Excitation processes of infrared atmospheric emissions

Excitation rates of the infrared emissions which are likely to occur in the mesosphere and thermosphere are quantitatively evaluated. They include the 9.6 μm band of O₃, the 15 and 4.3 μm bands of CO₂ and the 5.3 and 2.8 μm bands of NO. These emissions may be excited through nonthermal processes such as chemiluminescent reactions and resonant fluorescence in the thermosphere, whereas they are of thermal origin in the stratosphere and mesosphere. Increase of the non-thermal excitation rate caused by precipitating electrons could be responsible for the enhancement of the 4.3 μm band of CO₂, and the 5.3 and 2.8 μm bands of NO observed in the auroral thermosphere.     

Mesopheric odd nitrogen enhancements during relativistic electron precipitation events

The behavior of mesospheric odd nitrogen species during and following relativistic and diffuse auroral precipitation events is simulated Below 75 km nitric oxide is enhanced in proportion to the ion pair production function associated with the electron precipitation and the length of the event. Nitrogen dioxide and nitric acid are also enhanced. At 65 Ian the percentage of odd nitrogen for N is 0.1%, HNO₃ is 1.6%, NO₂ is 15%, and NO is 83.3%. Between 75 and 85 km, NO is depleted during particle events due to the faster destruction of NO by N relative to the production of NO by N reacting with O₂ Recovery of NO depends on transport from the lower thermosphere, where NO is produced in abundant amounts during particle events.     

Chemical budgets of the stratosphere

A review is given of the stratospheric budgets of odd oxygen, odd nitrogen, nitrous oxide, methane and carbonyl sulfide. The stratospheric column production rate of NO by the reaction N₂O + O(¹D) → 2 NO is 1.1–1.9 × 10⁸ molecules cm^?2 s^?1. The stratospheric loss rates for N₂O, CH₄ and COS are equal to 0.9–1.4 × 10⁹, 1 × 10¹⁰ and 0.5 × 10⁷ molecules cm^?2 s^?1, respectively. From currently available information on the global distributions of N₂O and CH₄ there are some indications of about two times smaller OH concentrations below 35 km than those which are calculated based on the latest compilation of kinetic data.Most significantly, however, it is shown that photochemical models and available ozone observations cannot be reconciled and that there may be particularly severe problems in the 25–35 km region. This issue is thoroughly discussed.Volcanic emissions of SO₂ to the stratosphere may locally lead to much enhanced ozone concentrations and heating rates. These may influence the dynamic behaviour of volcanic plumes before their dispersion over large volumes of the stratosphere.     

Possible new atmospheric sources and sinks of odd nitrogen: 2. A revisit with O2(B) and discussions of other possibilities

Recently, modelers have expressed a concern that the currently known chemistry of atmospheric NO_y is deficient. It is therefore necessary to explore possible sources and sinks of atmospheric NO_x that may have been overlooked. In this context, it is noteworthy that the experimentally observed, four-center, Woodward-Hoffman forbidden, reaction 0₂(B ³Σ) + N₂ → NO(X) + NO (X) is atmospherically significant. In the 20 to 30 km region NO_x production from this reaction may potentially exceed the production from the “classical” N₂0 + O(¹D) reaction, and may provide a new mechanism to couple the solar UV variability and stratospheric ozone. The avoidance of the non-conservation of the orbital symmetry via the production of one NO in the excited electronic state being endothermic, it appears that the interaction of 0₂(B ³Σ) with the adjoining ¹Λ, ³Λ and ³Σ_u⁺ states might be responsible for the reaction. Experimental studies of the reaction as a function of the vibrational levels of the B-state, temperature and pressure are needed for reliable atmospheric applications of this reaction. At altitudes greater than about 50 km the production of NO from 0₂(B) begins to decrease rapidly. The NO production from 0₂ (A ³Σ₊⁺) + N₂ → NO + NO reaction may become important here, if the reaction is confirmed by experiments. These new sources of NOx call for new sinks of this species. In the upper stratosphere and mesosphere the chemical acceleration of NO dissociation via the reactions of electronically and vibrationally excited NO with 0₂ may help. In the lower atmosphere there is a possibility of the annihilation of NO, N0₂pair leading to the recreation of a stable NN bond. This might happen if N₂0₃ from NO and N0₂ recombination may photodissociate as N₂0 + 0₂. Unfortunately the requirements are stringent, and only experiments can tell whether or not this mechanism operates in the atmosphere.     

Transport of thermospheric NO to the upper stratosphere?

The rate of production of NO in the thermosphere is expected to vary greatly over the course of an 11-year solar cycle because the fluxes of both extreme ultraviolet radiation and auroral particles are known to increase substantially from solar minimum to solar maximum. In the stratosphere, NO participates in a catalytic cycle which constitutes the dominant photochemical destruction mechanism for stratospheric ozone. If appreciable long range transport of NO from the thermosphere to the upper stratosphere occurs, its effects should therefore be manifested in upper atmospheric ozone density variations over the 11-year solar cycle. In this paper, model predictions of the seasonal and latitudinal variations in upper stratospheric O₃ associated with NO transport for different levels of solar activity are compared to satellite observations of upper stratospheric ozone abundances.     

The aeronomic dissociation of nitric oxide

A detailed study is made of the atmospheric attenuation of the dissociation of nitric oxide in the mesosphere and stratosphere. The nitric oxide dissociation profile depends on the absorption of the discrete Schumann-Runge bands of O₂. The major contribution to the dissociation rate of NO is the predissociation of the δ(0-0) and δ(1-0) bands which can reach the stratosphere.     

The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

We have investigated the role of several ion-molecule reactions in the conversion of N₂O₅ to HNO₃. In the proposed conversion, an N₂O₅ molecule would react with an H₂O molecule clustered to an inert ion to produce two HNO₃ molecules. Subsequent clustering of an H₂O molecule to the inert ion would make the reaction catalytic. If such an ion-catalysed conversion of N₂O₅ to HNO₃ occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. In this paper we present reaction rate constant measurements made in a flowing afterglow apparatus for hydrated H₃O⁺, H⁺(CH₃CN)_m (m = 1, 2, 3), and several negative ions reacting with N₂O₅. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N₂O₅ conversion by ion-molecule reactions.     

Simultaneous measurements of No and No2 in the stratosphere

Simultaneous measurements of NO and NO₂ in the stratosphere leading to an NO_x determination have been performed by means of i.r. absorption spectrometry using the Sun as a source in the 5·2 μm band of NO and in the 6·2 μm band of NO₂. The observed abundance of NO_P peaks at 26 km where it is equal to (4·2 ± 1) × 10⁹ cm^?3. The volume mixing ratio of NO_p was observed to vary from 1·3 × 10^?9 at 20 km to 1·3 × 10^?8 at 34 km.     

Photochemistry of nitrogen in the Martian atmosphere

Models are developed for the photochemistry of a CO₂H₂ON₂ atmosphere on Mars and estimates are given for the concentrations of N, NO, NO₂, NO₃, N₂O₅, HNO₂, HNO₃, and N₂O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO₂ of order 10^?8. Deposition rates for nitrite and nitrate minerals could be as large as 3× 10⁵ N equivalent atoms cm^?2 sec^?1 under present conditions and may have been higher in the past.     

Chemical response of the middle atmosphere to changes in the ultraviolet solar flux

Time variations in the solar flux between 1000 and 4000 Å induce changes in the concentrations of minor constituents in the upper stratosphere and mesosphere. The response of mesospheric ozone to variations in the Lyman α line over the course of several solar rotations may be of measurable magnitude. Large Lyman α fluxes lead to small O₃ densities above 65 km due to the enhanced dissociation of H₂O and resultant destruction of odd oxygen by odd hydrogen. An increase in continuum and Lyman α fluxes causes a slight enhancement in both the odd oxygen and hydrogen concentrations in the upper stratosphere.     

Magnesium ion chemistry in the stratosphere

Laboratory measurements of reaction rate constants of magnesium ions and magnesium containing ions with O₃, NO, HNO₃, and H₂O₂ have been carried out in a flowing afterglow experiment. Mg⁺ ions react with O₃ to produce MgO⁺ ions, which in turn react with O₃ to produce Mg⁺ ions. Mg⁺ ions react with HNO₃ and H₂O₂ to produce MgOH⁺ ions. MgOH⁺ ions react rapidly with HNO₃ to produce NO⁺₂ ions and Mg(HO)₂. One can therefore conclude that Mg⁺, MgO⁺, or MgOH⁺ ions could not have significant concentrations in the stratosphere if gas phase magnesium compounds were present. The failure to observe these ions therefore cannot be used as evidence that the stratospheric magnesium, resulting from meteor ablation at higher altitudes, is in condensed phases. This is in contrast to the case for sodium where the ion chemistry is such that the failure to observe hydrated Na⁺ ions proves that gas phase sodium compounds are not present in the stratosphere.     

A numerical response of the middle atmosphere to the 11-year solar cycle

A two-dimensional numerical model with coupled photochemistry and dynamics has been used to investigate the response of the middle atmosphere (16–116 km) to changes in solar activity over the 11-year solar cycle. Model inputs that vary with solar cycle include solar radiation, cosmic ray and auroral ionization rates and the flux of NO_x at the model's upper boundary.In this study, the results of model runs for solar cycle minimum and maximum conditions are compared. In the stratosphere, using currently accepted estimates of changes in solar radiation at wavelengths longer than 180 nm, only small responses in ozone, temperature and zonal winds are obtained. On the other hand, changes at shorter wavelengths, and the effects of particle precipitation, lead to large variations in the abundances of trace species in the thermosphere and upper mesosphere. In particular, very large abundances of NO_x are produced above 90 km by auroral particle precipitation. Considerable amounts of NO_x are transported subsequently to the stratosphere by the global mean meridional circulation. It is shown that this excess NO_x can lead to significant decreases in ozone concentrations at high latitudes and that it may explain observations of nitrate deposition in Antarctic snow.     

Stratospheric observations of NO3 and its experimental and theoretical distribution between 20 and 40 km

A simultaneous night-time observation of NO₃ and 0₃ has been made by means of a balloon-borne spectrophotometer pointing at the rising planet Venus. The spectrum recorded between 642 and 672 nm makes it possible to determine the NO₃ and O₃ absorptions in the 662 nm band and the Chappuis bands, respectively. The NO₃ vertical distribution is deduced, and is found to reach a peak of (3.4 ± 0.4) 10⁷ molecules cm^?3at 35 km. Such an observational result can be interpreted in terms of a theoretical profile deduced from a one-dimension time-dependant photochemical model which takes account of the night-time stratospheric NO₂, NO₃ and N₂O₅ constituents and the latest kinetic and photochemical data for the rate constants.     

Interaction of photochemical and radiative processes in the stratosphere: An application on the retrieval of concentration profiles from satellite measurements

A new method is developed to determine the concentration profiles of chemical species from satellite measurements. The method takes into account the interaction of photochemical and radiative processes in the stratosphere and is applied for chemical species (nitric oxide and nitrogen dioxide) experiencing large diurnal changes. It is found that if the interaction of the photochemical and radiative processes is neglected, that is if the temporal and spatial variations of NO and NO₂ are not considered in the radiative transfer calculations, the resulting errors for the concentration profiles for altitudes less than 20 km reach 100 and 5% respectively, for both sunset and sunrise. A photochemical scheme is developed capable of providing the mixing ratio profiles of NO and NO₂ for different latitudes, altitudes and seasons and a retrieval code combining an iterative inversion algorithm, working from top of the atmosphere downwards, and a parameterization of the variability of NO and NO₂ is also constructed. The method is used to examine the accuracy of the retrieval of the vertical concentration profiles and the new results show that the recovered profiles are in good agreement (error 5–15%) with measured profiles (WMO, 1985) and reflect the trends of NO and NO₂ at sunset and sunrise.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

The effect of particle precipitation events on the neutral and ion chemistry of the middle atmosphere—I. Odd nitrogen

A one-dimensional, time-dependent model of the neutral and ion composition of the middle atmosphere is used to study the processes controlling the production and loss of odd nitrogen species during particle ionization events. From consideration of the cross-sections for the relevant ionization and dissociation reactions we conclude that between 1.3 and 1.6 odd nitrogen atoms per ion pair are produced in the middle atmosphere. The value in the thermosphere is larger due to the role of atomic oxygen. The time-dependent mutual destruction of odd nitrogen by the reaction N(⁴S) +NO→ N₂+O must be included and the assumption of a nitric oxide production normalized to the ionization rate is invalid. A simulation of the 1972 August solar proton event is presented. The calculated ozone depletion occurring during the event due to the increase in odd nitrogen agrees well with the measured ozone changes.     

The ozone budget in the stratosphere: Results of a one-dimensional photochemical model

The ozone concentration in the stratosphere results from the combined action of various catalytic cycles involving nitrogen oxides, HO_x and Cl_x radicals, as well as from transport processes. The results of our one-dimensional model allow the relative efficiency o those cycles to be evaluated as a function of altitude. To take into account the chemical couplings between stratospheric species, a self-consistent scheme is used to determine the budget of O_x NO_x Cl_x and HO_x species. Furthermore, the concept of chemical relaxation time is developed for ozone and the other species. It leads to a better understanding of the role of “temporary reservoir” species in the stratospheric photochemistry.It is found that, in the upper stratosphere, the ozone budget can be established in a straightforward manner, whereas in the lower stratosphere, chemical couplings are more complex and transport processes increasingly important. Due to the oversimplified transport parametrization used in this model, results for this region of the atmosphere must be viewed with caution.The model evaluations of the impact of chlorofluorocarbon release and nitrous oxide and methane increase on the ozone layer are also presented. These results can be interpreted in terms of perturbation to the budget of O_x NO_x Cl_x and HO_x species. Nevertheless model predictions should be taken with caution because large uncertainties still remain in some key reaction rates and in the behaviour of most of the source gases. In addition, inadequacies in the model formulation are difficult to assess and contribute to the overall uncertainty.     

Photodissociation of nitric oxide in the middle and upper atmosphere

Absorption of solar radiation of wavelengths between 175 to 205 nm plays a fundamental role in the photochemistry of the middle atmosphere. Nitric oxide photodissociates in the δ(0-0) and δ(1-0) bands near 191 and 183 nm, respectively, initiating the primary mechanisms for NO_x removal in the middle atmosphere. The spectrally rich Schumann-Runge (S-R) bands of O₂ are the main source of atmospheric opacity at these wavelengths. A re-evaluation of O₂ absorption has been made based on recent advances in understanding of S-R line shapes, leading to differences with conventional approaches assuming Voigt line profiles in line-by-line calculations of the O₂ cross section. The new results are used to examine the impact of O₂ transmission on the photodissociation of NO in the δ(0,0) and δ(1,0) bands.     

Influence of peroxyacetyl nitrate (PAN) on odd nitrogen in the troposphere and lower stratosphere

Nonmethane hydrocarbon breakdown in the atmosphere produces aldehydes of which a fraction are transferred into peroxyacetyl nitrates (PAN) in the presence of NO and NO₂. Since ethane is destroyed photochemically primarily above 1 km, PAN can be introduced into the upper troposphere and lower stratosphere without the need to be transported from the boundary layer where most hydrocarbons are destroyed and where PAN may be lost due to thermal decomposition and heterogeneous loss. Mixing ratios of ethane in the lower troposphere increase by a factor of 4–8 from equatorial to northern mid-latitudes. This difference is directly translatable into a PAN latitude gradient. At mid-latitudes the concentration of PAN below 20 km is 0.1 ppb comparable to and in some instances larger than predicted HO₂NO₂ mixing ratios. Like HO₂NO₂ and HNO₃, PAN serves as a reservoir for odd nitrogen.     

The solar spectral irradiance and its action in the atmospheric photodissociation processes

A critical analysis has been made of solar irradiance in the spectral region covering wavelengths from 100 nm upwards; the absorption characteristics of molecules of oxygen and ozone have been taken into account with a view to the direct application of the results to atmospheric photochemistry. The absorption of radiation by these molecules results in the photodissociation of both of them in the homosphere, and it also makes possible the penetration of solar radiation from the thermosphere, through the mesosphere and the stratosphere, down to the troposphere.Special attention has been given to each of the following spectral regions: Lyman-alpha radiation at 121.6 nm, the O₂ Schumann-Runge continuum at wavelengths less than 175 nm, the O₂ Schumann-Runge band system from 200 to 175 nm, and the O₂ Herzberg continuum at 242.4 nm. For absorption by ozone, the solar spectrum has been analysed in the following regions: the Hartley band at wavelengths less than 310 nm, the Huggins bands at wavelengths above 310 nm and the visible Chappuis bands. Finally, for the photodissociation of O₃, particular attention has been given to the transition region (300–320 nm) in which there is a change-over from the production of the excited atom O(¹D) to that of the atom in its ground state O(³p).