Observed OH and HO_2 in the upper troposphere suggest a major source from convective injection of peroxides

ER-2 aircraft observations of OH and HO_2 concentrations in the upper troposphere during the NASA/STRAT campaign are interpreted using a photochemical model constrained by local observations of O_3, H_2O, NO, CO, hydrocarbons, albedo and overhead ozone column. We find that the reaction Q(^(1)D) + H_2O is minor compared to acetone photolysis as a primary source of HO_x (= OH + peroxy radicals) in the upper troposphere. Calculations using a diel steady state model agree with observed HO_x concentrations in the lower stratosphere and, for some flights, in the upper troposphere. However, for other flights in the upper troposphere, the steady state model underestimates observations by a factor of 2 or more. These model underestimates are found to be related to a recent (< 1 week) convective origin of the air. By conducting time-dependent model calculations along air trajectories determined for the STRAT flights, we show that convective injection of CH_3OOH and H_2O_2 from the boundary layer to the upper troposphere could resolve the discrepancy. These injections of HO_x reservoirs cause large HO_x increases in the tropical upper troposphere for over a week downwind of the convective activity. We propose that this mechanism provides a major source of HO_x in the upper troposphere. Simultaneous measurements of peroxides, formaldehyde and acetone along with OH and HO_2 are needed to test our hypothesis

Are models of catalytic removal of O_3 by HO_x accurate? Constraints from in situ measurements of the OH to HO_2 ratio

Measurements of the ratio OH/HO_2, NO, O_3, ClO, and BrO were obtained at altitudes from 15–20 km and latitudes from 15–60°N. A method is presented for interpreting these simultaneous in situ observations that constrains the rates of chemical transformations that 1) are responsible for over half the ozone removal rate in the lower stratosphere via reactions of HO_2 and 2) control the abundance of HO_2 through coupling to nitrogen and halogen radicals. The results show our understanding of the chemical reactions controlling the partitioning of OH and HO_2 is complete and accurate and that the potential effects of “missing chemistry” are strictly constrained in the region of the atmosphere encompassed by the observations. The analysis demonstrates that the sensitivity of the ratio OH/HO_2 to changes in NO is described to within 12% by current models. This reduces by more than a factor of 2 the effect of uncertainty in the coupling of hydrogen and nitrogen radicals on the analysis of the potential effects of perturbations to odd nitrogen in the lower stratosphere

K-shell photoionization of ground-state Li-like boron ions [B2+^{2+}]: Experiment and Theory

Absolute cross sections for the K-shell photoionization of ground-state Li-like boron [B$^{2+}$(1s$^2$2s $^2$S)] ions were measured by employing the ion-photon merged-beams technique at the Advanced Light Source synchrotron radiation facility. The energy ranges 197.5--200.5 eV, 201.9--202.1 eV of the [1s(2s\,2p)$^3$P]$^2$P${\rm ^o}$ and [1s(2s\,2p)$^1$P] $^2$P${\rm ^o}$ resonances, respectively, were investigated using resolving powers of up to 17\,600. The energy range of the experiments was extended to about 238.2 eV yielding energies of the most prominent [1s(2$\ell$\,n$\ell^{\prime}$)]$^2$P$^o$ resonances with an absolute accuracy of the order of 130 ppm. The natural linewidths of the [1s(2s\,2p)$^3$P] $^2$P${\rm ^o}$ and [1s(2s\,2p)$^1$P] $^2$P${\rm ^o}$ resonances were measured to be $4.8 \pm 0.6$ meV and $29.7 \pm 2.5$ meV, respectively, which compare favourably with theoretical results of 4.40 meV and 30.53 meV determined using an intermediate coupling R-matrix method.Comment: 6 figures and 2 table

The Central Temperature of the Sun can be Measured via the 7^7Be Solar Neutrino Line

A precise test of the theory of stellar evolution can be performed by measuring the difference in average energy between the neutrino line produced by ${\rm ^7Be}$ electron capture in the solar interior and the corresponding neutrino line produced in a terrestrial laboratory. The high temperatures in the center of the sun broaden the line asymmetrically, FWHM = 1.6~keV, and cause an average energy shift of 1.3~keV. The width of the $^7$Be neutrino line should be taken into account in calculations of vacuum neutrino oscillations.Comment: RevTeX file, 9 pages. For hardcopy with figure, send to [email protected]. Institute for Advanced Study number AST 93/4

Observation of Stratospheric Ozone Depletion associated with Delta II Rocket Emissions

Ozone, chlorine monoxide, methane, and submicron particulate concentrations were measured in the stratospheric plume wake of a Delta II rocket powered by a combination of solid (NH4ClO4/Al) and liquid (LOX/kerosene) propulsion systems. We apply a simple kinetics model describing the main features of gas-phase chlorine reactions in solid propellant exhaust plumes to derive the abundance of total reactive chlorine in the plume and estimate the associated cumulative ozone loss. Measured ozone loss during two plume encounters (12 and 39 minutes after launch) exceeded the estimate by about a factor of about two. Insofar as only the most significant gas-phase chlorine reactions are included in the calculation, these results suggest that additional plume wake chemical processes or emissions other than reactive chlorine from the Delta II propulsion system affect ozone levels in the plume

NO(y) partitioning from measurements of nitrogen and hydrogen radicals in the upper troposphere

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

The role of HO_x in super- and subsonic aircraft exhaust plumes

The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO_(2) emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO_(2) in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO_(2) (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde

Performance of the Space Telescope Imaging Spectrograph after SM4

On May 17, 2009, during the fourth EVA of SM4, astronauts Michael Good and Mike Massimino replaced the failed LVPS-2 circuit board on the Space Telescope Imaging Spectrograph (STIS), restoring this HST instrument to operation after a nearly 6 year hiatus. STIS after this 2009 repair operates in much the same way as it did during the 2001-2004 period of operations with the Side-2 electronics. Internal and external alignments of the instrument are similar to what they had been in 2004, and most changes in performance are modest. The STIS CCD detector continued to experience radiation damage during the hiatus in operations, leading to decreased charge transfer efficiency (CTE) and an increased number of hot pixels. The sensitivities for most modes are surprisingly close to what was expected from simple extrapolation of the 2003-2004 trends, although the echelle modes show somewhat more complex behavior. The biggest surprise was that the dark count rate for the NUV MAMA detector after SM4 has been much larger than had been expected; it is currently about 2.5 times bigger than it was in 2004 and is only slowly decreasing. We discuss how these changes will affect science with STIS now and in the future

Observations of large reductions in the NO/NO_y ratio near the mid-latitude tropopause and the role of heterogeneous chemistry

During the 1993 NASA Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE), anomalously low nitric oxide (NO) was found in a distinct sunlit layer located above the mid-latitude tropopause. The presence of a significant amount of reactive nitrogen (NO_y) in the layer implies the systematic removal of NO, which is without precedent in stratospheric in situ observations. Large increases in measured chlorine monoxide (ClO) and the hydroperoxyl radical (HO_2) also were observed in the layer. Heterogeneous reaction rate constants of chlorine nitrate (ClONO_2) with hydrogen chloride (HCl) and H_2O to form nitric acid (HNO_3) on sulfate aerosol are enhanced in the NO removal layer by local increases in H_2O and aerosol surface area. The associated conversion of NO_x (= NO + NO_2) to HNO_3 is the most likely cause of the observed low NO and NO_x/NO_y values and high ClO values

The role of HO\u3csub\u3ex\u3c/sub\u3e in super- And subsonic aircraft exhaust plumes

The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2 emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO2 in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO2 (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde