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Nitrous oxide (N2O) plays important roles in atmospheric chemistry both as a greenhouse gas and in stratospheric ozone depletion. Isotopic measurements of N2O have provided an invaluable insight into understanding its atmospheric sources and sinks. The preference for 15N fractionation between the central and terminal positions (the "site preference") is particularly valuable because it depends principally on the processes involved in N2O production or consumption, rather than the 15N content of the substrate from which it is formed. Despite the value of measurements of the site preference, there is no internationally recognized standard reference material of accurately known and accepted site preference, and there has been some lack of agreement in published studies aimed at providing such a standard. Previous work has been based on isotope ratio mass spectrometry (IRMS); in this work we provide an absolute calibration for the intramolecular site preference of 15N fractionation of working standard gases used in our laboratory by a completely independent technique—high-resolution Fourier transform infrared (FT-IR) spectroscopy. By reference to this absolute calibration, we determine the site preference for 25 samples of tropospheric N2O collected under clean air conditions to be 19.8‰ ± 2.1‰. This result is in agreement with that based on the earlier absolute calibration of Toyoda and Yoshida (Toyoda, S.; Yoshida, N. Anal. Chem. 1999, 71, 4711-4718) who found an average tropospheric site preference of 18.7‰ ± 2.2‰. We now recommend an interlaboratory exchange of working standard N2O gases as the next step to providing an international reference standard. [ABSTRACT FROM AUTHOR]

Continuous records of isotope behaviour in the environment are invaluable to understanding mass and energy fluxes. Although techniques such as isotope ratio mass spectrometry provide high precision data, they are not well suited to the analysis of a large number of samples and are currently restricted to use in the laboratory. Fourier transform infrared spectrometers are relatively cheap and sufficiently portable and robust to be taken into the field to collect continuous records of gas-phase isotope behaviour. Several examples of the application of this technique will be presented. One data set provides half-hourly determinations of vertical profiles of D / H in water vapour above agricultural fields over a 3-week period; the same infrared spectra can also be used to determine 13 C/ 12 C in CO 2 . The technique has also been applied to the study of CO 2 in ambient air and in a limestone cave system. Some of the features and complications associated with the method will also be considered. [ABSTRACT FROM AUTHOR]

Summary The stable isotopes of water are useful tracers of water sources and hydrological processes. Stable water isotope-enabled land surface modeling is a relatively new approach for characterizing the hydrological cycle, providing spatial and temporal variability for a number of hydrological processes. At the land surface, the integration of stable water isotopes with other meteorological measurements can assist in constraining surface heat flux estimates and discriminate between evaporation (E) and transpiration (T). However, research in this area has traditionally been limited by a lack of continuous in-situ isotopic observations. Here, the National Centre for Atmospheric Research stable isotope-enabled Land Surface Model (ISOLSM) is used to simulate the water and energy fluxes and stable water isotope variations. The model was run for a period of one month with meteorological data collected from a coastal sub-tropical site near Sydney, Australia. The modeled energy fluxes (latent heat and sensible heat) agreed reasonably well with eddy covariance observations, indicating that ISOLSM has the capacity to reproduce observed flux behavior. Comparison of modeled isotopic compositions of evapotranspiration (ET) against in-situ Fourier Transform Infrared spectroscopy (FTIR) measured bulk water vapor isotopic data (10 m above the ground), however, showed differences in magnitude and temporal patterns. The disparity is due to a small contribution from local ET fluxes to atmospheric boundary layer water vapor (∼1% based on calculations using ideal gas law) relative to that advected from the ocean for this particular site. Using ISOLSM simulation, the ET was partitioned into E and T with 70% being T. We also identified that soil water from different soil layers affected T and E differently based on the simulated soil isotopic patterns, which reflects the internal working of ISOLSM. These results highlighted the capacity of using the isotope-enabled models to discriminate between different hydrological components and add insight into expected hydrological behavior. [ABSTRACT FROM AUTHOR]