Atmospheric Chemistry and Physics
The D/H isotope ratio is used to attribute boundary layer humidity changes to the set of contributing fluxes for a case following a snowstorm in which a snow pack of about 10 cm vanished. Profiles of H2O and CO2 mixing ratio, D/H isotope ratio, and several thermodynamic properties were measured from the surface to 300 m every 15 min during four winter days near Boulder, Colorado. Coeval analysis of the D/H ratios and CO2 concentrations find these two variables to be complementary with the former being sensitive to daytime surface fluxes and the latter particularly indicative of nocturnal surface sources. Together they capture evidence for strong vertical mixing during the day, weaker mixing by turbulent bursts and low level jets within the nocturnal stable boundary layer during the night, and frost formation in the morning. The profiles are generally not well described with a gradient mixing line analysis because D/H ratios of the end members (i.e., surface fluxes and the free troposphere) evolve throughout the day which leads to large uncertainties in the estimate of the D/H ratio of surface water flux. A mass balance model is constructed for the snow pack, and constrained with observations to provide an optimal estimate of the partitioning of the surface water flux into contributions from sublimation, evaporation of melt water in the snow and evaporation from ponds. Results show that while vapor measurements are important in constraining surface fluxes, measurements of the source reservoirs (soil water, snow pack and standing liquid) offer stronger constraint on the surface water balance. Measurements of surface water are therefore essential in developing observational programs that seek to use isotopic data for flux attribution.