Some aspects of the stratospheric Cl-ClO-Cl cycle: Possible roles of ClO, ClNO3 and HOCl

Depending on such factors as (a) the probabilities of exciting the various vibrational states in ClO formed in the reaction of Cl with O₃, (b) the radiative lifetime of ClO^*, (c) ΔH_ƒ(ClO₃), and (d) the rate coeffic`ient of the relevant three-body reaction, the production of ClO₃ via the reaction ClO^* +O₂ +M→ClO₃ +M may be quite substantial in the stratosphere. The significance of this result lies in the subsequent elimination (from the stratosphere) of ClO₃ and its associated chlorine atom as HClO₄, in the manner recently suggested by Samonaitis and Heicklen. In the stratosphere, ClO₃ most probably photodissociates primarily into OClO and O. Upon photodissociation, OClO may also yield atomic oxygen. Thus the formation of ClO₃ from ClO^* and O₂, and the above-mentioned photodissociation steps constitute an interesting, indirect mechanism of O₂ dissociation into two odd oxygen species. Other aspects of ClO^* chemistry, applicable in stratospheric conditions, also deserve attention in view of Nicholl's recent interpretation of the Umkehr measurements by Brewer et al. The reactions of ClO with HO₂, and NO₂, possess the potential of significantly obstructing the completion of the C1-ClO-Cl cycle, at least in the region below 35 km. An accurate and critical study of the chemistry of oxyacids, higher oxides, and nitrates of chlorine in the stratospheric environment is needed. Obviously, this is only a partial list of the difficult problems associated with a proper understanding of stratospheric chlorine chemistry which appears to be far more complex than what is implied in the literature. (See also notes added in proof stage.)     

Changes in thermospheric molecular oxygen abundance inferred from twilight 6300 A airglow

When the local solar zenith angle, χ_L, is < 105° the 6300 A line is much stronger than expected on the basis of F region ionic recombination alone. Between 95 and 105° the additional intensity is quantitatively explained by production of O(¹D) from photolysis of O₂ in the Schumann-Runge continuum, (λλ 1300–1750 A) using current values for solar flux, atmospheric composition and quenching of O(¹D) by N₂. The Schumann-Runge (SR) component exhibits a large seasonal variation with a maximum in summer. We interpret this variation as implying a seasonal change in thermospheric O₂ abundance; the change seems largely to reflect a variation in O₂ density at the base of the diffusive regime although some contribution may come from changes in thermospheric temperature structure. Large changes in the SR component exist from day to day and with a 27 day period following a major magnetic storm. The photodissociation source becomes inadequate when x_l < 95°; at 90° more than half of the intensity comes from still another source which we identify as local photoelectron excitation of O atoms.     

The winter anomaly in ionospheric absorption and the D-region ion chemistry

A detailed analysis of the D-region ion composition measurements performed by Zbinden et al. (1975), during a winter day of high ionospheric absorption, has been carried out. The study examines the interactive mesosphere-D-region processes which occur in such anomalous conditions and their implication for water cluster ion chemistry. Two clustering regimes for NO⁺ have been observed in the data. Association with N₂ is identified as the dominant process below 76 km. Between 76 and 78 km altitude the effective loss rate of NO⁺ drops by two orders of magnitude. Above 77 km, the three-body reaction NO⁺ + CO₂+M→NO⁺CO₂+M seems to be the main NO⁺ loss. A mesospheric temperature profile could be derived from the ion composition data. This indicates the presence of a strong inversion above 76 km altitude. The wavelike structure obtained, is shown to be consistent with in situ winter temperature measurements. The sharp suppression of the N₂ association reaction could, thus, be explained by an increase in the collisional break-up of the NO⁺N₂ ion because of the enhanced temperature. In conclusion, our study indicates that, besides the increase in the production of NO⁺ and O₂⁺, due to an enhancement in the minor ionizable constituents, an additional thermal mesosphere-D-region interaction seems necessary to explain this winter anomalous ion composition data.     

Chemistry of the nightside ionosphere of Venus

We have constructed a one-dimensional model of the nightside ionosphere of Venus in which it is assumed that the ionization is maintained by day-to-night transport of atomic ions. Downward fluxes of O⁺, C⁺ and N⁺ in the ratios measured on the dayside at high altitudes are imposed at the upper boundary of the model (about 235 km). We discuss the resulting sources and sinks of the molecular ions NO⁺,CO⁺,N₂⁺,CO₂⁺ and O₂⁺. As the O⁺ flux is increased, the peak density of O⁺ increases proportionally and the altitude of the peak decreases. The O₂⁺ peak density is approximately proportional to the square root of the O⁺ flux and the peak rises as the O⁺ flux increases. NO⁺ densities near the peak are relatively unaffected by changes in the O⁺ flux. If the ionosphere is maintained mostly by transport, the ratio of the peak densities of O⁺ and O₂⁺ indicates the downward flux ofO⁺, independent of the absolute magnitudes of the densities. The densities of mass-28 ions are, however, still considered to be the most sensitive indicator of the importance of electron precipitation. We examine here the inbound and outbound portions of six early nightside orbits with low periapsis and use data from the Pioneer Venus orbiter ion mass spectrometer, the retarding potential analyzer and the electron temperature probe to determine the relative importance of ion transport and electron precipitation. For most of the orbits, precipitation is inferred to be of low to moderate importance. Only for orbit 65, which was the first nightside orbit published by Taylor et al. [J. geophys. Res. 85, 7765 (1980)] and for the inbound portion of orbit 73 does the ionization structure appear to be greatly affected by electron precipitation.     

First model of negative ion composition in the troposphere

A chemical model of negative ions in the troposhere (0–15 km) is presented. This model is an extension of the negative ion composition model in the lower stratosphere (Kawamoto and Ogawa, 1984, Planet. Space Sci. 32, 1223) with some modifications. The computed result shows that the predominant ions are NO₃⁻HNO₃H₂O below 10km and NO⁻₃(HNO₃)₂ above 10km, and that the fractional abundance of cluster ions having a HSO⁻₄ core increases with height below 12km and decreases with height above it. The ions having CO⁻₃ cores are at most 2% in fractional abundance. The other kinds of negative ions are far smaller in fractional abundance than the NO⁻₃, HSO⁻₄ and CO⁻₃ core ions. The result is compared with the two mass spectrometric observed results (Heitmann and Arnold, 1983, Nature, Lond. 306, 747; Perkins and Eisele, 1984, J. geophys. Res. 89, 9649). The problems on the tropospheric negative ions which arose are discussed.     

Twilight effects of solar ionizing radiation

The absorption of solar ionizing radiation during twilight is investigated. Ion production rates are obtained as a function of altitude and twilight intensities and altitude profiles of emissions arising from the fluorescence of solar ionizing radiation are calculated for various solar depression angles. For an atmosphere with an exospheric temperature of 750°K, the predicted overhead intensity from fluorescence of the O⁺(²P — ²D) lines at 7319–7330 diminishes from 175 R at dusk to 10 R at a solar depression angle of 10°. The predicted overhead intensities from fluorescence of the N₂⁺ Meinel and first negative systems are respectively about 175 R and 20 R at dusk diminishing to respectively 1.5 R and 0.1 R at a solar depression angle of 10°.

It is suggested that a charge transfer reaction of O⁺²D in N₂ is a significant source of N₂⁺ ions. This reaction offers a possible explanation for the high apparent rotational temperatures in the first negative system observed by Broadfoot and Hunten. Other excitation and ionization mechanisms are briefly discussed.     

Improved absorption cross-sections of oxygen in the wavelength region 205–240 nm of the Herzberg continuum

The laboratory values of the Herzberg continuum absorption cross-section of oxygen at room temperature from Cheung et al. (1986, Planet. Space Sci. 34, 1007), Jenouvrier et al. (1986a, Planet. Space Sci. 34, 253) and Jenouvrier et al. (1986, J. quant. Spectrosc. radiat. Transfer 36, 349) have been compared and re-analyzed. There is no discrepancy between the absolute values of these two sets of independent measurements. These values have been combined together in a linear least-squares fit to obtain improved values of the Herzberg continuum cross-section of oxygen at room temperature throughout the wavelength region 205–240 nm. Agreement with in situ and other laboratory measurements is discussed.     

Laboratory studies of helium ion loss processes of interest in the ionosphere

Preliminary measurements of reaction rates for loss of thermal helium ions in reaction with molecular oxygen and nitrogen establish rather conclusively that the helium ions in the ionosphere will be lost in reaction with molecular nitrogen rather than molecular oxygen in contrast to previous assumptions based on theoretical considerations. The rate of thermal He⁺ loss in reaction with N₂ is measured to be 1·2 ± 0·3 times the rate for reaction with O₂. This conclusion is of considerable significance to atmospheric physics because the oxygen loss process contained the possibility of leading to terrestrial helium escape and therefore the possibility of a steady state helium atmosphere. The nitrogen loss process does not have this possibility so that no satisfactory mechanism has yet been proposed which will allow a steady state helium atmosphere. The interpretation of recent atmospheric helium ion profiles obtained by rocket borne mass spectrometers appear to be inconsistent with the laboratory loss rate constants and current atmospheric theory.     

Origin of the ten degree Solar System dust bands

The Solar System dust bands discovered by IRAS are toroidal distributions of dust particles with common proper inclinations. It is impossible for particles with high eccentricity (approximately 0.2 or greater) to maintain a near constant proper inclination as they precess, and therefore the dust bands must be composed of material having a low eccentricity, pointing to an asteroidal origin. The mechanism of dust band production could involve either a continual comminution of material associated with the major Hirayama asteroid families, the equilibrium model (Dermott et al. (1984) Nature 312, 505–509) or random disruptions in the asteroid belt of small, single asteroids (Sykes and Greenberg (1986) Icarus 65, 51–69). The IRAS observations of the zodiacal cloud from which the dust band profiles are isolated have excellent resolution, and the manner in which these profiles change around the sky should allow the origin of the bands, their radial extent, the size-frequency distribution of the material and the optical properties of the dust itself to be determined. The equilibrium model of the dust bands suggests Eos as the parent of the 10° band pair. Results from detailed numerical modeling of the 10° band pair are presented. It is demonstrated that a model composed of dust particles having mean semimajor axis, proper eccentricity and proper inclination equal to those of the Eos family member asteroids, but with a dispersion in proper inclination of 2.5°, produces a convincing match with observations. Indeed, it is impossible to reproduce the observed profiles of the 10° band pair without imposing such a dispersion on the dust band material. Since the dust band profiles are matched very well with Eos, Themis and Koronis type material alone, the result is taken as strong evidence in favor of the equilibrium model. The effects of planetary perturbations are included by imposing the appropriate forced elements on the dust particle orbits (these forced elements vary with heliocentric distance). A subsequent model in which material is allowed to populate the inner solar system by a Poynting-Robertson drag distribution is also constructed. A dispersion in proper inclination of 3.5° provides the best match with observations, but close examination of the model profiles reveals that they are slightly broader than the observed profiles. If the variation of the number density of asteroidal material with heliocentric distance r is given by an expression of the form 1/r^τ then these results indicate that γ < 1 compared with γ = 1 expected for a simple Poynting-Robertson drag distribution. This implies that asteroidal material is lost from the system as it spirals in towards the Sun, owing to interparticle collisions.     

Rocket measurements of the 6300 Å and 3914 Å dayglow features

Rocket results are presented on the OI 6300 Å line and on the N₂⁺ 3914 Å band in the dayglow. An altitude range of 78–335 km is covered. Theoretical interpretations are given, using results of simultaneous measurements of electron density and electron temperature. The apparent brightness of the 6300 Å line at the base of the emitting region is found to be 13 kR, of which 5.5 kR are ascribed to excitation through the Schumann-Runge dissociation of O₂ by the solar UV radiations, 0.55 kR to the dissociative recombination of O₂⁺ and NO⁺ ions, and 0.03 kR to the excitation of O by thermal electrons. An additional source of excitation above 280 km is suggested. The deactivation of O(¹D) by O₂(X³Σ_g⁻) is found to be appreciable below 200 km, and its rate coefficient is estimated to be 2 × 10⁻¹⁰ cm³/sec. The apparent brightness of the 3914 Å band at the base of the emitting region is found to be 6.5 kR, decreasing to 3.2 kR at 330 km. Assuming that fluorescent scattering of solar radiation is the mechanism involved the distribution of N₂⁺ ions is calculated. The rate coefficients for the loss of these ions are hence calculated.     

A survey of flux transfer events recorded by the UKS spacecraft magnetometer

The UKS spacecraft operated from August 1984 through to January 1985. During that time, it made multiple crossings of the magnetopause in local time sectors extending from mid-afternoon to just behind the dawn meridian. We have surveyed the magnetometer records from these magnetopause encounters and have compiled a catalogue of flux transfer events (FTEs using criteria identical to those employed by Rijnbeek et al. (1984, J. Geophys. Res. 89, 786) in their survey of ISEE spacecraft magnetometer data. Using the catalogue, we find that FTE occurrence determined from the UKS data set is substantially less than that detected using data from the early ISEE 1/2 spacecraft orbits. The UKS data set shows a correlation between FTE occurrence and southward external magnetic field, but there are several instances of passes in which no FTEs are detected but for which the external field was unam- biguousluy southward. The passes with the largest number of events are those for which the field outside the magnetopause has a large B_M component. We conclude that the lower latitude of the UKS encounters is responsible for the discrepancy with the ISEE occurrence. The most likely source region appears to be near the subsolar region.     

A review of satellite, observations of atmospheric ozone

Since the first satellite ozone measurements in 1960, basically three methods have been developed: backscattered solar ultraviolet, infrared emission, and occultation. In a review article by Krueger et al. (1980, Phil. Trans. R. Soc. Lond. A296, 191), the authors examine the above satellite methods and data covering the period up to about 1980. Our purpose is to review the development of the satellite ozone methodology since about 1980 with particular emphasis on the relationship of satellite data to the continued need for ground-based observations. Finally, we look toward the future to the Upper Atmosphere Research Satellite, to be launched in about 1991, and the view that this is to be a collective experiment, not a series of independent measurements, focusing on the photochemistry and dynamics of the stratosphere.     

ETON 6: A rocket measurement of the O2 Infrared Atmospheric (0-0) band in the nightglow

Co-ordinated rocket measurements of the O₂(a¹Δ_g−X³Σ_g⁻) Infrared Atmospheric (0-0) band emission profile and the atomic oxygen densities in an undisturbed night-time atmosphere are used to investigate the processes responsible for the excitation of O₂(a¹Δ_g) in the terrestrial nightglow. It is shown that three-body recombination of atomic oxygen, and subsequent energy transfer processes, can explain only part of the observed emission profile and that at least two other sources of O₂(a¹Δ_g) emission must exist. One of these additional sources, responsible for most of the emission observed below 90km, is identified as arising from the night-time residual of the very large dayglow ¹Δ_g population. The other additional source is required to explain most of the emission observed above 95km. The processes responsible for this high altitude component cannot be identified but the vertical distribution of the required source function strongly resembles the profile of the atomic oxygen density squared and suggests that a two-body radiative recombination process may be involved. However, the measured zenith emission rates can also be explained without the high altitude source of O₂(a¹Δ_g) if optical emission at 1.27 μm was induced by the rocket as it penetrated the nightglow layer.     

Photometric measurements of the O2 U.V. nightglow

Measurements of the O₂(A³Σ − X³Σ) Herzberg system in the night airglow have been made with the ESRO TD-1 satellite in the wavelength range 2400–3100 A. The slant emission rate varies from 3.5 to 15 kR, indicating an irregular structure of the atomic oxygen near the turbopause. A statistical maximum intensity is found near the tropic in the winter hemisphere. The intensity profile is consistent with excitation by three-body recombination of oxygen atoms. The observed total emission rate can be accounted for by reasonable atomic oxygen densities and an O₂(A³Σ) production efficiency of about 20% if quenching by N₂ occurs at the rate deduced from laboratory and other airglow measurements.     

A kinematic study of the Galaxy

Using the proper motion and parallax data for 1011 O-B stars in the Hipparcos Catalogue we have derived the Oort constants, A = 17.60 ± 0.21 (km/s)/kpc, B = −14.62 ± 0.20 (km/s)/kpc, and a solar velocity V = 16.7 ± 0.10 km/s in the direction l = 45.3° ± 2.8°, b = 21.0° ± 2.3°. For a galactocentric distance of the sun of R₀ = 8.5 kpc, we then get a galactic rotational velocity of the solar neighbourhood of V_lsr = 273.9 km/s, obviously much higher than the IAU published value of 220 km/s. We have investigated the cause for this difference.     

Tianjin photographic zenith tube observations

In this paper we analyse the observational data obtained by the Chinese-made PZT in the two periods 1979 Feb – 1980 May and 1981 Dec – 1983 March. The internal accuracy of single star is found to be m_u = ±13.0 ms, m_φ = ±0. “144 for the first period, and m_u = ±14.6 ms, m_φ = ±0.” 152 for the second. Correction of star position is found by the chain method. The systematic error caused by the sealed window of the evacuated chamber and the temperature effect of the plate scale are investigated. Monthly means of time and latitude are given.     

Excitation of the Aπu state of N by electrons

Absolute values of the emission cross sections for five vibrational bands in the Meinel system of N₂⁺,A²π_u to X²Σ_g⁺, excited by electron impact are presented. From these, a value was obtained for the total excitation cross section of the A²π_u state at 100 eV of 26·5 × 10⁻¹⁸ cm². The results are compared with those of other workers and with theory. Collisional transfer of the excitation energy from the levels of the A²π_u state was also observed with a transfer cross section of approximately 10⁻¹⁴ cm².     

Maximum likelihood estimation of the mean parallax and kinematic parameters of the Pleiades

A simultaneous, maximum-likelihood determination of the distance and kinematic parameters of the Pleiades is made. The results are: distance of the cluster d = 135.56 ± 0.72 pc, dispersion σ_d = 7.66 ± 0.80 pc; space velocity V = 25.94 ± 0.13 km/s, dispersion σ_v = 0.58 ± 0.09 km/s coordinates of the convergent point A = 101.95° ± 0.47°, D = −41.36° ± 0.29°.     

Deuterium enrichment in giant planets

Recently published laboratory measurements of the isotopic exchange rate constant k⁻(T) between CD₄ and H₂ are used to calculate f(z)—the isotopic enrichment factor between CH₄ and H₂—at every level in the outer atmosphere of the giant planets. The variation of f(z) with local vertical velocity, temperature and pressure has been calculated under the assumption that atmospheres are convective and uncertainties have been calculated by error propagation. Considering only the random errors—mainly the uncertainty on k⁻(T)—the f values in the observable upper atmospheres of giant planets (i.e. at z = 0, P = 1 bar) are: f(0) = 1.25 ± 0.05, 1.38 ± 0.06, 1.68 ± 0.09, and 1.61 ± 0.08 for Jupiter, Saturn, Uranus, and Neptune, respectively. Additional systematic errors due to the uncertainty in calculating the vertical velocity in the framework of the mixing length Prandtl theory lead to an overall uncertainty on f(0) of ±0.12, ±0.15, ±0.23, and ±0.21 for each planet, respectively. The D/H ratios in H₂ derived from the measured CH₃D/CH₄ ratios in the upper atmosphere of the four giant planets are then recalculated. Uranus and Neptune seem to be enriched in deuterium with respect to the protosolar nebula but depleted relative to the Standard Mean Oceanic Water on the Earth (SMOW). However calculations based on current interior models of Neptune suggest that ices which formed the core of the planet had a D/H ratio of the order of the SMOW. The deuterium abundance in proto-Uranian ices remains uncertain. The case where water is a major constituent of the fluid envelope of Neptune is discussed. It is shown that the D/H ratio of the planet would then be higher than the value measured in hydrogen. Even in this case, the D/H ratio in proto-Neptunian ices is less than the recently revised value in P/Halley and less than the value measured in water of the Semarkona meteorite. These results suggest that the ices which formed the core of Neptune did not have an interstellar origin. Similarly, the comparison of the most recent determination of the D/H ratio in the atmosphere of Titan with the value of D/H in P/Halley suggests that this atmosphere was not formed by infalling comets but more likely from grains embedded in the sub-nebula of Saturn.     

Observation and Study of the CO, CO, HCO and N2H Molecular Lines Towards IRAS 02232+6138

Using the 13.7 m millimeter-wave telescope at the Qinghai Station of Purple Mountain Observatory, we have made observations of ¹³CO, C¹⁸O, HCO⁺ and N₂H⁺ molecular lines towards IRAS 02232+6138. As the excitation density of the probe molecule increases from ¹³CO to HCO⁺, the size of the cloud core associated with IRAS 02232+6138 decreases from 2.40 pc to 0.54 pc, and the virial mass of the cloud core decreases from 2.2 × 10³M to 5.1 × 10²M. A bipolar molecular outflow is found towards IRAS 02232+6138. Using the power function n(r) ∝ r⁻ to fit the spatial density structure of the cloud core, we obtain the power-law index  = 2.3 − 1.2; and we find that, as the probed density increases, the power function becomes more flat. The abundance ratio of ¹³CO to C¹⁸O is 12.4 ± 6.9, comparable with the values 11.8 ± 5.9 for dark clouds and the values 9.0–15.6 for massive cores. The abundance of N₂H⁺ molecules is 3.5 ± 2.5 × 10⁻¹⁰, consistent with the value 1.0 − 5.0 × 10⁻¹⁰ for dark cloud cores and the value 1.2 − 12.8 × 10⁻¹⁰ for massive cores. The abundance of HCO⁺ molecules is 0.9 ± 0.5 × 10⁻⁹, close to the value 1.6 − 2.4 × 10⁻⁹ for massive cores. An increase of HCO⁺ abundance in the outflow region was not found. Combining with the IRAS data, the luminosity-mass ratio of the cloud core is obtained in the range 37–163(L/M). Based on the IRAS luminosity, it is estimated that a main-sequence O7.5 star is probably embedded in the IRAS 02232+6138 cloud core.