On-line in situ determination of deuterium content in water via FTIR spectroscopy

Hydrogen stable isotope ratios are critical indicators in environmental geochemical studies for characterizing runoff, determination of groundwater groups and water uptake by plants etc. (generally used in combination with ¹⁸O analysis). While the common technique for this hydrogen isotope measurement is Mass Spectrometry, FTIR (Fourier transform infra-red) spectroscopy may be an alternative method, with the advantage of direct and simple operating measurements. The FTIR spectrometer has the advantage of performing in situ measurements, which can delineate continuous geochemical processes. In situ measurements decrease errors that may be a consequence of sample delivery to the laboratory and off-site analysis procedures. In this study, we have developed a new simple procedure for in situ hydrogen stable isotope ratio measurements. We discovered that the HDO (hydrogen, deuterium, and oxygen) absorbance peak at 2504 cm^-1 is the most suitable for water sample direct analysis, with the FTIR device, using a circular sample cell for liquid samples. A case study analyzing water samples from a karstic cave (Sif cave, Israel) verified the following: (a) on-line determination of water D/H ratio can be carried out with the portable FTIR spectrometer (and thus can be used for field measurements such as in the Sif cave) and (b) the D concentration sensitivity achieved was at a 0.01‰ level, with a standard deviation of 0.006‰.