Temperature and solar zenith angle control of D-region positive ion chemistry

A numerical model is utilized to investigate the temperature (T) and solar zenith angle (χ) control of D-region positive ion chemistry between 75 and 90 km. It is assumed that NO^? is the precursor ion in a chain which involves three-body formation of the intermediary cluster ions NO⁺(H₂O)_m?1(X) (m = 1–3), where X can be N₂,O₂, H₂O, or CO₂, switching reactions which convert these weakly bound clusters to hydrates of NO⁺ and reaction of the third hydrate of NO⁺ with H₂O to initiate the chain to form H⁺(H₂O)_n (n = 1–7). Zonal mean and tidal temperatures from rocket observations and theory are synthesized to obtain the best available estimate of mean latitudinal, seasonal and local time variations of temperature in this height region. Relative compositions of NO⁺(H₂O)_m and H⁺(H₂O)_n are found to vary widely over the complete range of realistic conditions; however, the relative ion populations are entirely explicable in terms of the effects of χ and T on the relative life-times of the intermediary ion clusters with respect to recombination, switching and thermal decomposition. For instance, as χ increases (and electron production decreases) beyond 60° for a given temperature, the recombination times of the intermediate ion cluster species lengthen with respect to the formation time of the H⁺ water clusters, causing the relative H⁺ water cluster population to increase and thus raise the level where the cluster ion and NO⁺ concentrations are equal from about 85 km (normal midday) to 90 km. For a given χ the concentrations of NO⁺H₂O and H⁺(H₂O)₄ increase (decrease) for temperatures less than (greater than) 190 and 205 K, respectively. The transition occurs when the temperature becomes sufficiently high that the lifetimes of intermediary ion clusters with respect to thermal decomposition become less than their lifetimes with respect to H₂O switching (which ultimately leads to the third hydrate of NO⁺ and entry into the water chain). At this point, the formation time of H⁺(H₂O)₄ becomes long compared with its lifetime with respect to thermal decomposition and its relative concentration decreases also. Implications of these results with respect to studies of the D-region are discussed.     

The evolution of charged particles in a model of contracting cloud

The evolution of the charged particles are followed during contraction of a model of an interstellar cloud, with initial density number of n = 10 cm^–3. The contraction is followed up to density increase by five orders of magnitude. Special care is given to the details of the negative ions. In addition, we have tested the ambipolar diffusion according to the results of the ion density.The results predict the importance of atomic ions in the diffuse regions. H⁺ and C⁺ are distinctly enhanced in the beginning of contraction but decrease as contraction proceeds. Molecular ions enhance as contraction proceeds and becomes important in dense regions. The most enhanced molecular ions are HCO⁺, O₂ ⁺, C₂H₃ ⁺, H₃O⁺ and SO⁺, H₃ ⁺ is less abundant. The atomic ions (except metalic ions) decrease noticeably as density increases. In general the negative ions are of negligible fractional abundances. It has also been found that the time of ambipolar diffusion is shorter than the dynamical time, hence the magnetic field should be weakened in the central core as the central density increases to n = 10⁴ cm^–3.     

Carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter from the Murchison meteorite

Abstract— Low molecular weight monocarboxylic acids, including acetic acid, are some of the most abundant organic compounds in carbonaceous chondrites. So far, the ¹³C‐ and D‐enriched signature of water‐extractable carboxylic acids has implied an interstellar contribution to their origin. However, it also has been proposed that monocarboxylic acids could be formed by aqueous reaction on the meteorite parent body. In this study, we conducted hydrous pyrolysis of macromolecular organic matter purified from the Murchison meteorite (CM2) to examine the generation of monocarboxylic acids with their stable carbon isotope measurement. During hydrous pyrolysis of macromolecular organic matter at 270–330 °C, monocarboxylic acids with carbon numbers ranging from 2 (C₂) to 5 (C₅) were detected, acetic acid (CH₃COOH; C₂) being the most abundant. The concentration of the generated acetic acid increased with increasing reaction temperature; up to 0.48 mmol acetic acid/g macromolecular organic matter at 330 °C. This result indicates that the Murchison macromolecule has a potential to generate at least ?0.4 mg acetic acid/g meteorite, which is about four times higher than the amount of water‐extractable acetic acid reported from Murchison. The carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter is ?‐27‰ (versus PDB), which is much more depleted in ¹³C than the water‐extractable acetic acid reported from Murchison. Intramolecular carbon isotope distribution shows that methyl (CH₃‐)‐C is more enriched in ¹³C relative to carboxyl (‐COOH)‐C, indicating a kinetic process for this formation. Although the experimental condition of this study (i.e., 270–330 °C for 72 h) may not simulate a reaction condition on parent bodies of carbonaceous chondrite, it may be possible to generate monocarboxylic acids at lower temperatures for a longer period of time.     

Identification of C4H5, C4H4, C3H3 and CH3 radicals produced from the reaction of atomic carbon with propene: Implications for the atmospheres of Titan and giant planets and for the interstellar medium

We observed the products C₄H₅, C₄H₄, C₃H₃ and CH₃ of the C(³P) + C₃H₆ reaction using product time-of-flight spectroscopy and selective photoionization. The identified species arise from the product channels C₄H₅ + H, C₄H₄ + 2H and C₃H₃ + CH₃. Product isomers were identified via measurements of photoionization spectra and calculations of adiabatic ionization energy. Product C₄H₅ probably involves three isomers HCCCHCH₃, H₂CCCCH₃ and H₂CCCHCH₂. In contrast, products C₄H₄ and C₃H₃ involve exclusively HCCCHCH₂ and H₂CCCH, respectively. Reaction mechanisms are unraveled with crossed-beam experiments and quantum-chemical calculations. The ³P carbon atom attacks the π orbital of propene (C₃H₆) to form a cyclic complex c-H₂C(C)CHCH₃ that rapidly opens the ring to form H₂CCCHCH₃ followed by decomposition to HCCCHCH₃/H₂CCCCH₃/H₂CCCHCH₂ + H and H₂CCCH + CH₃; the corresponding branching ratios are 7:5:10:78 predicted with RRKM calculations at collision energy 4 kcal mol^?1. Nascent C₄H₅ with enough internal energy further decomposes to HCCCHCH₂ + H. Ratios of products C₄H₅, C₄H₄ and C₃H₃ are experimentally evaluated to be 17:8:75. This work provides a comprehensive look at product channels of the title reaction and gives implications for the formation of hydrocarbons in extra-terrestrial environments such as Titan and carbon-rich interstellar media. We suggest that the title reaction, hitherto excluded in any chemical networks, needs to be taken into account at least in the atmosphere of Titan and carbon-rich molecular clouds where rapid neutral–neutral reactions are dominant and carbon atoms and propene are abundant.     

Elemental and isotope behavior of macromolecular organic matter from CM chondrites during hydrous pyrolysis

Abstract— A new insight into carbon and hydrogen isotope variations of insoluble organic matter (IOM) is provided from seven CM chondrites, including Murchison and six Antarctic meteorites (Y‐791198, Y‐793321, A‐881280, A‐881334, A‐881458 and B‐7904) as well as Murchison IOM residues after hydrous pyrolysis at 270–330 °C for 72 h. Isotopic compositions of bulk carbon (δ¹³C_bulk) and hydrogen (δD) of the seven IOMs vary widely, ranging from ?15.1 to ?7.6%₀ and +133 to +986%₀, respectively. Intramolecular carboxyl carbon (δ13C_COOH) is more enriched in ¹³C by 7.5. 11%₀ than bulk carbon. After hydrous pyrolysis of Murchison IOM at 330 °C, H/C ratio, δ13C_bulk, δ13C_COOH, and δD values decrease by up to 0.31, 3.5%₀, 5.5%₀, and 961%₀, respectively. The O/C ratio increases from 0.22 to 0.46 at 270 °C and to 0.25 at 300 °C, and decreases to 0.10 at 330 °C. δ13C_bulk‐δD cross plot of Murchison IOM and its pyrolysis residues shows an isotopic sequence. Of the six Antarctic IOMs, A‐881280, A‐881458, Y‐791198 and B‐7904 lie on or near the isotopic sequence depending on the degree of hydrous and/or thermal alteration, while A‐881334 and Y‐793321 consist of another distinct isotope group. A δ13C_bulk‐δ13C_COOH cross‐plot of IOMs, including Murchison pyrolysis residues, has a positive correlation between them, implying that the oxidation process to produce carboxyls is similar among all IOMs. These isotope distributions reflect various degree of alteration on the meteorite parent bodies and/or difference in original isotopic compositions before the parent body processes.     

The production of water-cluster positive ions in the quiet daytime D region

In the quiet daytime D region, the primary positive-ion species is thought to be NO⁺, produced by solar Lyman-alpha ionization of NO. Below the altitude of the mesopause, however, the dominant ambient species observed are water-cluster ions of the general type H⁺(H₂O)_n. No satisfactory reaction scheme for producing these cluster ions from NO⁺ has yet been proposed. Following earlier suggestions, a model calculation has been carried out in which successive hydrations of NO⁺ take place through clustering with N₂ and CO₂, followed by “switching” reactions with H₂O. The third hydrate of NO⁺ is then converted into the water-cluster species H⁺(H₂O)₃, and the other water-cluster species are produced by successive clustering and thermal breakup reactions. Many of the reactions involved have not been measured in the laboratory, but reasonable estimates of their rates can be made on the basis of existing measurements of other species. Since both temperature and water-vapor content are of major importance in the model, calculations were carried out for two temperature profiles and two water-vapor profiles. It is shown that the results are in reasonably good agreement with observations as far as the water-cluster species are concerned. Under low-temperature conditions, the model predicts relatively large concentrations of various clusters of NO⁺, in agreement with some observations but in disagreement with others. The importance of sampling breakup of these weakly bound clusters, and their relevance to the free electron concentrations are discussed.     

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.     

Formation of CmSn compounds by photopolymerization of CS2 in the atmosphere of Jupiter

Abstract— Toluene extracts from two (CS_n)_x photopolymers were examined with high‐performance liquid chromatography (HPLC), matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, particle‐induced x‐ray emission (PIXE), and ¹²C(d,p)¹³C nuclear microprobing. the extracts contained elemental s and at least from 17 to 20 distinct c_ms_n compounds with m/z less than ～500 amu. Whereas H₂S is the dominant S‐bearing compound of the normal jovian atmosphere, elemental S, CS, and CS₂ were observed at Shoemaker‐Levy 9 cometary impact sites and at altitudes of the transiently disturbed jovian atmosphere where photodissociation and photopolymerization occur. It is uncertain whether the CS₂ molecular densities were sufficiently large for both to occur, but photopolymerization could have occurred during larger impacts of Jupiter's history. Because the known stable C_mS_n compounds are yellow, orange and deep red, they could contribute significantly to the colors of the jovian clouds.     

Radial distribution of production rates, loss rates and densities corresponding to ion masses ?40 amu in the inner coma of Comet Halley: Composition and chemistry

In this paper we have studied the chemistry of C, H, N, O, and S compounds corresponding to ions of masses ?40 amu in the inner coma of the Comet 1P/Halley. The production rates, loss rates, and ion mass densities are calculated using the Analytical Yield Spectrum approach and solving coupled continuity equation controlled by the steady state photochemical equilibrium condition. The primary ionization sources in the model are solar EUV photons, photoelectrons, and auroral electrons of the solar wind origin. The chemical model couples ion-neutral, electron-neutral, photon-neutral and electron-ion reactions among ions, neutrals, electrons, and photons through over 600 chemical reactions. Of the 46 ions considered in the model the chemistry of 24 important ions (viz., CH₃OH⁺₂, H₃CO⁺, NH⁺₄, H₃S⁺, H₂CN⁺, H₂O⁺, NH⁺₃, CO⁺, C₃H⁺₃, OH⁺, H₃O⁺, CH₃OH⁺, C₃H⁺₄, C₂H⁺₂, C₂H⁺, HCO⁺, S⁺, CH⁺₃, H₂S⁺, O⁺, C⁺, CH⁺₄, C⁺₂, and O⁺₂) are discussed in this paper. At radial distances <1000 km, the electron density is mainly controlled by 6 ions, viz., NH⁺₄, H₃O⁺, CH₃OH⁺₂, H₃S⁺, H₂CN⁺, and H₂O⁺, in the decreasing order of their relative contribution. However, at distances >1000 km, the 6 major ions are H₃O⁺, CH₃OH⁺₂, H₂O⁺, H₃CO⁺, C₂H⁺₂, and NH⁺₄; along with ions CO⁺, OH⁺, and HCO⁺, whose importance increases with further increase in the radial distance. It is found that at radial distances greater than ∼1000 km (±500 km) the major chemical processes that govern the production and loss of several of the important ions in the inner coma are different from those that dominate at distances below this value. The importance of photoelectron impact ionization, and the relative contributions of solar EUV, and auroral and photoelectron ionization sources in the inner coma are clearly revealed by the present study. The calculated ion mass densities are compared with the Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500, 3500, and 6000 km. There is a reasonable agreement between the model calculation and the Giotto measurements. The nine major peaks in the IMS spectra between masses 10 and 40 amu are reproduced fairly well by the model within a factor of two inside the ionopause. We have presented simple formulae for calculating densities of the nine major ions, which contribute to the nine major peaks in the IMS spectra, throughout the inner coma that will be useful in estimating their densities without running the complex chemical models.     

Complexly zoned chromium‐aluminum spinel found in situ in the Allende meteorite

Abstract— In addition to the Mg‐, Al‐, ¹⁶O‐rich spinels that are known to occur in refractory inclusions, the Murchison meteorite contains Cr‐rich, ¹⁶O‐poor spinels, most of whose sources are unknown because they are rarely found in situ. Here we report the in situ occurrence in Allende of Cr‐rich spinels, found in 13 chondrules and 4 “olivine‐rich objects”. The Allende spinels exhibit major and minor element contents, isotopic compositions, and zoning of Cr₂O₃ contents like those of the Cr‐spinels from Murchison. Some chondrules contain patchy‐zoned spinel (Simon et al., 1994), which suggests that such grains did not form by sintering but perhaps by formation of overgrowths on relic grains. Unlike the olivine‐rich objects, phases in all three chondrules that were analyzed by ion microprobe have uniform, near‐normal O‐isotopic compositions. One olivine‐rich object, ALSP1, has a huge (1 mm) fragment of chevron‐zoned spinel. This spinel has near‐normal O‐isotopic compositions that are quite distinct from those of adjacent forsteritic olivine, which are relatively ¹⁶O‐rich and plot on the calcium‐aluminum‐inclusion (CAI) line, like some isolated forsterite grains found in Allende. The spinel and olivine in this object are therefore not genetically related to each other. Another olivine‐rich object, ALSP11A, contains a rectangular, 150 ×s 100 μm, homogeneous spinel grain with 50 wt% Cr₂O₃ and 23 wt% FeO in a vuggy aggregate of finer‐grained (5–90 μm), FeO‐rich (Fo_47–55) olivine. The magnesian core of one olivine grain has a somewhat ¹⁶O‐rich isotopic composition like that of the large spinel, whereas the FeO‐rich olivine is relatively ¹⁶O‐poor. The composition of the spinel in ALSP11A plots on the CAI line, the first Cr‐rich spinel found to do so. Chevron‐zoned spinel has not been observed in chondrules, and it is unlikely that either ALSP1 or ALSP11A were ever molten. Calculations show that a spinel with the composition of that in ALSP1 can condense at 1780 K at a P^tot of 10^?3 atm and a dust/gas ratio of 100 relative to solar. The Cr‐rich spinel in ALSP11A could condense at ～1420 K, but this would require a dust/gas enrichment of 1000 relative to solar. The data presented here confirm that, as in Murchison, the coarse Cr‐rich spinels in Allende are relatively ¹⁶O‐depleted and are isotopically distinct from the ¹⁶O‐enriched MgAl₂O₄ from CAIs. Sample ALSP11A may represent a third population, one that is Cr‐rich and plots on the CAI line. That the O‐isotopic composition of ALSP1 is like those of Cr‐rich spinels from chondrules indicates that O‐isotopic compositions cannot be used to distinguish whether grains from such unequilibrated objects are condensates or are fragments from a previous generation of chondrules.     

The reaction of O+2 with atomic nitrogen and NO+· H2O and NO+2 with atomic oxygen

The reactions of atomic nitrogen with O⁺₂ and atomic oxygen and atomic nitrogen with NO⁺· H₂O and NO⁺₂ have been measured at 296 K. The rate constants are reported and the implication of the measurements to atmospheric ion chemistry is discussed.     

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.     

Chromium isotopic systematics of the Sutter's Mill carbonaceous chondrite: Implications for isotopic heterogeneities of the early solar system

Recent studies have shown that major meteorite groups possess their own characteristic ⁵⁴Cr values, demonstrating the utility of Cr isotopes for identifying genetic relationships between the planetary materials in conjunction with other classical tools, such as oxygen isotopes. In this study, we performed Cr isotope analyses for whole rocks and chemically separated phases of the new CM2 chondrite, Sutter's Mill (SM 43 and 51). The two whole rocks of Sutter's Mill show essentially identical ε⁵⁴Cr excesses (SM 43 = +0.95 ± 0.09ε, SM 51 = +0.88 ± 0.07ε), relative to the Earth. These values are the same within error with that of the CM2‐type Murchison (+0.89 ± 0.08ε), suggesting that parent bodies of Sutter's Mill and Murchison were formed from the same precursor materials in the solar nebula. Large ε⁵⁴Cr excess of up to 29.40ε is observed in the silicate phase of Sutter's Mill, while that of Murchison shows 15.74ε. Importantly, the leachate fractions of both Sutter's Mill and Murchison form a steep linear anticorrelation between ε⁵⁴Cr and ε⁵³Cr, cross‐cutting the positive correlation previously observed in carbonaceous chondrites. The fact that L4 acid leachate fraction contains higher ⁵⁴Cr excesses than that of L5 step designed to dissolve refractory minerals suggests that spinel is not a major ⁵⁴Cr carrier. We also note that L5 contains ⁵³Cr anomalies lower than the solar initial value, suggesting it carries a component of nucleosynthetic anomaly unrelated to the ⁵³Mn decay. We have identified five endmember components of nucleosynthetic origin among the early solar system materials.     

Models of the cometary coma in which abundances are calculated for various heliocentric distances

One-dimensional radial models of the chemistry in cometary comae have been constructed for heliocentric distances ranging from 2 to 0.125 AU. The coma's opacity to solar radiation is included and photolytic reaction rates are calculated. A parent volatile mixture similar to that found in interstellar molecular clouds is assumed. Profiles through the coma of number density and column density are presented for H₂O, OH, O, CN, C₂, C₃, CH, and NH₂. Whole-coma abundances are presented for NH₂, CH, C₂, C₃, CN, OH, CO⁺, H₂O⁺, CH⁺, N₂⁺, and CO₂⁺.     

Extraterrestrial amino acids and L‐enantiomeric excesses in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

The abundances, distributions, enantiomeric ratios, and carbon isotopic compositions of amino acids in two fragments of the Aguas Zarcas CM2 type carbonaceous chondrite fall and a fragment of the CM2 Murchison meteorite were determined via liquid chromatography time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. A suite of two‐ to six‐carbon aliphatic primary amino acids was identified in the Aguas Zarcas and Murchison meteorites with abundances ranging from ~0.1 to 158 nmol/g. The high relative abundances of α‐amino acids found in these meteorites are consistent with a Strecker‐cyanohydrin synthesis on these meteorite parent bodies. Amino acid enantiomeric and carbon isotopic measurements in both fragments of the Aguas Zarcas meteorites indicate that both samples experienced some terrestrial protein amino acid contamination after their fall to Earth. In contrast, similar measurements of alanine in Murchison revealed that this common protein amino acid was both racemic (D ≈ L) and heavily enriched in ¹³C, indicating no measurable terrestrial alanine contamination of this meteorite. Carbon isotope measurements of two rare non‐proteinogenic amino acids in the Aguas Zarcas and Murchison meteorites, α‐aminoisobutyric acid and D‐ and L‐isovaline, also fall well outside the typical terrestrial range, confirming they are extraterrestrial in origin. The detections of non‐terrestrial L‐isovaline excesses of ~10–15% in both the Aguas Zarcas and Murchison meteorites, and non‐terrestrial L‐glutamic acid excesses in Murchison of ~16–40% are consistent with preferential enrichment of circularly polarized light generated L‐amino acid excesses of conglomerate enantiopure crystals during parent body aqueous alteration and provide evidence of an early solar system formation bias toward L‐amino acids prior to the origin of life.     

An experimental study of the reaction kinetics of C2(XΣg) with hydrocarbons (CH4, C2H2, C2H4, C2H6 and C3H8) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets

The reactivity of C₂(X¹Σ⁺_g) with simple saturated (CH₄, C₂H₆ and C₃H₈) and unsaturated (C₂H₂ and C₂H₄) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ?10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ with the exception of methane for which the rate coefficient is one order of magnitude lower: ∼10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These results have been analyzed in terms of potential destruction sources of C₂(X¹Σ⁺_g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction ¹C₂ + CH₄ should be updated with our new data and that reactions with C₂H₂, C₂H₄ and C₂H₆ should also be included in the existing photochemical models.     

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.     

The role of hydrocarbons in the lonospheres of the outer planets

The role of hydrocarbons as a possible sink for H⁺ and H₃⁺ ions in the lower ionosphere of the outer planets is examined. Calculations indicate that H⁺ and H₃⁺ are efficiently converted to hydrocarbon ions on reaction with methane. The terminal ions, CH₅⁺ and C₂H₅⁺ are rapidly neutralized in dissociative recombination with electrons. Extreme ultraviolet photolysis of hydrocarbons as a potential additional source of lower elevation ions in investigated.