Deuterium excess in subtropical free troposphere water vapor: Continuous measurements from the Chajnantor Plateau, northern Chile

Abstract

Water vapor measured continuously by cavity ring-down spectroscopy from July 2012 to March 2013 on the hyperarid Chajnantor Plateau, northern Chile (elevation = 5080 m, pressure ≈ 550 hPa), has a mean deuterium excess (d-excess = δD - 8δ18O) of 46‰ ± 5‰ and frequently exceeds 100‰ at low water vapor mixing ratios (q ≤ 500 ppmv). These measurements provide empirical support for theoretical predictions of free troposphere d-excess. The d-excess measured at this site can be understood in terms of supersaturation with respect to ice at relative humidities between 100% and 130%, followed by mixing with moist midtropospheric or lower tropospheric air en route to the plateau. The d-excess measured at Chajnantor is consistent with predictions for d-excess in the upper troposphere from isotope-enabled general circulation models and with high vapor saturation over ice in cloud-resolving and microphysical models.