Water vapor δ2H, δ18O and δ17O measurements using an off-axis integrated cavity output spectrometer – sensitivity to water vapor concentration, delta value and averaging-time

Abstract

Rationale High-precision analysis of atmospheric water vapor isotope compositions, especially δ17O values, can be used to improve our understanding of multiple hydrological and meteorological processes (e.g., differentiate equilibrium or kinetic fractionation). This study focused on assessing, for the first time, how the accuracy and precision of vapor δ17O laser spectroscopy measurements depend on vapor concentration, delta range, and averaging-time. Methods A Triple Water Vapor Isotope Analyzer (T-WVIA) was used to evaluate the accuracy and precision of δ2H, δ18O and δ17O measurements. The sensitivity of accuracy and precision to water vapor concentration was evaluated using two international standards (GISP and SLAP2). The sensitivity of precision to delta value was evaluated using four working standards spanning a large delta range. The sensitivity of precision to averaging-time was assessed by measuring one standard continuously for 24 hours. Results Overall, the accuracy and precision of the δ2H, δ18O and δ17O measurements were high. Across all vapor concentrations, the accuracy of δ2H, δ18O and δ17O observations ranged from 0.10‰ to 1.84‰, 0.08‰ to 0.86‰ and 0.06‰ to 0.62‰, respectively, and the precision ranged from 0.099‰ to 0.430‰, 0.009‰ to 0.080‰ and 0.022‰ to 0.054‰, respectively. The accuracy and precision of all isotope measurements were sensitive to concentration, with the higher accuracy and precision generally observed under moderate vapor concentrations (i.e., 10000–15000 ppm) for all isotopes. The precision was also sensitive to the range of delta values, although the effect was not as large compared with the sensitivity to concentration. The precision was much less sensitive to averaging-time than the concentration and delta range effects. Conclusions The accuracy and precision performance of the T-WVIA depend on concentration but depend less on the delta value and averaging-time. The instrument can simultaneously and continuously measure δ2H, δ18O and δ17O values in water vapor, opening a new window to better understand ecological, hydrological and meteorological processes.