Biogeosciences Discussions, 6 (2), ISSN:1810-6277, ISSN:1810-6285

International audience; Nitrous oxide fluxes were measured at the Lägeren CarboEurope IP flux site over the multi-species mixed forest dominated by European beech and Norway spruce. Measurements were carried out during a four-week period in October?November 2005 during leaf senescence. Fluxes were measured with a standard ultrasonic anemometer in combination with a quantum cascade laser absorption spectrometer that measured N2O, CO2, and H2O mixing ratios simultaneously at 5 Hz time resolution. To distinguish insignificant fluxes from significant ones it is proposed to use a new approach based on the significance of the correlation coefficient between vertical wind speed and mixing ratio fluctuations. This procedure eliminated roughly 56% of our half-hourly fluxes. Based on the remaining, quality checked N2O fluxes we quantified the mean efflux at 0.8 ± 0.4 ?mol m?2 h?1 (mean ± standard error). Most of the contribution to the N2O flux occurred during a 6.5-h period starting 4.5 h before each precipitation event. No relation with precipitation amount could be found. Visibility data representing fog density and duration at the site indicate that wetting of the canopy may have as strong an effect on N2O effluxes as does below-ground microbial activity. It is speculated that above-ground N2O production from the senescing leaves at high moisture (fog, drizzle, onset of precipitation event) may be responsible for part of the measured flux. In comparison with the annual CO2 budget of ?342 g C m?2 yr?1 it is estimated that concurrent N2O fluxes offset at least 5% of the greenhouse forcing reduction via net CO2 uptake.