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

The response of ClO radical concentrations to variations in NO_2 radical concentrations in the lower stratosphere

The response of ClO concentrations to changes in NO_2 concentrations has been inferred from simultaneous observations of [ClO], [NO], [NO_2] and [O_3] in the mid-latitude lower stratosphere. This analysis demonstrates that [ClO] is inversely correlated with [NO_2], consistent with formation and photolysis of [ClONO_2]. A factor of ten range in the concentration of NO_2 was sampled (0.1 to 1×10^9 mol/cm^3), with a comparable range in the ratio of [ClO] to total available inorganic chlorine (1% ≤ [ClO]/[Cl_y] ≤ 5%). This analysis leads to an estimate of [ClONO_2]/[Cl_y] = 0.12 (×/÷2), in the mid-latitude, lower-stratospheric air masses sampled

The Diurnal Variation of Hydrogen, Nitrogen, and Chlorine Radicals: Implications for the Heterogeneous Production of HNO2

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower stratosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N205 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and H02 observed near sunrise and sunset. The morning burst of [OH] and [HO2] coincides with the rise of [NO] from photolysis of N02, suggesting a new source of HO, that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HN02 results in an excellent simulation of the diurnal variations of [OH] and [HO2]

The diurnal variation of hydrogen, nitrogen, and chlorine radicals: implications for the heterogeneous production of HNO_2

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower stratosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N_(2)O_(5) on sulfate aerosols agree with measured concentrations of NO, NO_(2), and ClO throughout the day, but fail to account for high concentrations of OH and HO_(2) observed near sunrise and sunset. The morning burst of [OH] and [HO_(2)] coincides with the rise of [NO] from photolysis of NO_(2), suggesting a new source of HO_(x) that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HNO_(2) results in an excellent simulation of the diurnal variations of [OH] and [HO_(2)]

The distribution of hydrogen, nitrogen, and chlorine radicals in the lower stratosphere: Implications for changes in O_3 due to emission of NO_y from supersonic aircraft

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during SPADE are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N_2O_5 agree well with measured concentrations of NO and ClO, but concentrations of HO_2 and OH are underestimated by 10 to 25%, concentrations of NO_2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO_2] are reduced if we allow for higher yields of O(^1D) from O_3 photolysis and for heterogeneous production of HNO_2. The data suggest more efficient catalytic removal of O_3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O_3] in the lower stratosphere may be larger in response to inputs of NO_y from supersonic aircraft than estimated by current assessment models

Влияние интенсивности механической активации на структуру гексагонального нитрида бора

Изучено влияние интенсивности механической активации на микроструктуру и свойства гексагонального нитрида бора (hBN).Вивчено вплив інтенсивності механічної активації на мікроструктуру і властивості гексагонального нітриду бору (hBN).The mechanical activation intensity effect on the microstructure and properties of hexagonal boron nitride (hBN) has been studied