The first measurements of ClOOCl in the stratosphere have been acquired from a NASA ER‐2 aircraft, deployed from Kiruna, Sweden (68°N, 21°E), during the joint SOLVE/THESEO‐2000 mission of the winter of 1999/2000. ClOOCl is detected by thermal dissociation into two ClO fragments that are measured by the well‐known technique of chemical conversion, vacuum ultraviolet resonance fluorescence. Ambient ClO is detected simultaneously. Observations of the ratio [ClOOCl]/[ClO]2 (estimated uncertainty of ±25%, 1 σ) are used with a time‐dependent photochemical model, to test the model representation of the ratios of kinetic parameters J/kProd and kLoss/kProd for day and nighttime observations, respectively. Here, kProd and kLoss are the rate constants for ClOOCl production and loss, respectively, and J is the photolysis rate of ClOOCl. The observations are in good agreement with J based upon the 2002 JPL recommended cross sections for ClOOCl [Sander et al., 2003], if the true value of kProd is given by either the 2000 JPL recommendation [Sander et al., 2000] or the work of Trolier et al. [1990]. The larger values of kProd given by Bloss et al. [2001] and the 2002 JPL recommendation are consistent with the observations only if J is increased by a significant amount. This is accomplished if J is calculated with the larger ClOOCl cross sections measured by Burkholder et al. [1990]. The J values for ClOOCl based on the Huder and DeMore [1995] cross sections are too small, by factors of ∼1.6 to 2.5 for all values of kProd, based on the observations. Nighttime results suggest that, for 190 < T < 200 K, the values for KEq (the equilibrium constant, equal to the ratio of kProd/kLoss) of Cox and Hayman [1988] and Avallone and Toohey [2001] are in best agreement with the observations.

Simultaneous in situ measurements of the concentrations of OH, HO(2), ClO, BrO, NO, and NO(2) demonstrate the predominance of odd-hydrogen and halogen free-radical catalysis in determining the rate of removal of ozone in the lower stratosphere during May 1993. A single catalytic cycle, in which the rate-limiting step is the reaction of HO(2) with ozone, accounted for nearly one-half of the total O(3) removal in this region of the atmosphere. Halogen-radical chemistry was responsible for approximately one-third of the photochemical removal of O(3); reactions involving BrO account for one-half of this loss. Catalytic destruction by NO(2), which for two decades was considered to be the predominant loss process, accounted for less than 20 percent of the O(3) removal. The measurements demonstrate quantitatively the coupling that exists between the radical families. The concentrations of HO(2) and ClO are inversely correlated with those of NO and NO(2). The direct determination of the relative importance of the catalytic loss processes, combined with a demonstration of the reactions linking the hydrogen, halogen, and nitrogen radical concentrations, shows that in the air sampled the rate of O(3) removal was inversely correlated with total NOx, loading.

The rate constant for the reaction of ClO with HO2, k1, was measured over the temperature range 235⩽T⩽393 K using laser magnetic resonance detection to monitor directly the concentrations of both reactants. Measurements were made at low pressures, 0.8⩽P⩽3.4 Torr, in three different discharge-flow tubes, 14.0, 25.4, and 36.7 mm i.d., and with two different sources for ClO radicals, Cl+O3 and Cl+Cl2O. The observed temperature dependence is fitted by the expression, k1=3.3×10−11 exp(−850/T)+4.5×10−12 (T/300)−3.7 cm3 molecule−1 s−1 The products of the reaction were not detected but the possible channels HOCl+O2 and HCl+O3 have important implications for stratospheric chemistry.

Abstract. We report here on the details of the first, in situ, real-time measurements of H-1211 (CBrC1F2) 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 $F6, 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 (CC13F), 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-11 mixing ratios greater than 150 ppt. For stratospheric air parcels with CFC-11 mixing ratios less than 50 ppt (mean age >5 years) we calculate inorganic bromine mixing ratios that are approximately 20% less than the photochemical, 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

No abstract