Atmosphere-Snow Exchange Explains Surface Snow Isotope Variability.

The climate signal imprinted in the snow isotopic composition allows to infer past climate variability from ice core stable water isotope records. The concurrent evolution of vapor and surface snow isotopic composition between precipitation events indicates that post-depositional atmosphere-snow humidity exchange influences the snow and hence the ice core isotope signal. To date, however, this is not accounted for in paeleoclimate reconstructions from isotope records. Here we show that vapor-snow exchange explains 36% of the summertime day-to-day δ18O variability of the surface snow between precipitation events, and 53% of the δD variability. Through observations from the Greenland Ice Sheet and accompanying modeling we demonstrate that vapor-snow exchange introduces a warm bias on the summertime snow isotope value relevant for ice core records. In case of long-term variability in atmosphere-snow exchange the relevance for the ice core signal is also variable and thus paleoclimate reconstructions from isotope records should be revisited.

Non-Equilibrium Fractionation Factors for D/H and 18O/16O During Oceanic Evaporation in the North-West Atlantic Region.

Ocean isotopic evaporation models, such as the Craig-Gordon model, rely on the description of nonequilibrium fractionation factors that are, in general, poorly constrained. To date, only a few gradient-diffusion type measurements have been performed in ocean settings to test the validity of the commonly used parametrization of nonequilibrium isotopic fractionation during ocean evaporation. In this work, we present 6 months of water vapor isotopic observations collected from a meteorological tower located in the northwest Atlantic Ocean (Bermuda) with the objective of estimating nonequilibrium fractionation factors (k, ‰) for ocean evaporation and their wind speed dependency. The Keeling Plot method and Craig-Gordon model combination were sensitive enough to resolve nonequilibrium fractionation factors during evaporation resulting into mean values of k 18 = 5.2 ± 0.6‰ and k 2 = 4.3 ± 3.4‰. Furthermore, we evaluate the relationship between k and 10-m wind speed over the ocean. Such a relationship is expected from current evaporation theory and from laboratory experiments made in the 1970s, but observational evidence is lacking. We show that (a) in the observed wind speed range [0-10 m s-1], the sensitivity of k to wind speed is small, in the order of -0.2‰ m-1 s for k 18, and (b) there is no empirical evidence for the presence of a discontinuity between smooth and rough wind speed regime during isotopic fractionation, as proposed in earlier studies. The water vapor d-excess variability predicted under the closure assumption using the k values estimated in this study is in agreement with observations over the Atlantic Ocean.

Evidence of Isotopic Fractionation During Vapor Exchange Between the Atmosphere and the Snow Surface in Greenland.

Several recent studies from both Greenland and Antarctica have reported significant changes in the water isotopic composition of near-surface snow between precipitation events. These changes have been linked to isotopic exchange with atmospheric water vapor and sublimation-induced fractionation, but the processes are poorly constrained by observations. Understanding and quantifying these processes are crucial to both the interpretation of ice core climate proxies and the formulation of isotope-enabled general circulation models. Here, we present continuous measurements of the water isotopic composition in surface snow and atmospheric vapor together with near-surface atmospheric turbulence and snow-air latent and sensible heat fluxes, obtained at the East Greenland Ice-Core Project drilling site in summer 2016. For two 4-day-long time periods, significant diurnal variations in atmospheric water isotopologues are observed. A model is developed to explore the impact of this variability on the surface snow isotopic composition. Our model suggests that the snow isotopic composition in the upper subcentimeter of the snow exhibits a diurnal variation with amplitudes in δ18O and δD of ~2.5‰ and ~13‰, respectively. As comparison, such changes correspond to 10-20% of the magnitude of seasonal changes in interior Greenland snow pack isotopes and of the change across a glacial-interglacial transition. Importantly, our observation and model results suggest, that sublimation-induced fractionation needs to be included in simulations of exchanges between the vapor and the snow surface on diurnal timescales during summer cloud-free conditions in northeast Greenland.

Ice-vapor equilibrium fractionation factor of hydrogen and oxygen isotopes: experimental investigations and implications for stable water isotope studies.

RATIONALE: The equilibrium fractionation factors govern the relative change in the isotopic composition during phase transitions of water. The commonly used results, which were published more than 40 years ago, are limited to a minimum temperature of -33°C. This limits the reliability in cold regions. With recent instrumental developments it is now possible to test the accuracy of the earlier results as well as extend the temperature range. METHODS: Novel measurements were made of the ice-vapor equilibrium fractionation factor α between 0°C and -40°C, from a unique experimental setup using both a Picarro cavity ringdown spectrometer and a TC/EA IRMS system. Using both systems allows for continuous monitoring of the equilibrium state of the system as well as testing for reproducibility. RESULTS: The results of the experiments show fractionation factors for δ(2) H and δ(18) O values, with a temperature dependency in accordance with theory for equilibrium fractionation. We obtain the following expressions for the temperature dependency of the fractionation coefficients: ln(αδ2H)=0.2133-(203.10/T+(48888/T2 ln(αδ18O)=0.0831-(49.192/T)+(8312.5/T2). Compared with previous experimental work, a significantly larger α for δ(2) H is obtained while, for δ(18) O, α is larger for temperatures below -20°C and slightly lower for temperatures above this. CONCLUSIONS: Using the new values for α, a Rayleigh distillation model shows significant changes in both magnitude and shape of an annual deuterium excess signal in Greenland. This emphasizes the importance of a well-defined value of α for accurate studies of the processes in the hydrological cycle and underlines the significance of the differences between the results of this work and earlier work.