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The Halogen Occultation Experiment (HALOE) experiment on Upper Atmosphere Research Satellite (UARS) performs solar occultation (sunrise and sunset) measurements to infer the composition and structure of the stratosphere and mesosphere. Two of the HALOE channels, centered at 5.26 gm and 6.25 gm, are designed to infer concentrations of nitric oxide and nitrogen dioxide respectively. The NO measurements extend from the lower stratosphere up to 130 km, while the NO2 results typically range from the lower stratosphere to 50 km and higher near the winter terminator. Comparison with results from various instruments are presented, including satellite-, balloon-, and ground-based measurements. Both NO and NO2 can show large percentage errors in the presence of heavy aerosol concentrations, confined to below 25 km and before 1993. The NO2 measurements show mean differences with correlative measurements of about 10 to 15% over the middle stratosphere. The NO2 precision is about 7.5x10 '13 arm, degrading to 2x10 -12 arm in the lower stratosphere. The NO differences are similar in the middle stratosphere but sometimes show a low bias (as much as 35%) between 30 and 60 km with some correlative measurements. NO precision when expressed in units of density is nearly constant at lx10 '12 atmospheres, or approximately 0.1 ppbv at 10.0 mb or, 1.0 ppbv at 1.0 mb, and so forth when expressed in mixing ratio. Above 65 km, agreement in the mean with Atmospheric Trace Molecule Spectroscopy (ATMOS) NO results is very good, typically + 15%. Model comparisons are also presented, showing good agreement with both expected morphology and diurnal behavior for both NO2 and NO. hydrogen chloride (HCI), hydrogen fluoride (HF), methane (CH4), water vapor (H20), nitric oxide (NO), nitrogen dioxide (NOy), and aerosol extinction. Retrieved profiles cover an altitude range from the upper troposphere, in some cases, to the lower thermosphere for nitric oxide. Fifteen spacecraft sunrises and sunsets are observed daily and usually in opposite hemispheres, although at certain times these measurements occur on the same day and almost overlap in space. Details of the HALOE experiment, including geographic coverage, discussion of the experiment and instrument techniques, instrument ground test results, error mechanisms, in-orbit performance, initial pressure versus latitude cross sections, and orthographic projections are included in the HALOE overview by Russell et. al. [1993]. The purpose of 'this paper is to describe steps taken and 'the status of efforts to validate data from the NO gas correlation channel and the NO2 radiometer channel. All results were inferred using the most current archived HALOE data, version 17, released in November 1994. Version numbers were liberally changed during the continuous validation and evolution of the HALOE processing system. Attainment of research quality results coincided with version 16 in late summer of 1994, which was the first version released to the general science community. However, a second general processing ...

The reaction HO2 + HO2 → H2O2 + O2 has been studied at 100 Torr and 222 K to 295 K. Experiments employing photolysis of Cl2/CH3OH/O2/N2 and F2/H2/O2/N2 gas mixtures to produce HO2 confirmed that methanol enhanced the observed reaction rate. At 100 Torr, zero methanol, k1 = (8.8 ± 0.9) 10−13 × exp[(210 ± 26)/T] cm3 molecule−1 s−1 (2σ uncertainties), which agrees with current recommendations at 295 K but is nearly 2 times slower at 231 K. The general expression for k1, which includes the dependence on bath gas density, is k1 = (1.5 ± 0.2) × 10−12 × exp[(19 ± 31)/T] + 1.7 × 10−33 × [M] × exp[1000/T], where the second term is taken from the JPL00‐3 recommendation. The revised rate largely accounts for a discrepancy between modeled and measured [H2O2] in the lower to middle stratosphere.

Global distributions of CH 4 in the mesosphere and stratosphere have been measured continuously since October 11, 1991, by the Halogen Occultation Experiment (HALOE) onboard the UARS. CH 4 mixing ratio is obtained using the gas filter correlation technique operating in the 3.3-grn region. Since measurements are made during solar occultation in the 57 ø inclination orbit, data are collected 15 times daily for both sunrises and sunsets. This provides coverage of one hemisphere in a month period. One complete hemispheric sweep (from equator to -80 ø latitude) is made during the spring and summer seasons of two hemispheres, and a partial sweep (from equator to around 50 ø latitude) is made during the fall and winter seasons of two hemispheres. HALOE CH 4 measurements are validated using direct comparisons with correlative data and internal consistency checks using other HALOE-measured tracers, HF, and aerosols. It is estimated for the 0.3-to 50-mbar region that the total error, including systematic and random components, is less than 15 % and that the precision is better than 7%. The CH4 gas filter channel does not depend significantly on the Pinatubo aerosol extinction. An experimentally accurate measurement of CH 4 is very important because CH 4 is a primary interfering gas in the HALOE HC1 channel and, subsequently, can cause HC1 measurement error. Simultaneous measurements of CH4 and other HALOE species (03, H20, NO, NO2, HC1, HF, and aerosol extinction coefficients) provide important information on atmospheric dynamic and chemical processes, since CH4 can be used as a tracer and an indicator of atmospheric transport processes. Several new pieces of infolsnation on previously unreported HALOE-observed features are also presented. Introduction Atmospheric methane, CH 4, naturally produced and released from the surface, has an important role in the greenhouse effect, causing a global warming, and in atmospheric chemistry, by removing hydroxyl radicals in the troposphere and in the stratosphere by converting reactive chlorine atoms to HC1 and producing hydrogen species to form water vapor by oxidation (see summary [World Meteorological Organization (WMO), 1982]). Methane can be used as a tracer to study atmospheric transport processes when enough measurements are made on a regional or global scale. For example, the features of CH 4 and other species observed by the Halogen Occultation Experiment (HALOE) were reported by Russell et al. [1993a] for the springtime Antarctic and by Park and Russell [1994] for the summertime polar region. Both papers used CH 4 as a tracer, and in the latter paper it was used to separate dynamical effects and to assess the importance of chemical processes for ozone deficiency in the polar regions. Methane measurements in the stratosphere before the Upper Atmosphere Research Satellite (UARS) [Reber, 1993] include the 1979 global measurements by stratospheric and mesospheric sounder (SAMS) on Nimbus 7 [Rodgers et al., 1984] and otherwise sparse individual profiles obtained by in situ sampli...