The observed presence of water vapor convectively injected deep into the stratosphere over the United States can fundamentally change the catalytic chlorine/bromine free-radical chemistry of the lower stratosphere by shifting total available inorganic chlorine into the catalytically active free-radical form, ClO. This chemical shift markedly affects total ozone loss rates and makes the catalytic system extraordinarily sensitive to convective injection into the mid-latitude lower stratosphere in summer. Were the intensity and frequency of convective injection to increase as a result of climate forcing by the continued addition of CO(2) and CH(4) to the atmosphere, increased risk of ozone loss and associated increases in ultraviolet dosage would follow.

[1] The goal of this study is to determine how H 2 O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H 2 O characteristics that are robust across data sets and that can be used to evaluate models. We evaluate the isotopic GCM LMDZ, accounting for the effects of spatiotemporal sampling and instrument sensitivity. We find that LMDZ reproduces the spatial patterns in the lower and mid troposphere remarkably well. However, it underestimates the amplitude of seasonal variations in isotopic composition at all levels in the subtropics and in midlatitudes, and this bias is consistent across all data sets. LMDZ also underestimates the observed meridional isotopic gradient and the contrast between dry and convective tropical regions compared to satellite data sets. Comparison with six other isotope-enabled GCMs from the SWING2 project shows that biases exhibited by LMDZ are common to all models. The SWING2 GCMs show a very large spread in isotopic behavior that is not obviously related to that of humidity, suggesting water vapor isotopic measurements could be used to expose model shortcomings. In a companion paper, the isotopic differences between models are interpreted in terms of biases in the representation of processes controlling humidity.Citation: Risi, C., et al. (2012), Process-evaluation of tropospheric humidity simulated by general circulation models using water vapor isotopologues: 1. Comparison between models and observations,

[1] In situ observations of H 2 O and HDO in the midlatitude stratosphere are used to evaluate the role of convection in determining the stratospheric water budget. The observations show that water vapor in the overworld stratosphere (potential temperature > 380 K) is isotopically heavier than expected. Measurements in an airmass with anomalously high concentrations of water vapor show isotopic water signatures that are characteristic of evaporated ice lofted from the troposphere during convective storms. Observed H 2 O and HDO concentrations in the plume of enhanced water and in the background stratosphere suggest that extratropical convection can account for a significant fraction of the observed water vapor in the summertime overworld stratosphere above the mid-North American continent. Citation: Hanisco, T. F., et al. (2007), Observations of deep convective influence on stratospheric water vapor and its isotopic composition, Geophys. Res. Lett., 34, L04814,

On 27 August 2013, during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys field mission, NASA's ER‐2 research aircraft encountered a region of enhanced water vapor, extending over a depth of approximately 2 km and a minimum areal extent of 20,000 km2 in the stratosphere (375 K to 415 K potential temperature), south of the Great Lakes (42°N, 90°W). Water vapor mixing ratios in this plume, measured by the Harvard Water Vapor instrument, constitute the highest values recorded in situ at these potential temperatures and latitudes. An analysis of geostationary satellite imagery in combination with trajectory calculations links this water vapor enhancement to its source, a deep tropopause‐penetrating convective storm system that developed over Minnesota 20 h prior to the aircraft plume encounter. High resolution, ground‐based radar data reveal that this system was composed of multiple individual storms, each with convective turrets that extended to a maximum of ~4 km above the tropopause level for several hours. In situ water vapor data show that this storm system irreversibly delivered between 6.6 kt and 13.5 kt of water to the stratosphere. This constitutes a 20–25% increase in water vapor abundance in a column extending from 115 hP to 70 hPa over the plume area. Both in situ and satellite climatologies show a high frequency of localized water vapor enhancements over the central U.S. in summer, suggesting that deep convection can contribute to the stratospheric water budget over this region and season.

[1] The redistribution of HNO 3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) were accompanied by the observation of condensed-phase HNO 3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO 3 with two independent channels of detection connected to separate forward and downward facing inlets that allow a determination of the amount of HNO 3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO 3 at temperatures of 197-224 K and pressures of 122-224 hPa. Maximum levels of condensed-phase HNO 3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4 Â 10 14 molecules cm À2 were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO 3 adsorption enthalpy of À11.0 kcal mol À1 , effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO 3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 mm and particle fall velocities up to 10 m s À1 , some observed clouds have significant potential to redistribute HNO 3 in the upper troposphere.