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.     

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.     

Reaction paths leading from O+2 to water clusters under cold mesospheric conditions

Arnold and Krankowsky (Int. Symp. Solar-Terrestrial Physics, Sao Paulo, 1974) have reported D-region positive ion measurements in which a number of new cluster ions of minor abundance were apparent. These ions, which they attributed to clusters with N₂, O₂, and CO₂ ligands, were observable due to enhanced O⁺₂ production and to the low temperatures during the flight. Here we consider these in situ ion data in view of recent laboratory ion-molecule reaction experiments which cast light on the mechanism leading from O⁺₂ to water clusters in air mixtures. Possible intermediates are discussed in terms of ion stability and existence of effective reaction paths under the given atmospheric conditions. These proposed intermediates are then fitted into a coherent reaction mechanism resulting in significant new pathways for the formation of protonated water clusters. A semiquantitative measure of the importance of each of the pathways is then calculated by the use of signal flow graph theory.     

Coupling between the F-region and protonosphere: Numerical solution of the time-dependent equations

This paper describes a new method of solution of the time-dependent continuity and momentum equations for H⁺ and O⁺ in mid-latitude magnetic field tubes from the F-region to the equator. For each ion the equations are expressed as an integro-differential equation. This equation is treated as an ordinary differential equation and solved by a searching method. By means of this method, the distribution of H⁺ in the O⁺?H⁺ transition region and the protonosphere can be investigated and the influence of H⁺ fluxes on the F layer examined.As an example of application of the method a suggestion by Park (1971) about observed night-time enhancements of N_mF2 is examined. He suggested that lowering of the F layer some hours after a magnetic substorm may cause N_mF2 to increase because of increased ion influx from the protonosphere. In the present calculations the Flayer is maintained around a constant height for some time and then abruptly lowered. Under the conditions adopted the resulting increase in downward H⁺ flux is sufficient to maintain N_mF2 against the increased recombination but not to increase N_mF2 significantly. It is emphasised that these results are not conclusive.     

H-implantation in SO2 and CO2 ices

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H⁺, Oⁿ⁺, Sⁿ⁺, etc.), it can concur to the formation of new molecules.Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices.In this work, we describe some experiments of 15-100 keV H⁺ and He⁺ implantation in pure sulfur dioxide (SO₂) at 16 and 80 K and carbon dioxide (CO₂) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H₂CO₃) is formed after H-implantation in CO₂, vice versa H-implantation in SO₂ at both temperatures does not produce measurable quantity of sulfurous acid (H₂SO₃). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO₂ and it is continuously bombarded with H⁺ ions caught in Jupiter's magnetosphere.     

Energy transfer from excited N2 and O2 as a source of O(1S) in the Aurora

It is proposed that energy transfer from excited O₂ contributes to the production of O(¹S) in aurora. An analysis is presented of the OI5577 Å emission in an IBC II⁺ aurora between 90 and 130 km. The volume emission rate of the emission at these altitudes is consistent with the production rate of O(¹S) by energy transfer to O(³P) from N₂ in the A³Σ₂⁺ state and O₂ in the A³Σ_u⁺, C³Δc¹Σ_u^? states, the N₂A state being populated by direct electron impact excitation and B → A cascade and the excited O₂ states by direct excitation. Above the peak emission altitude (~105 km), energy transfer from N₂A is the predominant production mechanism for O(¹S). Below it, the contribution from quenching of the O₂ states becomes significant.     

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

Measured fractional abundances for stratospheric positive ions are reported for the first time. The measurements which were obtained from balloon-borne ion mass spectrometer experiments relied on recent simulation studies of electric field induced cluster ion dissociation conducted at our laboratory.The ion abundance data provide strong support for identifications of the observed ions as H⁺(H₂O)_n and Hx⁺x_L(H₂O)_m proposed previously. Moreover, it is found that x most likely cannot be identified as NaOH or MgOH which implies that gaseous metal compounds do not exist in the middle stratosphere in significant abundances.Implications of the present findings for the composition and chemistry of stratospheric ions as well as for stratospheric aerosols are discussed.     

Measured ion-molecule reaction rates for modelling Titan's atmosphere

Rate coefficients for several two- and three-body ion-molecule reactions involving hydrocarbons have been determined at thermal energies and above using drift tube-mass spectrometer techniques. The measured rates for clustering and breakup reactions involving CH₅⁺ and C₂H₅⁺ ions in methane are found to be strongly temperature dependent in the range from 80 to 240 K. The equilibrium constants determined for these reactions differ somewhat from those of Hiraoka and Kebarle. Rate coefficients for two-body reactions of CH₅⁺, C₂H₅⁺, N⁺, H⁺ and D⁺ ions with methane and/or ethane have been measured. The results indicate that the product yields of several of the fast ion-molecule reactions depend strongly on ion energy (temperature), and therefore previous room-temperature results may be of limited value for model calculations of Titan's atmosphere.     

Ground-based observations of O2 (b1Σ+g−X3Σ−g) atmospheric bands in high latitude auroras

Analysis of observed spectrograms is based on comparison with synthetic spectra. The O₂(b¹Σ⁺_g?X³Σ^?_g Atm. (1,1) band in high latitude auroras observed from the ground is found to be the strongest in the Δv = 0 sequence. It is enhanced with altitude relative to the N₂ 1P(2, 0)and N⁺₂ M(2,0) bands, but the O₂ Atm. (2, 2) band has an unexpected low intensity. The range of rotational temperatures of the O₂ Atm. bands varies from approx. 200 to above 500 K which indicates that the altitude of the centroid of the emission region varies from about 100 km to the F-region. The highest temperature is found in the midday aurora associated with the magnetospheric cusp. Conspicuous relative variations between the intensities of N₂ and O₂ spectra are documented, but a satisfactory explanation of the variety is not given. Deviations of the observed O₂ Atm. band intensities from the vibrational intensity distribution predicted by Franck-Condor factors indicate that the excitation of the O₂ Atm. bands in aurora is not mainly due to particle impact on O₂, and the contribution due to energy transfer from hot O(¹D) atoms has to be found in future research.     

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.     

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.     

The first height measurements of the negative ion composition of the stratosphere

For the first time, height profiles of the stratospheric negative ion composition are presented. The results are from two nights of balloon borne mass spectrometers and cover an altitude range from 23.8 to 38.9 km. Below approx. 30km, NO^?₃ · mHNO₃ ions are dominant. These are replaced by HSO₄^? · nH₂SO₄ · oHNO₃ ions above this height. There are indications that the most abundant ions above 32 km have masses greater than 280 atomic mass units (amu), the instruments' mass range. The fractional ion count rates as a function of altitude are presented and their significance for neutral trace gas analysis and ion sampling is discussed.     

Collisional vibrational quenching of O2+(v) and other molecular ions in planetary atmospheres

New experimental techniques have yielded several thermal energy vibrational quenching rate constants for O₂⁺(v). Rates for quenching of O₂⁺(v = 1) by O₂, N₂, Ar, CO₂, H₂, and CH₄ are 3(?10), 2(?12), 1(?12), 1(?10), 2.5(?12), and 6(?10) cm³s^?1 at 300 K. The quenching is somewhat faster for O₂⁺(v = 2). The triatomic ions CO₂⁺, NO₂⁺, N₂O⁺, SO₂⁺, and H₂O⁺ are all vibrationally deexcited with an efficiency greater than 10^?3 in Ar or Ne collisions. A theoretical rationalization of the experimental results leads to the prediction that vibrational quenching in planetary atmospheres will generally be efficient, k > 1(?12) cm³s^?1 for almost all ion and neutral gas pairs.     

Electronic Sputtering Analysis of Astrophysical Ices

Experimental results on fast ion collision with icy surfaces having astrophysical interest are presented. ²⁵²Cf fission fragments projectiles were used to induce ejection of ionized material from H₂O, CO₂, CO, NH₃, N₂, O₂ and Ar ices; the secondary ions were identified by time-of-flight mass spectrometry. It is observed that all the bombarded frozen gas targets emit cluster ions which have the structure X_nR^±, where X is the neutral ice molecule and R^± is either an atomic or a molecular ion. The shape of the positive or negative ion mass spectra is characterized by a decreasing yield as the emitted ion mass increases and is generally described by the sum of two exponential functions. The positive ion water ice spectrum is dominated by the series (H₂O)_nH₃O⁺ and the negative ion spectrum by the series (H₂O)_nOH⁻ and (H₂O)_nO⁻. The positive ion CO₂ ice spectrum is characterized by R⁺ = C⁺, O⁺, CO⁺, O₂⁺ or CO₂⁺ and the negative one by R⁻ = CO₃⁻. The dominant series for ammonia ice correspond to R⁺ = NH₄⁺ and to R⁻ = NH₂⁻. The oxygen series are better described by (O₃)_nO_m⁺ secondary ions where m = 1, 2 or 3. Two positive ion series exist for N₂ ice: (N₂)_nN₂⁺ and (N₂)_nN⁺. For argon positive secondary ions, only the (Ar)_nAr⁺ series was observed. Most of the detected molecular ions were formed by one-step reactions. Ice temperature was varied from ∼20 K to complete sublimation.     

H3 as a trap for noble gases: 1—The case of Argon

The possibility of H₃⁺ playing a role as a sink for noble gases has been investigated in the case of Argon. Elaborate quantum methods (ab initio Coupled Cluster and density functional BH&HLYP levels of theory) have been shown to reproduce the rotational constants within 0.3% together with the only known IR frequency on the test case of Ar…D₃⁺. Dissociation energies of (Ar)_n…H₃⁺ as a function of cluster size, i.e. 7.2 (n=1), 3.7 (n=2), 3.6 (n=3), 1.6 (n=4), 1.7 (n=5) kcal/mol, follow the pattern established experimentally for (Ar)_n…H₃⁺ and (H₂)_n…H₃⁺ series. Rotational constants and harmonic frequencies of (Ar)_n…H₃⁺ (n=1-3) are presented.     

Relative flow of H+ and O+ ions in the topside ionosphere at mid-latitudes

Theoretical results on the daily variation of O⁺ and H⁺ field-aligned velocities in the topside ionosphere are presented. The results are for an L = 3 magnetic field tube under sunspot minimum conditions at equinox. They come from calculations of time-dependent O⁺ and H⁺ continuity and momentum balance in a magnetic field tube which extends from the lower F2 region to the equatorial plane (Murphy et al., 1976).There are occasions when ion counterstreaming occurs, with the O⁺ velocity upward and H⁺ velocity downward. The conditions causing this counterstreaming are described: the H⁺ layer is descending whilst O⁺ is supplied from below either to increase the O⁺ concentration at fixed heights or to replace O⁺ ions lost by charge exchange with neutral H. It is suggested that the results of observations at Arecibo by Vickrey et al. (1976) of O⁺ and H⁺ concentrations and counterstreaming velocities are significantly affected by $\text{E}\text{×}\text{B}$ drift.     

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.     

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.     

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.     

Effects of ion excitation on charge transfer reactions of the Mars, Venus, and Earth ionospheres

The absolute reaction cross sections and reaction rate coefficients as a function of photoionisation energy for 25 ion-molecule reactions (charge transfer reactions except for one) have been measured between the most abundant species present as ions or neutral in the Mars, Venus and Earth ionospheres: O₂, N₂, NO, CO, Ar and CO₂.This study shows the strong influence of electronic as well as vibrational internal energy on most ion-molecule reactions. In particular endothermic charge transfer reactions are driven by electronic excitation of O₂⁺ and NO⁺ ions in their a⁴Π_u and a³Σ⁺ metastable states, respectively. Moreover, it is shown that lifetimes of these metastable states are sufficient to survive the mean free path in the lowest part of ionospheres and therefore express their enhanced reactivity. The reactions of O₂⁺ with NO as well as the reactions of CO₂⁺ with NO, O₂, CO and to a less extent N₂ are driven by vibrational excitation. N₂⁺ and CO⁺ reactions vary much less with photon energy than the other ones, except for the case of reactions with Ar. The effects of the molecular ion internal energy content on their reactivity must be included in the ionospheric models for most of the reactions investigated in the present work. It is also the case for the effect of collision energy on the CO⁺+M reactions as we expect that a significant proportion of these CO⁺ could be produced with translational energy by dissociation of doubly charged CO₂²⁺, in particular in the Mars ionosphere. Recommended effective rate constant values are given as a function of VUV photon energy.