Search

Nitrous oxide ([N.sub.2]O) plays important roles in atmospheric chemistry both as a greenhouse gas and in stratospheric ozone depletion. Isotopic measurements of [N.sub.2]O have provided an invaluable insight into understanding its atmospheric sources and sinks. The preference for [15.sup]N fractionation between the central and terminal positions (the 'site preference') is particularly valuable because it depends principally on the processes involved in [N.sub.2]O production or consumption, rather than the [sup.15]N 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 [sup.15]N 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 [N.sub.2]O collected under clean air conditions to be 19.8 [per thousand] [+ or -] 2.1 [per thousand]. 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 [per thousand] [+ or -] 2.2 [per thousand]. We now recommend an interlaboratory exchange of working standard [N.sub.2]O gases as the next step to providing an international reference standard.

The stable isotopic composition of water vapour provides information about moisture sources and processes that is difficult to obtain with traditional measurement techniques. Recently, it has been proposed that the D-excess (dv = δ2H - 8 × δ18O) of water vapour can provide a diagnostic tracer of continental moisture recycling. However, D-excess exhibits a diurnal cycle that has been observed across a variety of ecosystems and may be influenced by a range of processes beyond regional scale moisture recycling, including local evaporation (ET) fluxes. There is a lack of measurements of D-excess in evaporation (ET) fluxes, which has made it difficult to assess how ET fluxes modify the D-excess in water vapour (dv). With this in mind, we employed a chamber based approach to directly measure D-excess in ET (dET) fluxes. We show that ET fluxes imposed a negative forcing on the ambient vapour and could not explain the higher daytime dv values. The low dET observed here was sourced from a soil water pool that had undergone an extended drying period, leading to low D-excess of the soil moisture. A strong correlation between daytime dv and locally measured relative humidity was consistent with an oceanic moisture source, suggesting that remote hydrological processes were the major contributor to daytime dv variability. During the early evening, ET fluxes into a shallow nocturnal inversion layer caused a lowering of the dv values near the surface. In addition, transient mixing of vapour with a higher D-excess from above the nocturnal inversion modified these values, causing large within night variability. These results indicate dET can generally be expected to show large spatial and temporal variability and to depend on the soil moisture state. For long periods between rain events, common in semi-arid environments, ET would be expected to impose negative forcing on the surface dv. The variability of D-excess in ET fluxes therefore needs to be considered when using dv to study moisture recycling and during extended dry periods may act as a tracer of the relative humidity of the oceanic moisture source. [ABSTRACT FROM AUTHOR]

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]

Monitoring the development of vegetation height through time provides a key indicator of crop health and overall condition. Traditional manual approaches for monitoring crop height are generally time consuming, labor intensive and impractical for large-scale operations. Dynamic crop heights collected through the season allow for the identification of within-field problems at critical stages of the growth cycle, providing a mechanism for remedial action to be taken against end of season yield losses. With advances in unmanned aerial vehicle (UAV) technologies, routine monitoring of height is now feasible at any time throughout the growth cycle. To demonstrate this capability, five digital surface maps (DSM) were reconstructed from high-resolution RGB imagery collected over a field of maize during the course of a single growing season. The UAV retrievals were compared against LiDAR scans for the purpose of evaluating the derived point clouds capacity to capture ground surface variability and spatially variable crop height. A strong correlation was observed between structure-from-motion (SfM) derived heights and pixel-to-pixel comparison against LiDAR scan data for the intra-season bare-ground surface (R2 = 0.77 − 0.99, rRMSE = 0.44% − 0.85%), while there was reasonable agreement between canopy comparisons (R2 = 0.57 − 0.65, rRMSE = 37% − 50%). To examine the effect of resolution on retrieval accuracy and processing time, an evaluation of several ground sampling distances (GSD) was also performed. Our results indicate that a 10 cm resolution retrieval delivers a reliable product that provides a compromise between computational cost and spatial fidelity. Overall, UAV retrievals were able to accurately reproduce the observed spatial variability of crop heights within the maize field through the growing season and provide a valuable source of information with which to inform precision agricultural management in an operational context. [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 13C/12C in CO2. The technique has also been applied to the study of CO2 in ambient air and in a limestone cave system. Some of the features and complications associated with the method will also be considered.