title: Persistent Water-Nitric Acid Condensate with Saturation Water Vapor Pressure Greater than That of Hexagonal Ice.
abstract: A laboratory chilled mirror hygrometer (CMH), exposed to an airstream containing water vapor (H2O) and nitric acid (HNO3), has been used to demonstrate the existence of a persistent water-nitric acid condensate that has a saturation H2O vapor pressure greater than that of hexagonal ice (Ih). The condensate was routinely formed on the mirror by removing HNO3 from the airstream following the formation of an initial condensate on the mirror that resembled nitric acid trihydrate (NAT). Typical conditions for the formation of the persistent condensate were a H2O mixing ratio greater than 18 ppm, pressure of 128 hPa, and mirror temperature between 202 and 216 K. In steady-state operation, a CMH maintains a condensate of constant optical diffusivity on a mirror through control of only the mirror temperature. Maintaining the persistent condensate on the mirror required that the mirror temperature be below the H2O saturation temperature with respect to Ih by as much as 3 K, corresponding to up to 63% H2O supersaturation with respect to Ih. The condensate was observed to persist in steady state for up to 16 h. Compositional analysis of the condensate confirmed the co-condensation of H2O and HNO3 and thereby strongly supports the conclusion that the Ih supersaturation is due to residual HNO3 in the condensate. Although the exact structure or stoichiometry of the condensate could not be determined, other known stable phases of HNO3 and H2O are excluded as possible condensates. This persistent condensate, if it also forms in the upper tropical troposphere, might explain some of the high Ih supersaturations in cirrus and contrails that have been reported in the tropical tropopause region.
authors.affiliation: Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration , Boulder, Colorado 80305-3337, United States.
authors.forename: Ru-Shan
authors.initials: RS
authors.lastname: Gao
authors.affiliation: Cooperative Institute for Research in Environmental Sciences, University of Colorado , Boulder, Colorado 80305, United States.|Department of Chemistry, University of Warsaw , Warsaw, Poland.
authors.forename: Tomasz
authors.initials: T
authors.lastname: Gierczak
authors.affiliation: Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration , Boulder, Colorado 80305-3337, United States.|Cooperative Institute for Research in Environmental Sciences, University of Colorado , Boulder, Colorado 80305, United States.
authors.forename: Troy D
authors.initials: TD
authors.lastname: Thornberry
authors.affiliation: Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration , Boulder, Colorado 80305-3337, United States.|Cooperative Institute for Research in Environmental Sciences, University of Colorado , Boulder, Colorado 80305, United States.
authors.forename: Andrew W
authors.initials: AW
authors.lastname: Rollins
authors.affiliation: Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration , Boulder, Colorado 80305-3337, United States.
authors.forename: James B
authors.initials: JB
authors.lastname: Burkholder
authors.affiliation: Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration , Boulder, Colorado 80305-3337, United States.|Cooperative Institute for Research in Environmental Sciences, University of Colorado , Boulder, Colorado 80305, United States.
authors.forename: Hagen
authors.initials: H
authors.lastname: Telg
authors.affiliation: Deutsches Zentrum für Luft- und Raumfahrt, Institut für Physik der Atmosphäre , Oberpfaffenhofen, Germany.
authors.forename: Christiane
authors.initials: C
authors.lastname: Voigt
authors.affiliation: Laboratorium für Atmosphärenphysik, ETH-Zurich , CH-8093 Zurich, Switzerland.
authors.forename: Thomas
authors.initials: T
authors.lastname: Peter
authors.affiliation: Earth System Research Laboratory, Chemical Sciences Division, National Oceanic and Atmospheric Administration , Boulder, Colorado 80305-3337, United States.|Cooperative Institute for Research in Environmental Sciences, University of Colorado , Boulder, Colorado 80305, United States.
authors.forename: David W
authors.initials: DW
authors.lastname: Fahey