文章基本信息

标题：Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds
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作者：Kara D. Lamb ; Benjamin W. Clouser ; Maximilien Bolot 等
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2017
卷号：114
期号：22
页码：5612-5617
DOI：10.1073/pnas.1618374114
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (−40 °C), conditions necessary to form cirrus clouds in the Earth’s atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122–127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H₂O equilibrium fractionation between vapor and ice ( α eq ) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of α eq , and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice–vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems.
关键词：isotopic fractionation ; water vapor ; cirrus clouds ; ice deposition ; diffusivity ratio