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We use the first simultaneous in situ measurements of ClONO2, ClO, and HCl acquired using the NASA ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission to test whether these three compounds quantitatively account for total inorganic chlorine (Cly) in the lower stratosphere in 1997. We find (ClO + ClONO2 + HCl)/Cly = 0.92 +/- 0.10, where Cly is inferred from in situ measurements of organic chlorine source gases. These observations are consistent with our current understanding of the budget and partitioning of Cly in the lower stratosphere. We find no evidence in support of missing inorganic chlorine species that compose a significant fraction of Cly. We apply the analysis to earlier ER-2 observations dating from 1991 to investigate possible causes of previously observed discrepancies in the inorganic chlorine budget. Using space shuttle, satellite, balloon, and aircraft measurements in combination with ER-2 data, we find that the discrepancy is unlikely to have been caused by missing chlorine species or an error in the photolysis rate of chlorine nitrate. We also find that HCl/Cly is not significantly controlled by aerosol surface area density in the lower stratosphere.

Dehydration of more than 0.5 ppmv water was observed between 18 and 19 km (0-450-465 K) at the edge of the Arctic polar vortex on February 1, 1996. More than half the reactive nitrogen (NO(y)) had also been removed, with layers of enhanced NO(y) at lower altitudes. Back trajectory calculations show that air parcels sampled inside the vortex had experienced temperatures as low as 188 K within the previous 12 days, consistent with a small amount of dehydration. The depth of the dehydrated layer (approximately 1 km) and the fact that trajectories passed through the region of ice saturation in one day imply selective growth of a small fraction of particles to sizes large enough (>10 microns) to be irreversibly removed on this timescale. Over 25% of the Arctic vortex in a 20-30 K range of 0 is estimated to have been dehydrated in this event.

Dehydration of more than 0.5 ppmv water was observed between 18 and 19 km (theta about 450-465 K) at the edge of the Arctic polar vortex on February 1, 1996. More than half the reactive nitrogen (NO(sub y)) had also been removed, with layers of enhanced (sub y) at lower altitudes. Back trajectory calculations show that air parcels sampled inside the vortex had experienced temperatures as low as 188 K within the previous 12 days, consistent with a small amount of dehydration. The depth of the dehydrated layer (about 1 km) and the fact that trajectories passed through the region of ice saturation in one day imply selective growth of a small fraction of particles to sizes large enough (>10 micron) to be irreversibly removed on this timescale. Over 25% of the Arctic vortex in a 20-30 K range of theta is estimated to have been dehydrated in this event.

Dehydration of more than 0.5 ppmv water was observed between 18 and 19 km (theta approximately 450-465 K) at the edge of the Arctic polar vortex on February 1, 1996. More than half the reactive nitrogen (NO(y)) had also been removed, with layers of enhanced NO(y) at lower altitudes. Back trajectory calculations show that air parcels sampled inside the vortex had experienced temperatures as low as 188 K within the previous 12 days, consistent with a small amount of dehydration. The depth of the dehydrated layer (approximately 1 km) and the fact that trajectories passed through the region of ice saturation in one day imply selective growth of a small fraction of particles to sizes large enough (>10 micrometers) to be irreversibly removed on this timescale. Over 25% of the Arctic vortex in a 20-30 K range Transport of theta is estimated to have been dehydrated in this event.

We report here on the details of the first, in situ, real-time measurements of H-1211 (CBrClF2) and sulfur hexafluoride (SF6) mixing ratios in the stratosphere up to 20 km. Stratospheric air was analyzed for these gases and others with a new gas chromatograph, flown aboard a National Aeronautics and Space Administration ER-2 aircraft as part of the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft mission conducted in 1994. The mixing ratio of SF6, with its nearly linear increase in the troposphere, was used to estimate the mean age of stratospheric air parcels along the ER-2 flight path. Measurements of H-1211 and mean age estimates were then combined with simultaneous measurements of CFC-11 (CCl3F), measurements of brominated compounds in stratospheric whole air samples, and records of tropospheric organic bromine mixing ratios to calculate the dry mixing ratio of total bromine in the lower stratosphere and its partitioning between organic and inorganic forms. We estimate that the organic bromine-containing species were almost completely photolyzed to inorganic species in the oldest air parcels sampled. Our results for inorganic bromine are consistent with those obtained from a photochemical, steady state model for stratospheric air parcels with CFC- I I mixing ratios greater than 150 ppt. For stratospheric air parcels with CFC-11 mixing ratios less than 50 ppt (mean age greater than or equal to 5 years) we calculate inorganic bromine mixing ratios that are approximately 20% less than the photo-chemical, steady state model. There is a 20% reduction in calculated ozone loss resulting from bromine chemistry in old air relative to some previous estimates as a result of the lower bromine levels.

We compare volume mixing ratio profiles of N2O, CFC-11, CFC-12, CCl4, SF6, and HCl in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov. 1994. Good agreement is found between ATMOS and in situ correlations of [CFC-11], [CFC-12], and [SF6] with [N2O]. ATMOS measurements of [CCl4] are 15% high compared to ER-2 data, but agree within the systematic uncertainties. ATMOS observations of [HCl] vs [N2O] are within approximately 10% of ER-2 data for [HCl] > 1 ppbv, but exceed in situ measurements by larger fractional amounts for smaller [HCl]. ATMOS measurements of [ClONO2] agree well with values inferred from in situ observations of [ClO], [NO], and [O3]. The sum of [HCl] and [ClONO2] observed by ATMOS, supplemented by a minor contribution from [ClO] estimated with a photochemical model, is consistent with the levels of inorganic chlorine inferred from in situ measurements of chlorine source gases.

We have compared volume mixing ration profiles of N2 O, CFC-11, CFC-12, CCI4 , SF6, and HCI measured for the mid-latitude stratosphere by the ATMOS Fourier transform spectrometer during the ATLAS-3 Space Shuttle mission of NOvember 1994 with in situ measurements acquired aboard the NASA ER-2 aircraft during the same time period.

We compare the mixing rations of N2O, CFC-11, CFC-12, CCI4, SF6, and HCI in the mid-latitude stratosphere measured by the ATMOS Fourier transform spectrometer with in situ measurements acquired aboard the NASA ER-2 aircraft during November 1994. Good agreement is found between ATMOS and in situ correlations of CFC-11, CFC-12, and SF6 with N2O. ATMOS observations of CCI4 are approx. 15 percent higher than the ER-2 data, but within the systematic uncertainties.

We analyze the hydrogen budget of the lower stratosphere using simultaneous in situ measurements of northern hemispheric water vapor (H2O) and methane (CH4) obtained during the spring Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE), as well as previously published in situ H2 data. Based on this data, we conclude that approximately two H2O molecules are produced for each CH4 molecule destroyed. This implies that H2 production from CH4 oxidation is balanced by H2 oxidation. The uncertainty in this analysis is greatly reduced by the use of multiple data sets. Additionally, we infer that, on an annual and global average, H2O enters the stratosphere with a mixing ratio of 4.2 +/- 0.5 ppmv, and that the quasi-conserved quantity 2 x CH4 + H2O has a value of 7.6 +/- 0.6 ppmv in these northern hemishere air parcels (where xi denotes the mixing ratio of the constituent xi).