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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.

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.

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.

The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the ENVISAT satellite provides profiles of temperature and various trace-gases from limb-viewing mid-infrared emission measurements. The stratospheric nitric acid (HNO3) from September 2002 to March 2004 was retrieved from the MIPAS observations using the science-oriented data processor developed at the Institut für Meteorologie und Klimaforschung (IMK), which is complemented by the component of non-local thermodynamic equilibrium (non-LTE) treatment from the Instituto de Astrofísica de Andalucía (IAA). The IMK-IAA research product, different from the ESA operational product, is validated in this paper by comparison with a number of reference data sets. Individual HNO3 profiles of the IMK-IAA MIPAS show good agreement with those of the balloon-borne version of MIPAS (MIPAS-B) and the infrared spectrometer MkIV, with small differences of less than 0.5 ppbv throughout the entire altitude range up to about 38 km, and below 0.2 ppbv above 30 km. However, the degree of consistency is largely affected by their temporal and spatial coincidence, and differences of 1 to 2 ppbv may be observed between 22 and 26 km at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Statistical comparisons of MIPAS IMK-IAA HNO3 VMRs with respect to those of satellite measurements of Odin/SMR, ILAS-II, ACE-FTS, as well as the MIPAS ESA product show good consistency. The mean differences are generally ±0.5 ppbv and standard deviations of the differences are of 0.5 to 1.5 ppbv. The maximum differences are 2.0 ppbv around 20 to 25 km. This gives confidence in the general reliability of MIPAS HNO3 VMR data and the other three satellite data sets., Upprättat; 2007; 20071113 (mmilz)

The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the ENVISAT satellite provides profiles of temperature and various trace-gases from limb-viewing mid-infrared emission measurements. The stratospheric nitric acid (HNO3) from September 2002 to March 2004 was retrieved from the MIPAS observations using the science-oriented data processor developed at the Institut für Meteorologie und Klimaforschung (IMK), which is complemented by the component of non-local thermodynamic equilibrium (non-LTE) treatment from the Instituto de Astrofísica de Andalucía (IAA). The IMK-IAA research product, different from the ESA operational product, is validated in this paper by comparison with a number of reference data sets. Individual HNO3 profiles of the IMK-IAA MIPAS show good agreement with those of the balloon-borne version of MIPAS (MIPAS-B) and the infrared spectrometer MkIV, with small differences of less than 0.5 ppbv throughout the entire altitude range up to about 38 km, and below 0.2 ppbv above 30 km. However, the degree of consistency is largely affected by their temporal and spatial coincidence, and differences of 1 to 2 ppbv may be observed between 22 and 26 km at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Statistical comparisons of MIPAS IMK-IAA HNO3 VMRs with respect to those of satellite measurements of Odin/SMR, ILAS-II, ACE-FTS, as well as the MIPAS ESA product show good consistency. The mean differences are generally ±0.5 ppbv and standard deviations of the differences are of 0.5 to 1.5 ppbv. The maximum differences are 2.0 ppbv around 20 to 25 km. This gives confidence in the general reliability of MIPAS HNO3 VMR data and the other three satellite data sets., Upprättat; 2007; 20071113 (mmilz)

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ∼20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (∼2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification. Copy

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ∼20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (∼2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification. Copy

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ∼20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (∼2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification. Copy

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ~20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (~2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification.

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ∼20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (∼2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification. Copy

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ∼20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (∼2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification. Copy

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ~20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (~2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification.

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar vortex to altitudes sampled by the ER-2 aircraft (i.e., ∼20 km) and mix isentropically with extravortex air. Observed correlations of CH4 and N2O are used to quantify the degree of subsidence and mixing for individual air masses. On the basis of these results the expected mixing ratio of NOy resulting from subsidence and mixing, defined here as NOy**, is calculated and compared with the measured mixing ratio of NOy. Values of NOy and NOy** agree well during most parts of the flights. A slight deficit of NOy versus NOy** is found only for a limited region during the ER-2 flight on April 26, 1997. This deficit is interpreted as indication for weak denitrification (∼2-3 ppbv) in that air mass. The small degree of denitrification is consistent with the general synoptic-scale temperature history of the sampled air masses, which did not encounter temperatures below the frostpoint and had relatively brief encounters with temperatures below the nitric acid trihydrate equilibrium temperature. Much larger degrees of denitrification would have been inferred if mixing effects had been ignored, which is the traditional approach to diagnose denitrification. Our analysis emphasizes the importance of using other correlations of conserved species to be able to accurately interpret changes in the NOy/N2O relation with respect to denitrification. Copy

The Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment uses a Fourier-transform spectrometer on board the Space Shuttle to record infrared solar occultation spectra of the atmosphere at 0.01-cm^(-1) resolution. The current version of the molecular spectroscopic database used for the analysis of the data obtained during three Space Shuttle missions between 1992 and 1994 is described. It is an extension of the effort first described by Brown et al. [Appl. Opt. 26, 5154 (1987)] to maintain an up-to-date database for the ATMOS experiment. The three-part ATMOS compilation contains Line parameters of 49 molecular species between 0 and 10000 cm^(-1), The main list, with nearly 700,000 entries, is an updated version of the HITRAN 1992 database. The second compilation contains supplemental line parameters, and the third set consists of absorption cross sections to represent the unresolvable features of heavy molecules. The differences between the ATMOS database and other public compilations are discussed.

The Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment uses a Fourier-transform spectrometer on board the Space Shuttle to record infrared solar occultation spectra of the atmosphere at 0.01-cm^(-1) resolution. The current version of the molecular spectroscopic database used for the analysis of the data obtained during three Space Shuttle missions between 1992 and 1994 is described. It is an extension of the effort first described by Brown et al. [Appl. Opt. 26, 5154 (1987)] to maintain an up-to-date database for the ATMOS experiment. The three-part ATMOS compilation contains Line parameters of 49 molecular species between 0 and 10000 cm^(-1), The main list, with nearly 700,000 entries, is an updated version of the HITRAN 1992 database. The second compilation contains supplemental line parameters, and the third set consists of absorption cross sections to represent the unresolvable features of heavy molecules. The differences between the ATMOS database and other public compilations are discussed.