The Chicago Water Isotope Spectrometer (ChiWIS-lab): A tunable diode laser spectrometer for chamber-based measurements of water vapor isotopic evolution during cirrus formation.

Abstract

We describe a new tunable diode laser (TDL) absorption instrument, the Chicago Water Isotope Spectrometer, designed for measurements of vapor-phase water isotopologues in conditions characteristic of the upper troposphere [190-235 K temperature and 2-500 parts per million volume (ppmv) water vapor]. The instrument is primarily targeted for measuring the evolving ratio of HDO/H2O during experiments in the "Aerosol Interaction and Dynamics in the Atmosphere" (AIDA) cloud chamber. The spectrometer scans absorption lines of both H2O and HDO near the 2.64 µm wavelength in a single current sweep, increasing the accuracy of isotopic ratio measurements. At AIDA, the instrument is configured with a 256-m path length White cell for in situ measurements, and effective sensitivity can be augmented by enhancing the HDO content of chamber water vapor by an order of magnitude. The instrument has participated to date in the 2012-2013 IsoCloud campaigns studying isotopic partitioning during the formation of cirrus clouds and in the AquaVIT-II instrument intercomparison campaign. Realized precisions for 1-s measurements during these campaigns were 22 ppbv for H2O and 16 ppbv for HDO, equivalent to relative precisions of less than 0.5% for each species at 8 ppmv water vapor. The 1-s precision of the [HDO]/[H2O] ratio measurement ranged from 1.6‰ to 5.6‰ over the range of experimental conditions. H2O measurements showed agreement with calculated saturation vapor pressure to within 1% in conditions of sublimating ice and agreement with other AIDA instruments (the AIDA SP-APicT reference TDL instrument and an MBW 373LX chilled mirror hygrometer) to within 2.5% and 3.8%, respectively, over conditions suitable for all instruments (temperatures from 204 K to 234 K and H2O content equivalent to 15-700 ppmv at 200 hPa).