1Institute of Environmental Physics, University of Bremen, 28334 Bremen, Germany
2Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109, USA
3Dept. of Applied Mathematics and Theoretical Physics, University of Cambridge, Cambridge, CB3 0WA, UK
4Geology & Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA
5Sonoma Technology, Inc., Petaluma, CA 94954, USA
6Korean Polar Research Institute, Ansan 426-744, Korea
Abstract. Water plays a major role in the chemistry and radiative budget of the stratosphere. Air enters the stratosphere predominantly in the tropics, where the very low temperatures around the tropopause constrain water vapour mixing ratios to a few parts per million. Observations of stratospheric water vapour show a large positive long-term trend, which can not be explained by change in tropopause temperatures. Trends in the partitioning between vapour and ice of water entering the stratosphere have been suggested to resolve this conundrum. We present measurements of stratospheric H2O, HDO, CH4 and CH3D in the period 1991–2007 to evaluate this hypothesis. Because of fractionation processes during phase changes, the hydrogen isotopic composition of H2O is a sensitive indicator of changes in the partitioning of vapour and ice. We find that the seasonal variations of H2O are mirrored in the variation of the ratio of HDO to H2O with a slope of the correlation consistent with water entering the stratosphere mainly as vapour. The variability in the fractionation over the entire observation period is well explained by variations in H2O. The isotopic data allow concluding that the trend in ice arising from particulate water is no more than (0.01±0.13) ppmv/decade in the observation period. Our observations suggest that between 1991 and 2007 the contribution from changes in particulate water transported through the tropopause plays only a minor role in altering in the amount of water entering the stratosphere.