Erik J Oerter1, Michael Singleton1, Melissa Thaw1,2, M Lee Davisson1. 1. Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA, 94550, USA. 2. University of California, Merced, 5200 Lake Road, Merced, CA, 95340, USA.
Abstract
RATIONALE: Water vapor exposure experiments have applications for studying water physisorption and chemisorption hydration and hydroxylation reactions on a wide variety of material surfaces. The stable isotopes of hydrogen and oxygen in the water molecule are useful tracers of water exchange mechanisms and/or rates in such vapor exposure experiments. METHODS: We designed and built a humidity chamber system that uses membrane-mediated liquid-vapor exchange of water followed by mixing with dry air to control the relative humidity of air and its δ2 H and δ18 O isotopic composition. We tested the stability and precision of the humidity and its isotopic composition on hourly to 90-day timescales. RESULTS: The humidity chamber design reported here is capable of providing relative humidity control to within ±1%, and consistent δ2 H and δ18 O values of the water vapor that are similar to our cavity ringdown spectroscopy (CRDS) measurement precision (δ2 Hvap ± 0.7‰ and δ18 Ovap ± 0.24‰). We quantify the isotopic enrichment effects of Rayleigh distillation in the system and provide information on water reservoir sizes large enough to buffer isotopic enrichment effects to within measurement precision. CONCLUSIONS: The humidity chamber design reported here provides a means to create constant δ2 H and δ18 O values over the course of an exposure experiment. The design has applications to a wide range of studies of water sorption on material surfaces from foods and pharmaceuticals to geological materials.
RATIONALE: Water vapor exposure experiments have applications for studying water physisorption and chemisorption hydration and hydroxylation reactions on a wide variety of material surfaces. The stable isotopes of hydrogen and oxygen in the water molecule are useful tracers of water exchange mechanisms and/or rates in such vapor exposure experiments. METHODS: We designed and built a humidity chamber system that uses membrane-mediated liquid-vapor exchange of water followed by mixing with dry air to control the relative humidity of air and its δ2 H and δ18 O isotopic composition. We tested the stability and precision of the humidity and its isotopic composition on hourly to 90-day timescales. RESULTS: The humidity chamber design reported here is capable of providing relative humidity control to within ±1%, and consistent δ2 H and δ18 O values of the water vapor that are similar to our cavity ringdown spectroscopy (CRDS) measurement precision (δ2 Hvap ± 0.7‰ and δ18 Ovap ± 0.24‰). We quantify the isotopic enrichment effects of Rayleigh distillation in the system and provide information on water reservoir sizes large enough to buffer isotopic enrichment effects to within measurement precision. CONCLUSIONS: The humidity chamber design reported here provides a means to create constant δ2 H and δ18 O values over the course of an exposure experiment. The design has applications to a wide range of studies of water sorption on material surfaces from foods and pharmaceuticals to geological materials.