Water vapor delta H-2 and delta O-18 measurements using off-axis integrated cavity output spectroscopy

Abstract

We present a detailed assessment of a commercially available water vapor isotope analyzer (WVIA, Los Gatos Research, Inc.) for simultaneous in-situ measurements of delta H-2 and delta O-18 in water vapor. This method, based on off-axis integrated cavity output spectroscopy, is an alternative to the conventional water trap/isotope ratio mass spectrometry (IRMS) techniques. We evaluate the analyzer in terms of precision, memory effects, concentration dependence, temperature sensitivity and long-term stability. A calibration system based on a droplet generator is used to characterize the performance and to calibrate the analyzer. Our results show that the precision at an averaging time of 15 s is 0.16 parts per thousand for delta H-2 and 0.08 parts per thousand for delta O-18. The isotope ratios are strongly dependent on the water mixing ratio of the air. Taking into account this concentration dependence as well as the temperature sensitivity of the instrument we obtained a long-term stability of the water isotope measurements of 0.38 parts per thousand for delta H-2 and 0.25 parts per thousand for delta O-18. The accuracy of the WVIA was further assessed by comparative measurements using IRMS and a dew point generator indicating a linear response in isotopic composition and H2O concentrations. The WVIA combined with a calibration system provides accurate high resolution water vapor isotope measurements and opens new possibilities for hydrological and ecological applications.