Mass spectrometer measurements of the positive ion composition in the D- and E-regions of the ionosphere

On 14 December 1971, during the maximum of the Geminid Meteor Shower, the positive ion composition was measured in the D- and E-regions above Sardinia. The payload was launched at 12:11 UT, and measurements were made between 68.5 and 152 km altitude. A magnetic sector type mass spectrometer with dual collector and a liquid helium cryopump was used. The instrument covered the mass range from 11 to 73 AMU and had a resolution at the 1 % level of M/ΔM = 60.In the E-region two distinct metal ion layers were observed, centred at 95 and 119 km, respectively. In the lower layer Fe⁺ and Mg⁺ were the most abundant metal ions, and in the upper layer Si⁺ was dominant. Si⁺ ions were conspicuously absent in the lower layer (Si⁺/Mg⁺ < 2 × 10⁻³). This particular behaviour of Si could be due to the inability of atomic oxygen to reduce SiO, whereas in the upper layer Si⁺ions might be formed directly by the charge rearrangement reaction SiO + O⁺ → Si⁺+ O₂. In addition, Na⁺, Al⁺, K⁺, Ca⁺, Ti⁺, Cr⁺, Ni⁺ and Co⁺ were also identified. The metal oxide ions AlO⁺ and SiO⁺ were detected, and probably also MgO⁺ and SiOH⁺. The concentrations of NO⁺ and O₂⁺ show a deep minimum at the maximum of the lower metal ion layer. A very high neutral metal density of 6 × 10⁷ cm⁻³ would be required to explain this feature as resulting from charge transfer reactions between the molecular and metal ions Such a high metal density is in contradiction to direct measurements and to cosmic dust influx rates. The isotopic ratios of Mg⁺, Si⁺, and of the major isotopes of Fe⁺ and Ni⁺ were measured, some of them with an accuracy of a few per cent (²⁵Mg⁺/²⁴Mg⁺ = 0.124 ± 0.006; ²⁶Mg⁺/²⁴Mg⁺ = 0.139 ± 0.008; ²⁹Si⁺/²⁸Si⁺ = 0.050 ± 0.004; ⁵⁴Fe⁺/⁵⁶Fe⁺ = 0.069 ± 0.005; ⁵⁷Fe⁺/⁵⁶Fe⁺ = 0.029 ± 0.004; ⁶⁰Ni⁺/⁵⁸Ni⁺ = 0.31 ± 0.12). The isotopic ratios agree within the experimental errors with the corresponding terrestrial ratios, thus giving evidence that these elements have the same isotopic composition in the Geminid meteors as in the Earth's crust, in chrondrites, and in lunar material.In the D-region the ions Na⁺H₂O, Na⁺(H₂O)₂, NaO⁺ and NaOH⁺ were tentatively identified. Below 95 km altitude the relative abundances of the ions 32⁺, 33⁺ and 34⁺ deviate from the values expected for molecular oxygen isotopes. Their abundances can not be explained by the presence of S-ions only, and we conclude that HO₂⁺ and H₂O₂⁺ are present.The ion density profiles of the major D-region constituents show some remarkable deviations from typical D-region conditions. These deviations are related to the winter anomaly in ionospheric absorption observed over Spain during the launch day, and our data represent the first ion composition measurements during such conditions. In particular, H⁺(H₂O)₂ is the major ion only up to 77 km, and at 80 km altitude the NO⁺ concentration exceeds the total water cluster ion density by almost two orders of magnitude. An increase of the mesospheric NO, O₃ and O concentrations as well as of the O/H₂O ratio could explain the observed ion profiles. The low NO⁺/O₂⁺ ratios of approximately unity measured in the E-region are in agreement with a strong downward transport of NO and/or O into the mesosphere during the launch day. A simple four-ion model was used to interpret our D-region data. The calculated neutral NO concentration increases from about 2 × 10⁷ cm⁻³ at 85 km to 5 × 10⁷ cm⁻³ at 80 km. In addition, evidence for an increased O₂⁺ production rate above 83 km was found, probably due to an enhanced O₃ concentration. We conclude that our data strongly support vertical transport of minor neutral consituents as cause of the winter anomaly.     

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.     

Observations of solar wind stream with high abundance of heavy ions and relation with coronal conditions

Long intervals, during which heavy ions were detected in the high energy tail of the energy spectra of solar wind ions, were recorded by the plasma spectrometer SCS onboard the Prognoz-7 satellite. In particular, such a region with unusual features—low velocity, high density, low temperature of protons and, especially, low temperature of α-particles—was observed during 10–13 December 1978. The time dependence of these parameters makes it possible to recognize this event as “noncompressive density enhancement”. In this region heavy ions such as O⁺⁶, O⁺⁷, Si⁺⁷, Si⁺⁸, Si⁺⁹ and a group of iron from Fe⁺⁶ to Fe⁺¹³ were identified by the electrostatic analyzer.The abundance of these ions relative to protons was about ten times higher than had previously been observed. The coronal temperature, estimated from the ratios of the ion fluxes with different ionization states, is higher than that estimated earlier for the oxygen ions.     

Measurements of positive ion conversion and removal reactions relating to the Jovian ionosphere

Measured rates are presented for the reaction of He⁺ ions with H₂ (and D₂) molecules to form H⁺, H₂⁺, and HeH⁺ ions, as well as for the subsequent reactions of H⁺ and HeH⁺ ions with H₂ to form H₃⁺. The neutralization of H₃⁺ (and H₅⁺) ions by dissociative recombination with electrons is shown to be fast. The reaction He⁺ + H₂ is slow (k = 1.1 × 10^?13 cm³/sec at300°K) and produces principally H⁺ by the dissociative charge transfer branch. It is concluded that there may be a serious bottleneck in the conversion of two of the primary ions of the upper Jovian ionosphere, H⁺ and He⁺ (which recombine slowly), to the rapidly recombining H₃⁺ ion (α[H₃⁺]?3.4 × 10^?7 cm³/sec at 150°K).     

X-Ray Emission from Comet McNaught-Hartley (C/1999 T1)

Comet McNaught-Hartley was observed in five 1-h exposures on January 8-14 2001 using the advanced CCD imaging spectrometer on board the Chandra X-ray Observatory. The X-ray image of the comet does not show a crescent-like shape. The brightest region is offset from the nucleus between the sunward and comet velocity directions. The comet mean X-ray luminosity is equal to 7.8×10¹⁵ erg s⁻¹ for photon energy E>150 eV and aperture ρ=1.5×10⁵ km where the comet X-ray brightness exceeds 20% of the peak value. Gas production rate was 10²⁹ s⁻¹ during the observations, and the efficiency of X-ray excitation was equal to 4×10⁻¹⁴ erg AU^3/2. Day-to-day variations in X-rays reached a factor of 5. The strongest short-term variation was by a factor of 1.75 for 1600 s. This variation may be explained by a decline in the solar-wind flux by the same factor in ≈800 s. The comet and Earth were seeing different faces of the Sun, and time delay in the solar-wind events on the Earth and the comet was long, equal to 6 days. The best correlation between the comet X-ray luminosity and the solar-wind proton density is for the time delay of 5.5 days and may be explained by the higher velocity of heavy ions.Careful background subtraction made it possible to extract the comet spectrum from 150 to 1000 eV. No signal was detected at E>1000 eV, and a 3σ upper limit to any emission with E>1000 eV is 0.3% of the photon emission at 150-1000 eV. The best χ²-fit model to the spectrum consists of nine narrow emission features. The emission energies and intensities are in good agreement with a charge exchange spectrum calculated by us for the slow solar wind. Using this spectrum, we identify the observed emissions as (Ne⁷⁺+Mg⁷⁺+Mg⁸⁺) at 195 eV, (Mg⁸⁺+Mg⁹⁺+Si⁸⁺) at 250 eV, C⁵⁺ at 370 and 460 eV, O⁶⁺ at 560 eV, O⁷⁺ at 650, 780, and 840 eV, and Ne⁸⁺ at 940 eV. X-ray spectroscopy of comets may be used to diagnose the solar-wind composition and its interaction with comets.     

Druse clinopyroxene in D'Orbigny angritic meteorite studied by single‐crystal X‐ray diffraction,electron microprobe analysis,and Mössbauer spectroscopy

Abstract— The crystal structure of druse clinopyroxene from the D'Orbigny angrite, (Ca_0.944 Fe²⁺_0.042 Mg_0.010Mn_0.004) (Mg_0.469Fe²⁺_0.317Fe³⁺_0.035Al_0.125Cr_0.010Ti_0.044) (Si_1.742Al_0.258) O₆, a = 9.7684(2), b = 8.9124(2), c = 5.2859(1) Å, β = 105.903(1)°, V = 442.58 ų, space group C2/c, Z = 2, has been refined to an R₁ index of 1.92% using single‐crystal X‐ray diffraction data. The unit formula, calculated from electron microprobe analysis, and the refined site scattering values were used to assign site populations. The distribution of Fe²⁺and Mg over the M1 and M2 sites suggests a closure temperature of 1000 °C. Mössbauer spectroscopy measurements were done at room temperature on a single crystal and a powdered sample. The spectra are adequately fit by a Voigt‐based quadrupole‐splitting distribution model having two generalized sites, one for Fe²⁺with two Gaussian components and one for Fe³⁺with one Gaussian component. The two ferrous components are assigned to Fe²⁺at the M1 site, and arise from two different next‐nearest‐neighbor configurations of Ca and Fe cations at the M2 site: (3Ca,0Fe) and (2Ca,1Fe). The Fe³⁺/Fe_tot ratio determined by Mössbauer spectroscopy is in agreement with that calculated from the electron microprobe analysis. The results are discussed in connection with the redox and thermal history of D'Orbigny.     

Ionic and neutral concentrations of Mg and Fe near 92 km

Lidar observations of atmospheric sodium reveal a diurnally steady layer with a maximum concentration near 92 km of 3?5 × 10³cm^?3. These data imply that both Fe and Mg should have peak concentrations near 10⁵ cm^?3 on the basis of their relative abundance to sodium in chondritic meteorites. We review the available metallic ion data below 100 km and find typical maxima of 10² cm^?3 for Na and 10³ cm^?3 for both [Fe⁺] and [Mg⁺] for undisturbed daytime conditions. We argue that enhancements of up to 10⁴ cm^?3 for Fe⁺ and Mg⁺ during aurora support the viewpoint that [Fe] and [Mg] both approach 10⁵ cm^?3 near 92 km. We briefly discuss the lack of spectroscopic evidence for such concentrations. In our review of the metallic ion data we find evidence for about a factor of ten diurnal variation in both Fe⁺ and Mg⁺ and probably Na⁺. Minimum concentrations of 10² cm^?3 are attained just before dawn for [Fe⁺] and [Mg⁺].     

On the simultaneous ionization-excitation of the OII(λ834 Å) resonance transition by electron impact on atomic oxygen

Laboratory cross-section data on the excitation of the OII(2s 2p⁴⁴P → 2s² 2p³⁴S; λ834 Å) resonance transition and on the production of O⁺ and O²⁺ ions by electron impact on atomic oxygen are used to show that the ratio $\text{σ(λ834}\text{A}\text{?}\text{)}\text{σ(O}{}^{\mathrm{+}}\text{+ O}{}^{\mathrm{2+}}\text{)}$ is nearly constant for incident electron energies > 50 eV. Under auroral conditions, the total electron-ion pair production rate from electron impact on O can be inferred from λ834 Å volume emission rate measurements using the result that $\text{η(O}{}^{\mathrm{+}}\text{+ O}{}^{\mathrm{2+}}\text{)}\text{\$}\text{?}\text{8.4η(λ834}\text{A}\text{?}\text{)}$. These findings, along with earlier work on the simultaneous ionization-excitation of the 1 Neg (0,0) band of N₂⁺ and the 1 Neg (1, 0) band of O⁺₂, allow the specific ionization rates for the principal atmospheric constituents (O⁺, O⁺₂, N⁺₂), for the multiply-ionized species (O²⁺, O²⁺₂, N²⁺₂), and for the dissociatively produced atomic ions to be inferred in aurora from remote satellite observations.     

Mars: Photodesorption from mineral surfaces and its effects on atmospheric stability

A mechanism has been proposed for uv-accelerated desorption from Fe²⁺ sites on mineral surfaces that satisfies kinetic constraints determined in the laboratory by Huguenin. The process is an integral step of the photochemical weathering mechanism for producing dust on Mars, and it now appears that it may play primary roles in stabilizing CO₂ against dissociation by sunlight and in controlling the oxidation state of the atmosphere. We propose that adsorption occurs at octahedrally coordinated Fe²⁺ surface sites to form seven-coordinate transition-state complexes. These complexes acquire 16–18 kcal mole^?1 of ligand field stabilization energy. During illumination (λ ≤ 0.35 μm), electrons are photoemitted from the surfaced Fe²⁺, temporarily oxidizing them to Fe³⁺. Fe³⁺ has no ligand field stabilization energy, and the complexes lose 16–18 kcal mole^?1 of stabilization energy. This is a large fraction of the 19- to 28-kcal mole^?1 activation energy for dissociating the complexes, and desorption should proceed spontaneously. The gases that were observed to undergo adsorption-photodesorption include O₂, CO₂, CO, H₂O, N₂, and Ar. Photodesorption can drive several catalytic reactions, one of which is the oxidation of CO to CO₂. The rate of this reaction should be limited by the supply of CO and O₂ to the surface to ～2 × 10¹² cm^?2 sec^?1 (column photodissociation rate of CO₂). By including this surface reaction in models of Martian atmospheric CO₂ chemistry, CO₂ can be stabilized against photodissociation with eddy diffusion coefficients of only 3 × 10⁵?1 × 10⁷ cm² sec^?1 below 40 km, raising to ～ 10⁹ cm² sec^?1 at 140 km. Odd hydrogen is not needed to catalyze the oxidation of CO below 40 km, and odd hydrogen mixing ratios need only to be $\text{f}{}_{\mathrm{<mtext>H</mtext>}}\text{? 10}{}^{\mathrm{?10}}$ to depress ozone concentrations below the observed upper limit in equatorial regions. Another catalytic reaction that should be driven by photodesorption on Mars is $\text{20}\text{H}{}^{\mathrm{?}}{}_{\mathrm{<mtext>(</mtext><mtext>ads</mtext><mtext>)</mtext>}}\text{→}\text{H}{}_2\text{O}\text{+}\text{1}\text{2}\text{O}{}_{\mathrm{2(g)}}\text{+ 2e}{}^{\mathrm{?}}{}_{\mathrm{<mtext>crystal</mtext>}}$. This is an important source of atmospheric O₂, amounting to 7 × 10¹³?2 × 10¹⁷ O₂ molecules cm^?2 yr^?1, and it could have a significant effect on atmospheric oxidation state.     

Mutual neutralization rates of ionospherically important ions

Following our recently published measurements of the rate coefficients for mutual neutralization, α, of the ionospherically important reactions NO⁺ + NO₂^?(α₁) and NO⁺ + NO₃^?(α₂) carried out in ion-ion flowing afterglow plasmas at 300 K, we have determined the mutual neutralization rates for the water cluster ion H₃O⁺ · (H₂O)₃ with a mixture of several negative ions which are known to exist in the D region. The α coefficients for these cluster ion reactions do not differ significantly from alpha;₁ and α₂, all of these reactions having α ?6 × 10^?8 cm³/sec which is significantly smaller than values usually adopted in ionospheric calculations. Current information on the ionic composition of the D region and the implications of the present results to de-ionization rate calculations are discussed.     

On the properties of O and O2 ions in a hybrid model and in Mars Express IMA/ASPERA-3 data: A case study

We have performed a numerical simulation to analyze the energy spectra of escaping planetary O⁺ and O₂⁺ ions at Mars. The simulated time-energy spectrograms were generated along orbit no. 555 (June 27, 2004) of Mars Express when its Ion Mass Analyzer (IMA)/ASPERA-3 ion instrument detected escaping planetary ions. The simulated time-energy spectrograms are in general agreement with the hypothesis that planetary O⁺ and O₂⁺ ions far from Mars are accelerated by the convective electric field. The HYB-Mars hybrid model simulation also shows that O⁺ ions originating from the ionized hot oxygen corona result in a high-energy (E>1 keV) O⁺ ion population that exists very close to Mars. In addition, the simulation also results in a low-energy (E<0.1 keV) planetary ion population near the pericenter. In the analyzed orbit, IMA did not observe a clear high-energy planetary ion or a clear low-energy planetary ion population near Mars. One possible source for this discrepancy may be the Martian magnetic crustal anomalies because MEX passed over a strong crustal field region near the pericenter, but the hybrid model does not include the magnetic crustal anomalies.     

Ionospheric composition in SAR-arcs

The high electron temperatures existing within SAR-arcs can result in enhanced vibrational excitation of atmospheric N₂ molecules and, as a consequence, increase the rate coefficient of the reaction, O⁺ + N₂ → NO⁺ + N. This results in a change in the relative abundance of O⁺ and NO⁺+ in the SAR-arc region compared with that in the undisturbed ionosphere. Theoretical ion density profiles were computed by a triple ion analysis solving the mass, momentum and energy equations for O⁺, NO⁺ and O⁺₂ ions self-consistently. Although the electron temperature dependence of the recombination rate of NO⁺ is not well known, the results show that for a range of expected recombination rates NO⁺ still remains the dominant ion up to ca. 320 km at night within a bright SAR-arc. Studies were also made of the relative importance of a downward O⁺ flux and an upward ion drift in maintaining the F-region under SAR-arc conditions. It was found that the upward drift caused a marked increase in the NO⁺/O⁺ transition altitude as high as 460 km at night. However, for typical drift speeds up to 50 m sec^?1 the peak electron density was lower than experimental observations. The effect of a large, short-duration perpendicular electric field on the SAR-arc ion and electron density profiles was found to be small. In all cases considered the magnitude of the enhanced NO⁺ density as a result of vibrationally excited N₂ molecules was sufficient to prevent the electron density within the night-time SAR-arc from becoming vanishingly small.     

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.     

Ion composition in the E- and lower F- region above kiruna during sunset and sunrise

A magnetic type mass spectrometer has been flown on two ESRO sounding rockets from ESRANGE (Kiruna 68°N) on February 25 and 26, 1970. The first launch was at sunset (16:33 UT) and the second the next morning, during sunrise (04:47 UT). For both flights the solar zenith angle was approximately 98°. The instrument was measuring simultaneously the neutral gas and positive ion composition and the total ion density. In this paper the results of the ion composition measurements are presented. For both flights the main ion constituents measured between approximately 110–220 km were O⁺, NO⁺ and O₂⁺. Only at sunset were N⁺ and N₂⁺ detected above 200 km. In spite of the identical solar UV-radiation, pronounced sunset/sunrise variations in the positive ion composition were found. The total ion densities at sunrise were between 5×10³ and 5 × 10⁴ ions cm^?3 and therefore too high to be explained without a night-time ionization by precipitated particles. At sunrise the NO⁺ and O₂⁺ profiles show a correlated wavelike structure with three pronounced almost equally spaced layers in the E-region. Only the highest layer is present in the O⁺ profile. Locally enhanced field aligned ionization originated by particle precipitation and an E × B instability are the most likely source for this structure. In the E- and lower F-regions the $\text{NO}{}^{\mathrm{+}}\text{O}{}_2{}^{\mathrm{+}}$ ration increased overnight from values around 7 at sunset to 15 at sunrise, correlated with an increase of the local magnetic activity index K from 0⁺ to 2°. This could be explained if the NO density and magnetic activity are correlated.     

Theoretical ion densities in the lower ionosphere

We have solved the coupled momentum and continuity equations for NO⁺, O₂⁺, and O⁺ions in the E- and F-regions of the ionosphere. This theoretical model has enabled us to examine the relative importance of various processes that affect molecular ion densities. We find that transport processes are not important during the day; the molecular ions are in chemical equilibrium at all altitudes. At night, however, both diffusion and vertical drifts induced by winds or electric fields are important in determining molecular ion densities below about 200 km. Molecular ion densities are insensitive to the O⁺ density distribution and so are little affected by decay of the nocturnal F-region or by processes, such as a protonospheric flux, that retard this decay. The O⁺ density profile, on the other hand, is insensitive to molecular ion densities, although the O⁺ diffusion equation is formally coupled to molecular ion densities by the polarization electrostatic field. Nitric oxide plays an important role in determining the NO⁺ to O₂⁺ ratio in the E-region, particularly at night. Nocturnal sources of ionization are required to maintain the E-region through the night. Vertical velocities induced by expansion and contraction of the neutral atmosphere are too small to affect ion densities at any altitude.     

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.     

Evidence for excited states of CO3−1 and NO3−1 from collisional dissociation processes

Excitation functions for collision-induced dissociation reactions of CO ₃^? and NO₃^? to give O^? and the corresponding neutral species have been studied using an in-line tandem mass spectrometer. When these ions were prepared from certain gaseous mixtures, larger cross-sections and lower thresholds were observed for the dissociation processes than those found for the same ions in their apparent ground states. These observations suggest the existence of long-lived excited states of CO₃^?1 and NO₃^?1. The heats of formation of these excited ionic states were determined to be ?4.8 ± 0.1 and ?0.3 ± 0.2 eV for CO₃^?1 and NO₃^?1, respectively. Possible implications of these findings with respect to the D -region negative ion reaction scheme are discussed.     

The dissociative recombination of N2+ (v = 0, 1) as a source of metastable atoms in planetary atmospheres

The yield of metastable nitrogen atoms in dissociative recombination of N₂⁺ (v = 0, 1)ions has been tudied for different experimental conditions. In a first experiment, the branching ratio for N(²D) production was directly measured as being higher than 1.85; for N₂⁺ (v = 0) this implies that ²D + ²D is the main reaction channel; for N₂⁺ (v = 1) a minor channel could be ²P + ²D, ²P being then quenched toward ²D by electrons. In a second experiment, at higher electron densities, the influence of superelastic collisions was studied; a steady state analysis yields the quenching rate coefficient k₄, of ²D towards ⁴S equal to 2.4 × 10^?10 cm³ s^?1for T_e = 3900 K and shows that ²D + ²D is always the major channel of the reaction for N₂⁺ (v = 1), ²D + ²P being a minor channel. All these results are in good agreement with thermospheric models but imply that N₂⁺ dissociative recombination is a less important source for nitrogen escape of Mars.     

Maohokite,a post‐spinel polymorph of MgFe2O4 in shocked gneiss from the Xiuyan crater in China

Maohokite, a post‐spinel polymorph of MgFe₂O₄, was found in shocked gneiss from the Xiuyan crater in China. Maohokite in shocked gneiss coexists with diamond, reidite, TiO₂‐II, as well as diaplectic glasses of quartz and feldspar. Maohokite occurs as nano‐sized crystallites. The empirical formula is (Mg_0.62Fe_0.35Mn_0.03)²⁺Fe³⁺₂O₄. In situ synchrotron X‐ray microdiffraction established maohokite to be orthorhombic with the CaFe₂O₄‐type structure. The cell parameters are a = 8.907 (1) Å, b = 9.937(8) Å, c = 2.981(1) Å; V = 263.8 (3) ų; space group Pnma. The calculated density of maohokite is 5.33 g cm^?3. Maohokite was formed from subsolidus decomposition of ankerite Ca(Fe²⁺,Mg)(CO₃)₂ via a self‐oxidation‐reduction reaction at impact pressure and temperature of 25–45 GPa and 800–900 °C. The formation of maohokite provides a unique example for decomposition of Fe‐Mg carbonate under shock‐induced high pressure and high temperature. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2017‐047). The mineral was named maohokite after Hokwang Mao, a staff scientist at the Geophysical Laboratory, Carnegie Institution of Washington, for his great contribution to high pressure research.     

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.