Ion-ion mutual neutralization and ion-neutral switching reactions of some stratospheric ions

Following the recent mass spectrometric observations of the ambient stratospheric positive and negative ions we have carried out co-ordinated laboratory experiments using a selected ion flow tube apparatus and a flowing afterglow apparatus for the following purposes: (i) to consider whether CH₃CN is a viable candidate molecule for the species X in the observed stratospheric ion series H⁺ (H₂O_n (X)_m and (ii) to determine the binary mutual neutralization rate coefficients α_i for the reactions ofH⁺ (H₂O₄ and H⁺(H₂O)(CH₃CN)₃ with several of the negative ion species observed in the stratosphere. We conclude from (i) that CH₃CN is indeed a viable candidate for X and from (ii) that the α_i for stratospheric ions are within the limited range (5–6) × 10^?8 cm³ s^?1.     

Ozone and photochemistry of the Martian lower atmosphere

The calculation of number densities of CO₂, H₂O and N₂ photolysis products was carried out for the Martian atmosphere at heights up to 60 km. The ozone distributed in the atmosphere as a layer of 10 km width with [O₃] max = 2.5 × 10⁹ cm³ at height of 35 km which agree well with the results of u.v. observations on the evening terminator from the Mars-5 satellite. The calculated densities of O₂, CO and H₂O are also in good agreement with the measured data. The eddy diffusion coefficient is equal to 3 × 10⁶ in the troposphere (h ? 30 km) and 10⁸ cm² s^?1 above 40 km. The dependence of the total ozone content on water vapour amount in the atmosphere is considered; the hypothesis about the influence of water ice aerosol on the ozone formation is proposed to explain the high concentrations of ozone in the morning.     

Lightnings and nitric oxide on Venus

In an updating of energy characteristics of lightnings on Venus obtained from Venera-9 and -10 optical observations, the flash energy is given as 8 × 10⁸ J and the mean energy release of lightnings is 1 erg cm^?2 s which is 25 times as high as that on the Earth. Lightnings were observed in the cloud layer. The stroke rate in the near-surface atmosphere is less than 5 s^?1 over the entire planet if the light energy of the stroke exceeds 4 × 10⁵ J and less than 15 s^?1 for (1–4) × 10⁵ J.The average NO production due to lightnings equals 5 × 10⁸ cm^?2 s^?1, the atomic nitrogen production is equal to 7 × 10⁹ cm^?2s^?1,the N flux toward the nightside is 3.2 × 10⁹ cm^?2s^?1, the number densities [N] = 3 × 10⁷cm^?3 and [NO] = 1.8 × 10⁶cm^?3 at 135 km. Almost all NO molecules in the upper atmosphere vanish interacting with N and the resulting NO flux at 90-80 km equals 5 × 10⁵cm^?2s^?1, which is negligibly small as compared with lightning production. If the predissociation at 80–90 km is regarded as the single sink of NO, its mixing ratio, f_NO, is 4 × 10^?8, for the case of a surface sink f_NO = 0.8 × 10^?9 at 50 km. Excess amounts, $\text{f}{}_{\mathrm{<mtext>NO</mtext>}}\text{? 4 × 10}{}^{\mathrm{?8}}$, may exist in the thunderstorm region.     

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.     

Isotope identification in NO as a chemical tracer in the middle atmosphere

The nitrogen isotope ratio of middle atmosphere nitrogen oxide is predicted as a function of altitude. Nitrogen oxides originate photochemically either from stratospheric nitrous oxide reacting with O(¹D) or in the mesosphere and thermosphere from direct dissociation of N₂ and ionization-initiated reactions involving O₂ and N₂. During its formation process, N₂O acquires a nitrogen isotopic composition of N isotopes different than N₂. Photodissociation within the stratosphere also modifies the proportion of isotopes. Reaction of stratospheric NO with O₃ produces NO₂, which when photodissociated yields NO depleted in ¹⁵N relative to NO₂ in laboratory air. The value of δ¹⁵NO in the stratosphere is −100‰. In the altitude region between 50 and 65 km, NO is transformed into NO₂ and then returned to NO by reaction of NO₂ with O and by NO₂ photodissociation. These reactions determine the isotopic makeup of NO. Above 65 km, nitric oxide is produced by local ionization processes and gas phase photochemical reactions involving N₂ and excited O₂. These processes determine the isotopic composition of NO in the upper mesosphere and thermosphere. Here δ¹⁵NO is 0‰. Air transported into the mesosphere above 65 km will reflect the NO isotopic values of the region below, while mesospheric NO transported below 65 km will not be distinguishable from NO originating in the stratosphere.     

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 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.     

On the production of nitric oxide by cosmic rays in the mesosphere and stratosphere

Nitric oxide is formed in the atmosphere through the ionization and dissociation of molecular nitrogen by galactic cosmic rays. One NO molecule is formed for each ion pair produced by cosmic ray ionization.The height-integrated input (day and night) to the lower stratosphere is of the order of 6 × 10⁷ NO molecules cm^?2/sec in the auroral zone (geomagnetic latitude Φ ? 60°) during the minimum of the sunspot cycle and 4 × 10⁷ NO molecules cm^?2/sec in the subauroral belt and auroral region (Φ? 45°) at the maximum of solar activity. The tropical production is less than 10^?7 NO molecules cm^?2/sec above 17 km and at the equator the production is only 3 × 10⁶NO molecules cm^?2/sec.     

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.     

The CH4 Density in the Upper Atmosphere of Titan

Previous modeling by Banaszkiewicz et al. (2000a,b) showed that the CH₄ thermospheric mixing ratio on Titan could vary as much as 35-40% due to ion-neutral chemical reactions. A new vertical methane profile has been computed by simultaneously modifying the stratospheric methane mixing ratio and the K(z) previously considered by Lara et al. (1996) and Banaszkiewicz et al. (2000a,b). A satisfactory fit of the methane thermospheric abundance and stratospheric mixing ratio of other minor constituents is achieved by placing the homopause at ∼1000 km and increasing the methane stratospheric mixing ratio (q_CH4) up to 3.8%. The new proposed eddy diffusion coefficient steadily rises from 1×10⁷ cm² s⁻¹ at 700 km to 1×10¹⁰ cm² s⁻¹ at 1500 km, whereas the stratospheric values are in the range (4-20)×10³ cm² s⁻¹. Other likely ionization sources that can influence the methane distribution are (i) a metallic ion layer produced by micrometeoroid infall and (ii) frequent X-rays solar flares. Analysis of the effects of these ionization sources on the methane distribution indicates that, unlike previously assumed, CH₄ can suffer considerable variations. These variations, although proved in this work, must be cautiously regarded since several assumptions have to be made on the rate of N₂ and CH₄ ionization by the processes previously mentioned. Hence, these results are only indicative of methane sensitivity to ionospheric chemistry.     

Photochemistry of the stratosphere of Venus: Implications for atmospheric evolution

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, combined with the results of recent observations and laboratory studies. We examined three models, with H₂ mixing ratio equal to 2 × 10^?5, 5 × 10^?7, and 1 × 10^?13, respectively. All models satisfactorily account for the observations of CO, O₂, O₂(¹Δ), and SO₂ in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the uv albedo. Oxygen, derived from CO₂ photolysis, is primarily consumed by CO₂ recombination and oxidation of SO₂ to H₂SO₄. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO₂ by O occurs in the lower stratosphere. In the high-H₂ model (model A) the OO bond is broken mainly by S + O₂ and SO + HO₂. In the low-H₂ models additional reactions for breaking the OO bond must be invoked: NO + HO₂ in model B and ClCO + O₂ in model C. It is shown that lightning in the lower atmosphere could provide as much as 30 ppb of NO_x in the stratosphere. Our modeling reveals a number of intriguing similarities, previously unsuspected, between the chemistry of the stratosphere of Venus and that of the Earth. Photochemistry may have played a major role in the evolution of the atmosphere. The current atmosphere, as described by our preferred model, is characterized by an extreme deficiency of hydrogen species, having probably lost the equivalent of 10²–10³ times the present hydrogen content.     

Martian isotopic ratios and upper limits for possible minor constituents as derived from Mariner 9 infrared spectrometer data

The Mariner 9 infrared spectrometer obtained data over a large part of Mars for almost a year beginning late in 1971. Mars' infrared emission spectrum was measured from 200 to 2000 cm^?1 with an apodized resolution of 2.4 cm^?1. No significant deviation from terrestrial ratios of carbon (¹²C/¹³C) or oxygen (¹⁶O/¹⁸O; ¹⁶O/¹⁷O) isotopes was observed on Mars. The ¹²C/¹³C isotopic ratio was found to be terrestrial with an uncertainty of 15%. Upper limits have been calculated for several minor constituents. With an effective noise equivalent radiance of 1.2 × 10^?9 W cm^?2 sr^?1/cm^?1, new upper limits in centimeter-atmospheres of 2 × 10^?5 for C₂H₂, 4 × 10^?3 for C₂H₄, 3 × 10^?3 for C₂H₆, 2 × 10^?4 for CH₄, 1 × 10^?3 for N₂O, 1 × 10^?4 for NO₂, 4 × 10^?5 for NH₃, 1 × 10^?3 for PH₃, 7 × 10^?4 for SO₂, and 1 × 10^?4 for OCS have been derived.     

Titan’s aerosol and stratospheric ice opacities between 18 and 500 μm: Vertical and spectral characteristics from Cassini CIRS

Vertical distributions and spectral characteristics of Titan’s photochemical aerosol and stratospheric ices are determined between 20 and 560 cm^?1 (500–18 μm) from the Cassini Composite Infrared Spectrometer (CIRS). Results are obtained for latitudes of 15°N, 15°S, and 58°S, where accurate temperature profiles can be independently determined.In addition, estimates of aerosol and ice abundances at 62°N relative to those at 15°S are derived. Aerosol abundances are comparable at the two latitudes, but stratospheric ices are ～3 times more abundant at 62°N than at 15°S. Generally, nitrile ice clouds (probably HCN and HC₃N), as inferred from a composite emission feature at ～160 cm^?1, appear to be located over a narrow altitude range in the stratosphere centered at ～90 km. Although most abundant at high northern latitudes, these nitrile ice clouds extend down through low latitudes and into mid southern latitudes, at least as far as 58°S.There is some evidence of a second ice cloud layer at ～60 km altitude at 58°S associated with an emission feature at ～80 cm^?1. We speculate that the identify of this cloud may be due to C₂H₆ ice, which in the vapor phase is the most abundant hydrocarbon (next to CH₄) in the stratosphere of Titan.Unlike the highly restricted range of altitudes (50–100 km) associated with organic condensate clouds, Titan’s photochemical aerosol appears to be well-mixed from the surface to the top of the stratosphere near an altitude of 300 km, and the spectral shape does not appear to change between 15°N and 58°S latitude. The ratio of aerosol-to-gas scale heights range from 1.3–2.4 at about 160 km to 1.1–1.4 at 300 km, although there is considerable variability with latitude. The aerosol exhibits a very broad emission feature peaking at ～140 cm^?1. Due to its extreme breadth and low wavenumber, we speculate that this feature may be caused by low-energy vibrations of two-dimensional lattice structures of large molecules. Examples of such molecules include polycyclic aromatic hydrocarbons (PAHs) and nitrogenated aromatics.Finally, volume extinction coefficients Nχ_E derived from 15°S CIRS data at a wavelength of λ = 62.5 μm are compared with those derived from the 10°S Huygens Descent Imager/Spectral Radiometer (DISR) data at 1.583 μm. This comparison yields volume extinction coefficient ratios Nχ_E(1.583 μm)/Nχ_E(62.5 μm) of roughly 70 and 20, respectively, for Titan’s aerosol and stratospheric ices. The inferred particle cross-section ratios χ_E(1.583 μm)/χ_E(62.5 μm) appear to be consistent with sub-micron size aerosol particles, and effective radii of only a few microns for stratospheric ice cloud particles.     

Galilean satellite eclipse studies: III. Jovian methane abundance

The methane abundance in the lower Jovian stratosphere is measured using Galilean satellite eclipse light curves. Spectrally selective observations in and between absorption bands are compared. An average mixing ratio at the locations measured is [CH₄]/[H₂] ～ 1.3 × 10^?3, larger than the value 0.9 × 10^?3 expected for a solar abundance of carbon. Some zenographic variation of the mixing ratio may occur. Observationally compatible values are 1.3–2.0 × 10^?3 in the STZ, 1.3– 2.6 × 10^?3 on the GRS/STrZ edge, and 0.7–1.3 × 10^?3 in the GRS.     

Titan: Far-infrared and microwave remote sensing of methane clouds and organic haze

It is shown that Titan's surface and plausible atmospheric thermal opacity sources—gaseous N₂, CH₄, and H₂, CH₄ cloud, and organic haze—are sufficient to match available Earth-based and Voyager observations of Titan's thermal emission spectrum. Dominant sources of thermal emission are the surface for wavelenghts λ ? 1 cm, atmospheric N₂ for 1 cm ? λ ? 200 μm,, condensed and gaseous CH₄ for 200 μm ? λ ? 20 μm, and molecular bands and organic haze for λ ? 20 μm. Matching computed spectra to the observed Voyager IRIS spectra at 7.3 and 52.7° emission angles yields the following abundances and locations of opacity sources: CH₄ clouds: 0.1 g cm^? at a planetocentric radius of 2610–2625 km, 0.3 g cm^?2 at 2590–2610 km, total 0.4 ± 0.1 g cm^–2 above 2590 km; organic haze: $\text{4 ± 2 × 10}{}^{\mathrm{?6}}\text{,}\text{g cm}\text{,}{}^{\mathrm{?2}}$ above 2750 km; tropospheric H₂: 0.3 ± 0.1 mol%. This is the first quantitative estimate of the column density of condensed methane (or CH₄/C₂H₆) on Titan. Maximum transparency in the middle to far IR occurs at 19 μm where the atmospheric vertical absorption optical depth is $\text{?0.6}$ A particle radius $\text{r}\text{? 2 μ}\text{m}$ in the upper portion of the CH₄ cloud is indicated by the apparent absence of scattering effects.     

A global study of O2(1Δg) airglow: Day and twilight

Aircraft measurements of $\text{O}{}_2\text{(}{}^1\text{Δ}{}_{\mathrm{g}}\text{)}$ emission made over a 10-yr period provide information on the variation of ozone with latitude and season in the altitude region 50–90 km. Between 50 and 70 km there appears to be little variation (< ± 25%) whereas the abundance between 80 and 90 km exhibits a large seasonal change north of 30°N and much less at lower latitude. At mid and high latitude the column abundance above ～ 80 km changes from ? 1 × 10¹⁴ cm^?2 in summer to about 3 × 10¹⁴ cm^?2 in winter. There are occasional enhancements in both the day and twilight airglow which almost always occur in association with auroral activity or, at least, where such activity is statistically most likely. These enhancements appear to reflect a corresponding increase in the ozone mixing ratio in the upper stratosphere. While the gradient in ozone mixing ratio with latitude is generally small at altitudes between 50 and 90km there are occasions when a temporary latitude structure can be seen, particularly above 80 km.     

The measurement of ozone concentrations at high latitude during the twilight

The ozone height profile in the Arctic, at the end of the winter, has been measured up to an altitude of 100 km using a combined solar occultation and 1.27 μ oxygen emission technique. The typical two layer structure has been observed with a high altitude minimum near 80 km and a maximum at 86 km. The measured concentration in this ozone bulge was 5.1 × 10⁷cm^?3, typical of that measured at 52°N for the summer months. It is suggested that this reduced ozone concentration may have been associated with a stratospheric warming event that was in progress at the time of the measurement.     

On determining the ozone number density distribution from OAO-2 stellar occultation measurements

Stellar occultation data from the 2460 Å and 2980 Å channels of the OAO-2 stellar photometers have been used to derive the nighttime ozone number density distribution in the low latitude mesosphere. The nighttime ozone distribution obtained from both channels are similar indicating a maximum in the ozone distribution near 80km of 2–3 × 10³cm^?3.     

The atmosphere of Titan: An analysis of the Voyager 1 radio occultation measurements

Two coherently related radio signals transmitted from Voyager 1 at wavelengths of 13 cm (S-band) and 3.6 cm (X-band) were used to probe the equatorial atmosphere of Titan. The measurements were conducted during the occultation of the spacecraft by the satellite on November 12, 1980. An analysis of the differential dispersive frequency measurements did not reveal any ionization layers in the upper atmosphere of Titan. The resolution was approximately 3 × 10³ and 5 × 10³ electrons/cm³ near the evening and morning terminators, respectively. Abrupt signal changes observed at ingress and egress indicated a surface radius of 2575.0 ± 0.5 km, leading to a mean density of 1.881 ± 0.002 g cm^?3 for the satellite. The nondispersive data were used to derive profiles in height of the gas refractivity and microwave absorption in Titan's troposphere and stratosphere. No absorption was detected; the resolution was about 0.01 dB/km at the 13-cm wavelength. The gas refractivity data, which extend from the surface to about 200 km altitude, were interpreted in two different ways. In the first, it is assumed that N₂ makes up essentially all of the atmosphere, but with very small amounts of CH₄ and other hydrocarbons also present. This approach yielded a temperature and pressure at the surface of 94.0 ± 0.7°K and 1496 ± 20 mbar, respectively. The tropopause, which was detected near 42 km altitude, had a temperature of 71.4 ± 0.5°K and a pressure of about 130 mbar. Above the tropopause, the temperature increased with height, reaching 170 ± 15°K near the 200-km level. The maximum temperature lapse rate observed near the surface (1.38 ± 0.10°K/km) corresponds to the adiabatic value expected for a dry N₂ atmosphere—indicating that methane saturation did not occur in tbis region. Above the 3.5-km altitude level the lapse rate dropped abruptly to 0.9 ± 0.1°K/km and then decreased slowly with increasing altitude, crossing zero at the tropopause. For the N₂ atmospheric model, the lapse rate transition at the 3.5-km level appears to mark the boundary between a convective region near the surface having the dry adiabatic lapse rate, and a higher stable region in radiative equilibrium. In the second interpretation of the refractivity data, it is assumed, instead, that the 3.5 km altitude level corresponds to the bottom of a CH₄ cloud layer, and that N₂ and CH₄ are perfectly mixed below this level. These assumptions lead to an atmospheric model which below the clouds contains about 10% CH₄ by number density. The temperature near the surface is about 95°K. Arguments concerning the temperature lapse rates computed from the radio measurements appear to favor models in which methane forms at most a limited haze layer high in the troposphere.     

Cassini CIRS update on stratospheric ices at Titan's winter pole

A strong, broad spectral emission feature at 85° N latitude centered at 221 cm⁻¹ remains unidentified after candidate ices of H₂O and pure crystalline CH₃CH₂CN are unambiguously ruled out. A much shallower weak emission feature starts at 160 cm⁻¹ and blends into the strong feature at ∼190 cm⁻¹. This feature is consistent with one formed by an HCN ice cloud composed of ?5 μm radius particles that resides in the lower stratosphere somewhere below an altitude of 160 km. Titan's stratospheric aerosol appears to have a spectral emission feature at about 148 cm⁻¹. The aerosol abundance at 85° N is about a factor 2.2 greater than at 55° S.