Stratospheric negative ions—detailed height profiles

Balloon-borne mass spectrometers with extended mass range have been flown during controlled descents. This gave detailed height profiles of stratospheric negative ions between 15 and 34 km. The main ion families were HSO₄^?(H₂SO₄)_m(HNO₃)_n and NO₃^? (HNO₃)_n Information concerning trace gases is o well as an assessment of the problems of ion fragmentation and contamination. Finally, the data are used to derive information concerning the rate of H₂SO₄ clustering.     

Mass spectrometric measurements of fractional ion abundances in the stratosphere—Negative ions

Fractional abundances of stratospheric negative ions are for the first time explicitly reported. The measurements made by balloon-borne ion mass spectrometers also rely on recent studies of electric field induced collisional dissociation of negative cluster ions conducted at our laboratory. These indicate that the negative ion composition measurements around 36 km conducted by our group do not suffer from any significant dissociation. The new composition data support ion identifications NO₃^?(HNO₃)_b and HSO₄^?(H₂SO₄)_c(HNO₃)_d and the underlying ion reactions propo previously. Moreover, it is found that HSO₄^?(H₂SO₄)_g-ions appear to be particularly stable and that H₂SO₄-association is very fast. Implications of the ion composition data for ion processes are discussed.     

Ion-ion recombination rates in the earth's atmosphere

The temperature dependence of the binary recombination coefficient, α₂, for the reaction NO⁺+NO₂^? → products has been obtained over the range 185–530 K. It is found that the corresponding mean cross section $\text{σ}$ is described by the power law $\text{σ}\text{? A · T}{}^{\mathrm{?0.9}}$, and that α₂ ? B · T^?0.4. Data has also been obtained for two cluster ion recombination reactions which indicate that their recombination cross sections are only about 40% larger than for the parent ions at a given temperature, the cross sections for these reactions also apparently increasing with decreasing temperature. In the light of this data and by considering the most probable positive and negative ions existing at various altitudes up to 90km in the atmosphere, the most appropriate ionic recombination coefficients in various altitude ranges are deduced. Thus, between 30 and 90 km, where the recombination process is two-body, the coefficient varies over the narrow range 5–9 × 10^?8 cm³s^?1, while below 30 km the process is predominantly three-body with an effective two-body rate increasing rapidly to a maximum value ≈3 × 10^?6 cm³s^?1 in the troposphere, these deductions being based on published laboratory determinations of three-body recombination coefficients.     

The altitude dependence of the O2(A3Σu+) vibrational distribution in the terrestrial nightglow

A simple vibrational relaxation model which reproduces the observed altitude integrated vibrational distribution of the Herzberg I bands in the nightglow is used to derive the altitude profiles of the individual vibrational levels at 1 km intervals in the 85–115 km height range. The possible errors associated with using rocket-borne photometer measurements of a limited number of bands in the O₂(A³Σ_u⁺?X³Σ_g^?) system to infer the total Herzberg I emission profile are assessed.     

II. Combined numerical model of ion and neutral composition above 120 km

A coupled neutral-ionic photochemical model has been used to interpret the ionic composition of the Venusian dayside ionosphere measured by the orbiter retarding potential analyser (ORPA) experiment on board the NASA Pioneer-Venus orbiter spacecraft. The electron and ion temperatures also measured by the ORPA are used for calculating the plasma-diffusion coefficients and scale heights for ions. The neutral temperature profiles and the densities of neutral constituents, particularly CO₂ and O, play key roles in the determination of the height profiles of the ionic constituents. All these quantities vary substantially in the Venusian thermosphere near the terminator; the models presented are representatives of the solar zenith angle ～65°. The predicted O₂⁺ densities below ～200km agree particularly well with observations by the ORPA, but the model values are significantly less than those measured by the orbiter ion mass spectrometer (OIMS). Models predict much smaller densities than observed values for all molecular ions above ～200km. The reason for the turn-up trend of the concentration gradient of molecular ions observed at these heights by both ORPA and OIMS is unknown. One of the models can predict O⁺ ion densities above ～200km compatible with observations, if an effective vertical escape flux (φ10⁸cm^?2sec^?1) is assumed at the ionopause. The neutral air density required to explain the observed ion composition is about 1.4 times larger than the values measured by the orbiter neutral mass spectrometer (ONMS).     

Solar radiation scattered in the Venus atmosphere: The Venera 11,12 data

Results of the scattered solar radiation spectrum measurements made deep in the Venus atmosphere by the Venera 11 and 12 descent probes are presented. The instrument had two channels: spectrometric (to measure downward radiation in the range 0.45 < γ < 1.17 μm) and photometric (four filters and circular angle scanning in an almost vertical plane). Spectra and angular scans were made in the height range from 63 km above the planet surface. The integral flux of solar radiation is 90 ± 12 W m^?2 measured on the surface at the subsolar point. The mean value of surface absorbed radiation flux per planetary unit area is 17.5 ± 2.3 W m^?2. For Venera 11 and 12 landing sites the atmospheric absorbed radiation flux is ～15 W m^?2 for H >; 43 km and ～45 W m^?2 for H < 48 km in the range 0.45 to 1.55 μm. At the landing sites of the two probes the investigated portion of the cloud layer has almost the same structure: it consists of three parts with boundaries between them at about 51 and 57 km. The base of clouds is near 48 km above the surface. The optical depth of the cloud layer (below 63 km) in the range 0.5 to 1 μm does not depend on the wavelength and is ～29 and ～38 for the Venera 11 and 12 landing sites, respectively. The single-scattering albedo, ω₀, in the clouds is very close to 1 outside the absorption bands. Below 58 km the parameter (1 ? ω₀) is <10^?3 for 0.49 and 0.7 μm. The parameter (1 ? ω₀) obviously increases above 60 km. Below 48 km some aerosol is present. The optical depth here is a strong function of wavelength. It varies from 1.5 to 3 at λ = 0.49 μm and from 0.13 to 0.4 at 1.0 μm. The mean size of particles below the cloud deck is about 0.1 μm. Below 35 km true absorption was found at λ < 0.55 μm with the (1 ? ω₀) maximum at H ≈ 15 km. The wavelength and height dependence of the absorption coefficient are compatible with the assumption that sulfur with a mixing ratio ～2 × 10^?8 normalized to S₂ molecules is the absorber. The upper limits of the mixing ratio for Cl₂, Br₂, and NO₂ are 4 × 10^?8, 2 × 10^?11, and 4 × 10^?10, respectively. The CO₂ and H₂O bands are confidently identified in the observed spectra. The mean value of the H₂O mixing ratio is 3 × 10^?5 < F_H2O < 10^?4 in the undercloud atmosphere. The H₂O mixing ratio evidently varies with height. The most probable profile is characterized by a gradual increase from F_H2O = 2 × 10^?5 near the surface to a 10 to 20 times higher value in the clouds.     

The structure and microphysical properties of the Venus clouds: Venera 9, 10, and 11 data

Data processing and interpretation of the nephelometer measurements made in the Venus atmosphere aboard the Venera 9, 10 and 11 landers in the sunlit hemisphere near the equator are discussed. These results were used to obtain the aerosol distribution and its microphysical properties from 62 km to the surface. The main aerosol content is found in the altitude range between 62 km (where measurements began) and 48 km, the location of the cloud region. Three prominent layers labeled as I (between 62 and 57 km), II (between 57 and 51 km) and III (between 51 and 48 km), each with different particle characteristics are discovered within the clouds. The measured light-scattering patterns can be intrepreted as having been produced by particles with effective radii from 1 to 2 μm depending on height and indices of refractivity from 1.45 in layer I to 1.42 in layer III. These values do not contradict the idea that the droplets are made of sulfuric acid. In layers II and III the particle size distribution is at least bimodal rather than uni-modal. The index of refraction is found to decrease to 1.33 in the lower part of layer II, suggesting a predominant abundance of larger particles of different chemical origin, and chlorine compounds are assumed to be relevant to this effect. In the entire heightrange of the Venera 9–11 craft descents, the clouds are rather rarefied and are characterized by a mean volume scattering coefficient σ ～ 2 × 10^?5 cm^?1 that corresponds to the mean meteorological range of visibility of about 2 km. The average mass content of condensate is estimated to be equal to 4 × 10^?9 g/cm³, and the total optical depth of clouds to τ ～ 35. Near the bottom of layer III clouds are strongly variable. In the subcloud atmosphere a haze was observed between 48 and 32 km; that haze is mainly made of submicron particles, r_eff ～ 0.1μm. The atmosphere below that is totally transparent but separate (sometimes possibly disappearing) layers may be present up to a height of 8 km above the surface. A model of this region with a very low particle density (N ? 2–3 cm^?3) strongly refractive large particles (r_eff ? 2.5 μm; 1.7 < n < 2.0) provided satisfactory agreement. The optical depth of aerosol in the atmosphere below the subcloud haze does not exceed 2.5.     

Upper stratosphere negative ion composition measurements and inferred trace gas abundances

In situ composition measurements of atmospheric negative ions were made at 40.8 km altitude using a balloon-borne mass spectrometer with large mass range and improved mass resolution. The data obtained show marked differences compared to previous data obtained mostly around or below 33 km.It appears that these differences are mostly due to a higher atmospheric temperature, a lower nitric acid vapour abundance and a larger HSO₃-vapour abundance prevailing at the higher altitude.A particularly striking feature is the relatively large fractional abundance of HSO₃-containing cluster ions.Another interesting result is that nitric acid vapour abundances can be inferred from the negative ion composition data with better accuracy than is possible for lower altitudes. The reason being that collisional ion dissociation occurring during ion sampling is less disturbing.The inferred nitric acid vapour abundance for 40.8 km altitude is consistent with current 2-dimensional model calculations.     

The atmosphere of Io from Pioneer 10 radio occultation measurements

The occultation of the Pioneer 10 spacecraft by Io (JI) provided an opportunity to obtain two S-band radio occultation measurements of its atmosphere. The dayside entry measurements revealed an ionosphere having a peak density of about 6 × 10⁴ elcm^?3 at an altitude of about 100 km. The topside scale height indicates a plasma temperature of about 406 K if it is composed of Na⁺ and 495 K if N₂⁺ is principal ion. A thinner and less dense ionosphere was observed on the exit (night side), having a peak density of 9 × 10³ elcm^?3 at an altitude of 50 km. The topside plasma temperature is 160 K for N₂^? and 131 K for Na⁺. If the ionosphere is produced by photoionization in a manner analogous to the ionospheres of the terrestrial planets, the density of neutral particles at the surface of Io is less than 10¹¹?10¹² cm³, corresponding to a surface pressure of less than 10^?8 to 10^?9 bars. Two measurements of its radius were also obtained yielding a value of 1830 km for the entry and 192 km for the exit. The discrepancy between these values may indicate an ephemeris uncertainty of about 45 km. The two measurements yield an average radius of 1875 km, which is not in agreement with the results of the Beta Scorpii stellar occultation.     

Stratospheric in situ measurements of H2SO4 and HSO3 vapors during a volcanically active period

In situ measurements of stratospheric H₂SO₄ and HSO₃vapors using passive chemical ionization mass spectrometry were made in October 1982 after the eruption of volcano El Chichon. Data were obtained between about 20 and 41 km showing [H₂SO₄ + HSO₃] sum concentrations between about 10⁴ and 2 × 10⁵ cm^?3 below 29 km and a steep rise above this altitude. Maximum [H₂SO₄ + HSO₃] values of about 3 × 10⁶ cm^?3 are reached above 35 km.Partial [HSO₃] concentrations increase above 34 km reaching about $\text{4 × 10}{}^5\text{cm}{}^{\mathrm{?3}}$ around 40 km. From the measurements it is concluded that H₂SO₄ and probably HSO₃photolysis have an important influence above 34 km leading to the observed increase of [HSO₃] and a depletion of H₂SO₄vapor.It also seems that the data support the view of heterogeneous HSO₃ removal. If correct, this would imply that stratospheric aerosols are formed primarily from HSO₃ rather than H₂SO₄vapor.     

The lower ionosphere of Titan

Ionization of the atmosphere of Titan by galactic cosmic rays is a very significant process throughout the altitude range of 100 to 400 km. An approximate form of the Boltzmann equation for cosmic ray transport has been used to obtain local ionization rates. Models of both ion and neutral chemistry have been employed to compute electron and ion density profiles for three different values of the H₂/CH₄ abundance ratio. The peak electron density is of the order 10³ cm^?3. The most abundant positive ions are C₂H₉⁺ and C₃H₉⁺, while the predicted densities of the negative ions H^? and CH₃^? are very small (<10^?4 that of the positive ions). It is suggested that inclusion of the ion chemistry is important in the computation of the H and CH₃ density profiles in the lower ionosphere.     

Equatorial ozone profiles from the solar maximum mission—a comparison with theory

The u.v. spectrometer polarimeter on the Solar Maximum Mission has been utilized to measure mesospheric ozone vs altitude profiles by the technique of solar occultation. Sunset data are presented for 1980, during the fall equinoctal period within ± 20° of the geographic equator. Mean O₃, concentrations are 4.0 × 10¹⁰ cm^?3at 50 km, 1.6 × 10¹⁰ cm^?3 at 55 km. 5.5 × 10⁹ cm^?3 at 60 km and 1.5 × 10⁹ cm^?3 at 65 km. Som profiles exhibit altitude structure which is wavelike. The mean ozone profile is fit best with the results of a time-dependent model if the assumed water vapor mixing ratio employed varies from 6 ppm at 50 km to 2–4 ppm at 65 km.     

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.     

Ionospheric models of Saturn,Uranus, and Neptune

Model ionospheres are calculated for Saturn, Uranus, and Neptune. Protons are the major ions above 150 km altitude measured from a reference level where the hydrogen density is 1 × 10¹⁶ molecules cm^?3, while below 150 km quick conversion of protons to H₃⁺ ions by a three-body association mechanism leads to a rapid removal of ionization in dissociative recombination of H₃⁺. Electron density maxima are found at about 260 km for Saturn and Uranus and 200 km for Neptune. Present knowledge of the physical and chemical processes in the atmospheres of these planets suggests that their ionospheres probably will not be Jupiter-like.     

An SPE-disturbed D-region model

For the first time, a model of the daytime disturbed D-region is presented which is consistent with experimental solar proton event (SPE) data, that of the 2–5 November, 1969 event in particular. Sunset electron concentration profiles also are shown to be quite compatible with the experimental results, but computed sunrise electron concentrations are found to rise faster with solar elevation than do the measurements. In the daytime, O₂^?, O^?, CO₄^? and CO₃^? ions apparently do not retain electrons in contrast to NO₂^? and NO₃^? ions. Hydration of the latter two species is probably unimportant since photodetachment and/or photodissociation of these ions are insignificant processes even when they are unattached to water molecules. Difficulties at sunrise are thought to arise most likely from our omission of hydration processes for negative ions, the pre-sunrise negative ion populations undoubtedly having the highest diurnal hydration level. Sunset ozone computations using the latest chemistry are shown to match the data except for some problem at the highest altitude, near 70 km, for the earlier, more disturbed, of the two experimental profiles.     

Calculated photoelectron pitch angle and energy spectra

Calculations of the steady-state photoelectron energy and angular distribution in the altitude region between 120 and 1000 km are presented. The distribution is found to be isotropic at all altitudes below 250 km, while above this altitude anisotropies in both pitch angle and energy are found. The isotropy found in the angular distribution below 250 km implies that photoelectron transport below 250 km is insignificant, while the angular anisotropy found above this altitude implies a net photoelectron current in the upward direction. The energy anisotropy above 500 km arises from the selective backscattering of the low energy photoelectron population of the upward flux component by Coulomb collisions with the ambient ions. The total photoelectron flux attains its maximum value between about 40 and 70 km above the altitude at which the photoelectron production rate is maximum. The displacement of the maximum of the equilibrium flux is attributed to an increasing (with altitude) photoelectron lifetime. Photoelectrons at altitudes above that where the flux is maximum are on the average more energetic than those below that altitude. The flux of photoelectrons escaping to the protonosphere at dawn was found to be 2.6 × 10⁸ cm^?2 sec^?1, while the escaping flux at noon was found to be 1.5 × 10⁸ cm^?2 sec^?1. The corresponding escaping energy fluxes are: 4.4 × 10⁹ eV cm^?2 sec^?1 and 2.7 × 10⁹ eV cm^?2 sec^?1.     

Photochemistry of minor constituents in the troposphere

Altitude profiles for the number densities of NO, NO₂, NO₃, N₂O₅, HNO₂, CH₃O, CH₃O₂, H₂CO, OH, and HO₂ are calculated as a function of time of day with a steady-state photochemical model in which the altitude profiles for the number densities of H₂O, CH₄, H₂, CO, O₃, and the sum of NO and NO₂ are fixed at values appropriate to a summer latitude of 34°. Average daily profiles are calculated for the long-lived species, HNO₃, H₂O₂, and CH₃O₂H.The major nitrogen compound HNO₃ may have a number density approaching 5 × 10¹¹ molecules cm^?3 at the surface, although an effective loss path due to collisions with particulates could greatly reduce this value.The number density of OH remains relatively unchanged in the first 6 km and reaches 1 × 10⁷ molecules cm^?3 at noon, while the number density of HO₂ decreases throughout the lower troposphere from its noontime value of 8 × 10⁸ molecules cm^?3 at the surface.H₂O₂ and H₂CO both have number densities in the ppb range in the lower troposphere.Owing to decreasing temperature and water concentration, the production of radicals and their steady-state number densities decrease with altitude, reaching a noontime minimum of 1 × 10⁸ molecules cm^?3 for OH and 3 × 10⁷ molecules cm^?3 for HO₂ at the tropopause. The related minor species show even sharper decreases with increasing altitude.The primary path for interconverting OH and HO₂ serves as the major sink for CO and leads to a tropospheric lifetime for CO of ~0.1 yr.Another reaction cycle, the oxidation of CH₄, is quite important in the lower troposphere and leads to the production of H₂CO along with the destruction of CH₄ for which a tropospheric lifetime of ~2 yr is estimated.The destruction of H₂CO that was produced in the CH₄ oxidation cycle provides the major source of CO and H₂ in the atmosphere.     

Anion chemistry on Titan: A possible route to large N-bearing hydrocarbons

The reaction of CN^? with cyanoacetylene (HC₃N), has been studied as a function of the HC₃N pressure in a quadrupole tandem mass spectrometer. The mass spectra revealed the fast depletion of the CN^? parent ion and formation of larger anions of rapidly growing size. Most of the ions observed were found to belong to two series of products: (HC₃N)_x·C_2p+1N^? and (HC₃N)_x·C_2pN^? resulting from the sequential additions of HC₃N molecules and loss of HCN or HCCN molecules. The mechanism and energetics of the first two reaction steps are briefly discussed. The laboratory data are compared with those from the Cassini CAPS-ELS spectrometer. It is believed that the reactions observed could account for the growth of anions in Titan’s ionosphere.     

The hydrogen balmer lines and the structure of the quiet solar chromosphere

Spectra of Hα, Hβ and Hδ have been taken under good seeing conditions with the vacuum tower telescope of Sacramento Peak Observatory. Intensity curves are given at various wavelengths in these lines to permit further comparison with a theoretical model. Moreover, considering in each case the range of height in which the lines are almost optically thin and using a few approximations, the following results are derived: between 2000 and 6000 km above the limb the average thermal + turbulent velocity of the atoms is found to increase from 20 km s^?1 to 30 km s^?1 and the mean number of hydrogen atoms per cm³ in level 2 is given by $$\log n_2 {\text{ = }}4.5{\text{ }} - {\text{ 0}}{\text{.00056(}}z - 2000)$$ z being the altitude above the limb in km. For line profile computations a new interpolation formula is presented; it gives good profiles with a small number of scans, saving microphotometer time.     

Silicon negative ion chemistry in the atmosphere-in situ and laboratory measurements

The results of a rocket-borne mass spectrometer measurement indicate that large concentrations of negative ions exist above the bottom of the atmospheric atomic oxygen layer. A large majority of these ions have a mass greater than 100 amu. In addition, an ion at mass 76 was observed with concentrations too large to be CO₄^?. In order to explain these features, a number of reactions involving silicon oxide negative ions have been measured in a flowing afterglow system. The ion SiO₃^? is produced by reaction of O₃^?, and CO₃^?, with SiO. The SiO₃^? ion is extremely stable and does not react measurably with NO, NO₂, CO, CO₂, O₃ or O. Since meteoroid ablation produces a large silicon input into the atmosphere, it appears possible that the ions observed at mass 76 may be SiO₃^?. Possible production mechanisms for this ion as well as the heavy ions are discussed.