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We examine inorganic chlorine (Cly) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO2]/[HCl] by approximately 55-60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cly partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO2 measurement (too low). The high precision of our simulation (+/-15% 1-sigma for [ClONO2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.

During the 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, simultaneous in situ observations of NOx and HOx radicals, their precursors, and the radiation field were obtained in the lower stratosphere. We use these observations to evaluate the primary mechanisms that control NOx-HNO3 exchange and to understand their control over the partitioning between NO2 and HNO3 in regions of continuous sunlight. We calculate NOx production (PNOx) and loss (LNOx) in a manner directly constrained by the in situ measurements and current rate constant recommendations, using approaches for representing albedo, overhead O3 and [OH] that reduce model uncertainty. We find a consistent discrepancy of 18% between modeled rates of NOx production and loss (LNOx = 1.18P(sub NOx)), which is within the measurement uncertainty of +/- 27%. The partitioning between NOx production processes is [HNO3 + OH (41 +/- 2)%; HNO3 + hv (59 +/- 2)%] and between NOx loss processes is [NO2 + OH, 90% to >97%; BrONO2 + H2O, 10% to <3%]. The steady-state description of NOx-HNO3 exchange reveals the significant influence of the tight correlation between the photolysis rate of HNO3 and [OH] established by in situ measurements throughout the lower stratosphere. Parametrizing this relationship, we find: (1) the steady-state value of [NO2](sub 24h-avg)/[HNO3] in the continuously sunlit, lower stratosphere is a function only of temperature and number density; and (2) the partitioning of NOx production between HNO3 + OH and HNO3 + hv is nearly constant throughout most of the lower stratosphere. We describe a methodology (functions of latitude, day, temperature, and pressure) for accurately predicting the steady-state value of [NO2](sub 24h-avg)/[HNO3] and the partitioning of NOx production within these regions. The results establish a metric to compare observations of [NO2](sub 24h-avg)/[HNO3] within the continuously sunlit region and provide a simple diagnostic for evaluating the accuracy of models that attempt to describe the coupled NOx-HOx photochemistry in the lower stratosphere.

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.

The first in situ measurements of ClONO2 in the lower stratosphere, acquired using the NASA ER-2 aircraft during the Polar Ozone Loss in the Arctic Region in Summer (POLARIS) mission, are combined with simultaneous measurements of ClO, NO2, temperature, pressure, and the calculated photolysis rate coefficient (J(sub ClONO2)) to examine the balance between production and loss of ClONO2. The observations demonstrate the ClONO2 photochemical steady state measurement, [ClONO2](sup PSS) = k[ClO][No2]/J(sub ClONO2), is in good agreement with the direct measurement, [ClONO2](sup MEAS). For the bulk of the data (80%), where T > 220 K and latitudes > 45 N, [ClONO2](sup PPS) = 1.15 +/- 0.36(1-sigma)[ClONO2](sup MEAS), while for T< 220 K and latitudes < 45 N, the result is somewhat less at 1.01 +/- 0.30. The cause of the temperature and/or latitude trend is unidentified. These results are independent of solar zenith angle and air density, thus there is no evidence in support of a pressure-dependent quantum yield for photodissociation of ClONO2 at wavelengths > 300 nm. These measurements confirm the mechanism by which active nitrogen (NOx = NO + NO2) controls the abundance of active chlorine (Clx = ClO + Cl) in the stratosphere.

The Goddard trajectory chemistry model was used with ER-2 aircraft data to test our current knowledge of radical photochemistry during the POLARIS (Polar Ozone Loss in the Arctic Region In Summer) campaign. The results of the trajectory chemistry model with and without trajectories are used to identify cases where steady state does not accurately describe the measurements. Over the entire mission, using trajectory chemistry reduces the variability in the modeled NO(x) comparisons to data by 25% with respect to the same model simulating steady state. Although the variability is reduced, NO(x)/NO(y) trajectory model results were found to be systematically low relative to the observations by 20-30% as seen in previous studies. Using new rate constants for reactions important in NO(y) partitioning improves the agreement of NO(x)/NO(y) with the observations but a 5-10% bias still exists. OH and HO2 individually are underpredicted by 15% of the standard steady state model and worsen with the new rate constants. Trajectory chemistry model results of OH/HO2 were systematically low by 10-20% but improve using the new rates constants because of the explicit dependence on NO. This suggests that our understanding of NO(x) is accurate to the 20% level and HO(x) chemistry is accurate to the 30% level in the lower stratosphere or better for the POLARIS regime. The behavior of the NO(x) and HO(x) comparisons to data using steady state versus trajectory chemistry and with updated rate coefficients is discussed in ten-ns of known chemical mechanisms and lifetimes.

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