Kalman filtering real-time measurements of H2O isotopologue ratios by laser absorption spectroscopy at 2.73 microm.

Kalman adaptive filtering was applied for the first time, to our knowledge, to the real-time simultaneous determination of water isotopic ratios using laser absorption spectroscopy at 2.73 microm. Measurements of the oxygen and hydrogen isotopologue ratios delta(18)O, delta(17)O, and delta(2)H in water showed a 1-sigma precision of 0.72 per thousand for delta(18)O, 0.48 per thousand for delta(17)O, and 0.84 per thousand for delta(2)H, while sampling the output of the tuned Kalman filter at 1 s time intervals. Using a standard running average technique, averaging over approximately 30 s is required to obtain the same level of precision.

Development and airborne operation of a compact water isotope ratio infrared spectrometer.

A sensitive laser spectrometer, named IRIS (water isotope ratio infrared spectrometer), was developed for the in situ detection of the isotopic composition of water vapour in the upper troposphere and the lower stratosphere. Isotope ratio measurements can be used to quantify troposphere-stratosphere exchange, and to study the water chemistry in the stratosphere. IRIS is based on the technique of optical feedback cavity-enhanced absorption spectroscopy. It uses a room temperature near-infrared laser, and does not require cryogenic cooling of laser or detectors. The instrument weighs 51 kg including its support structure. Airborne operation was demonstrated during three flights aboard the European M55-Geophysica stratospheric research aircraft, as part of the AMMA/SCOUT-03 (African Monsoon Multidisciplinary Analysis/Stratospheric Climate links with emphasis on the Upper Troposphere and lower stratosphere) campaign in Burkina Faso in August 2006. One-second averaged, vertical profiles of delta(2)H, delta(17)O and delta(18)O in the upper troposphere are shown, as are the delta(17)O-delta(18)O and delta(2)H-delta(18)O relations. The data are discussed with reference to a Rayleigh distillation model. As expected, there is no indication of non-mass-dependent fractionation (also known as mass-independent fractionation) in the troposphere. Furthermore, improvements to the thermal management system and a move to a (cryogen-free) longer-wavelength laser source are discussed, which together should result in approximately two orders of magnitude improvement of the sensitivity.

Assessment of the amount of body water in the Red Knot (Calidris canutus): an evaluation of the principle of isotope dilution with 2H, (17)O, and (18)O as measured with laser spectrometry and isotope ratio mass spectrometry.

We have used the isotope dilution technique to study changes in the body composition of a migratory shorebird species (Red Knot, Calidris canutus) through an assessment of the amount of body water in it. Birds were quantitatively injected with a dose of water with elevated concentrations of 2H, (17)O, and (18)O. Thereafter, blood samples were taken and distilled. The resulting water samples were analysed using an isotope ratio mass spectrometry (for 2H and (18)O only) and a stable isotope ratio infrared laser spectrometry (2H, (17)O, and (18)O) to yield estimates of the amount of body water in the birds, which in turn could be correlated to the amount of body fat. Here, we validate laser spectrometry against mass spectrometry and show that all three isotopes may be used for body water determinations. This opens the way to the extension of the doubly labelled water method, used for the determination of energy expenditure, to a triply labelled water method, incorporating an evaporative water loss correction on a subject-by-subject basis or, alternatively, the reduction of the analytical errors by statistically combining the (17)O and (18)O measurements.

First real-time measurement of the evolving 2H/1H ratio during water evaporation from plant leaves.

We have studied the temporal behaviour of the deuterium isotope ratio of water vapour emerging from a freshly cut plant leaf placed in a dry nitrogen atmosphere. The leaf material was placed directly inside the sample gas cell of the stable isotope ratio infrared spectrometer. At the reduced pressure ( approximately 40 mbar) inside the cell, the appearance of water evaporating from the leaf is easily probed by the spectrometer, as well as the evolving isotope ratios, with a precision of about 1 per thousand. The demonstration experiment we describe measures the 2H/1H isotope ratio only, but the experiment can be easily extended to include the 18O/16O and 17O/16O isotope ratios. Plant leaf water isotope ratios provide important information towards quantification of the different components in the ecosystem water and carbon dioxide exchange.

Measuring delta13C of atmospheric air with non-dispersive infrared spectroscopy.

The potential use of non-dispersive infrared spectroscopy for measuring delta(13)C in air is demonstrated. This technique has already been successfully established for breath test analyses in medical diagnostics, where the CO(2) concentration ranges from 1 to 5 vol.% in the exhaled breath of vertebrates. For breath tests, the sensitivity and accuracy has been improved to reach a standard deviation of 0.2 per thousand (delta-value). Further adjustments were necessary to improve the sensitivity of the instrument at concentration levels typical of atmospheric air. The long-term stability is given by a standard deviation of 0.35 per thousand for CO(2) concentrations of about 400 ppm with signal averaging over 60 s.

Isotope analysis of water by means of near infrared dual-wavelength diode laser spectroscopy.

A novel diode laser spectrometer was developed using dualwavelength multiplexing, ensuring ideal conditions for high-precision and simultaneous measurements of the 2H/1H, 17O/16O, and 18O/16O isotope ratios in water. A 1.4-m diode laser probed a H16OH / HO2H line pair near 7198 cm-1, while a similar laser observed H16OH, H17OH, and H18OH rovibrational lines around 7183 cm-1, or a H16OH / H18OH line pair near 7200 cm-1. The 1-sigma standard deviation is 0.2 per thousand for 18O/16O, and 0.5 per thousand for the 2H/1H and 17O/16O isotope ratios. Preliminary experiments with repeated injections of a natural abundance sample point to an accuracy of about 1 per thousand for all three isotope ratios in natural samples.