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Simultaneous balloon-borne observations of ozone (O3) and nitrous oxide (N2O), a long-livedtracer of dynamical motion, are used to quantify the chemical loss of ozone in the Arctic vortexduring the winter of 1999/2000. Chemical loss of ozone occurred between altitudes of about 14 and22 km (pressures from ~120 to 30 mbar) and resulted in a 61 ± 13 Dobson unit reduction in totalcolumn ozone between late November 1999 and 5 March 2000 (the date of the last balloon-bornemeasurement considered here). This loss estimate is valid for the core of the vortex during the timeperiod covered by the observations. It is shown that the observed changes in the O3 versus N2Orelation were almost entirely due to chemistry and could not have been caused by dynamics. Thechemical loss of column ozone inferred from the balloon-borne measurements using the "ozoneversus tracer" technique is shown to compare well with estimates of chemical loss found usingboth the Match technique (as applied to independent ozonesonde data) and the "vortex-averageddescent" technique (as applied to Polar Ozone and Aerosol Measurement (POAM) III satellitemeasurements of ozone). This comparison establishes the validity of each approach for estimatingchemical loss of column ozone for the Arctic winter of 1999/2000.

Large losses of Arctic ozone occur during winters with cold, stable stratospheric circulations that result in the extensive occurrence of polar stratospheric clouds (PSCs). Reactions on the surface of PSCs lead to elevated abundances of chlorine monoxide (ClO) that, in the presence of sunlight, destroys ozone. Here we show that PSCs were more widespread during the 1999/2000 Arctic winter than for any other winter in the past two decades. We have used three fundamentally different approaches to derive the degree of chemical ozone loss from ozone sonde, balloon, aircraft and satelite instruments. We show that the ozone losses derived from these different instruments and approaches agree very well, resulting in a high level of confidence in the results. Chemical processes led to a 70% reduction of ozone for a ~1 km thick region of the lower stratosphere, the largest degree of local loss ever reported for the Arctic. The chemical loss of ozone in the total column amounted to about 100 DU by the end of the winter. This total column loss was balanced by transport, resulting in relatively constant total ozone between early January and late March, which is in contrast to the climatological increase of the total ozone column during this period, that is observed during most years.

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

Recent studies using NO, NO(y), OH and HO2 (HO(X)) observations have postulated acetone and convection of peroxides as significant sources of HO(X) in the upper troposphere (UT). This work focuses on the effect these additional HO(X) sources have on the modeled NO(y) partitioning and comparisons of the modeled NO(x)/NO(y) ratio to observations. The measured NO(x)/NO(y) ratio is usually much higher than predicted regardless of the presence of acetone in the model. The exception occurs for air parcels having low NO(y) and O3 values. For these air parcels the measured NO(x)/NO(y) ratio is much lower than the calculated ratio unless acetone is included in the model. In all cases acetone increases the fraction of NO(y) that is peroxy acetyl nitrate (PAN) from typical values of much less than 0.1 to values as high as 0.35. Including acetone also reduces the scatter in a comparison between modeled and observed NO(x)/NO(y) ratios.

Extensive airborne measurements of the reactive nitrogen reservoir (NOy) and its component nitric oxide (NO) have been made in the lower stratosphere. Box model simulations that are constrained by observations of radical and long-lived species and which include heterogeneous chemistry systematically underpredict the NOx (= NO + NO2) to NOy ratio. The model agreement is substantially improved if newly measured rate coefficients for the OH + NO2 and OH + HNO3 reactions are used. When included in 2-D models, the new rate coefficients significantly increase the calculated ozone loss due to NOx and modestly change the calculated ozone abundances in the lower stratosphere. Ozone changes associated with the emissions of a fleet of supersonic aircraft are also altered. Copyright 1999 by the American Geophysical Union.

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 compare measurements of six species taken aboard NASA DC-8 and ER-2 aircraft during two flight legs in the tropical middle troposphere near Hawaii. NO, NOy, O3, CH4, and N2O measurements agree to within the limits set by the known systematic errors. For CO2, which can be measured with better relative precision than the other five species, differences in measured values from the two platforms are slightly larger than expected if the air masses sampled by the two aircraft were indeed similar in CO2 composition to better than 0.08%. Copyright 1998 by the American Geophysical Union.