The Origin and Significance of Reverse Zoning in Melilite from Allende Type B Inclusions

In many Type B Allende inclusions, melilite is reversely-zoned over restricted portions of each crystal. Textural relationships and the results of dynamic crystallization experiments suggest that the reverselyzoned intervals in these Type melilites result from the co-precipitation of melilite with clinopyroxene from a melt, prior to the onset of anorthite precipitation. When clinopyroxene begins to precipitate, the Al/Mg ratio of the melt rises, causing the crystallizing melilite to become more gehlenitic, an effect which is negated by crystallization of anorthite. Because the equilibrium crystallization sequence in these liquids is anorthite before pyroxene, melilite reverse zoning can occur only when anorthite nucleation is suppressed relative to pyroxene. This has been achieved in our experiments at cooling rates as low as 0.5°C/hour. Our experiments further indicate, however, that reverse zoning does not form at cooling rates ≥50°C/hour , probably because the clinopyroxene becomes too Al-rich to drive up the Al/Mg ratio of the liquid. Type inclusions with reversely-zoned melilites must have cooled at rates greater than those at which anorthite begins to crystallize before clinopyroxene but <50°C/hour. Such rates are far too slow for the Type droplets to have cooled by radiation into a nebular gas but are much faster than the cooling rate of the solar nebula itself. One possibility is that Type B's formed in local hot regions within the nebula, where their cooling rate was equal to that of their surrounding gas. Other possibilities are that their cooling rates reflect their movement along nebular temperature gradients or the influence of a heat source. The sun or viscous drag on inclusions as they moved through the nebular gas are potential candidates for such heat sources

Image and compositional characteristics of the LDEF Big Guy impact crater

A 5.2 mm crater in Al-metal represents the largest found on LDEF. We have examined this crater by field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) and time-of-flight/secondary ion mass spectroscopy (TOF-SIMS) in order to determine if there is any evidence of impactor residue. Droplet and dome-shaped columns, along with flow features, are evidence of melting. EDS from the crater cavity and rim show Mg, C, O and variable amounts of Si, in addition to Al. No evidence for a chondritic impactor was found, and it hypothesized that the crater may be the result of impact with space debris

Hypervelocity impact survivability experiments for carbonaceous impactors, part 2

Hypervelocity impact experiments were performed to further test the survivability of carbonaceous impactors and to determine potential products that may have been synthesized during impact. Diamonds were launched by the Ames two-stage light gas gun into Al plate at velocities of 2.75 and 3.1 km sec(exp -1). FESEM imagery confirms that diamond fragments survived in both experiments. Earlier experiments found that diamonds were destroyed on impact above 4.3 km sec(exp -1). Thus, the upper stability limit for diamond on impact into Al, as determined from our experimental conditions, is between 3.1 and 4.3 km sec(exp -1). Particles of the carbonaceous chondrite Nogoya were also launched into Al at a velocity of 6.2 km sec (exp -1). Laser desorption (L (exp 2) MS) analyses of the impactor residues indicate that the lowest and highest mass polycyclic aromatic hydrocarbons (PAH's) were largely destroyed on impact; those of intermediate mass (202-220 amu) remained at the same level or increased in abundance. In addition, alkyl-substituted homologs of the most abundant pre-impacted PAH's were synthesized during impact. These results suggest that an unknown fraction of some organic compounds can survive low to moderate impact velocities and that synthesized products can be expected to form up to velocities of, at least, 6.5 km sec(exp -1). We also present examples of craters formed by a unique microparticle accelerator that could launch micron-sized particles of almost any coherent material at velocities up to approximately 15 km sec(exp -1). Many of the experiments have a direct bearing on the interpretation of LDEF craters

Electron Microprobe/SIMS Determinations of Al in Olivine: Applications to Solar Wind, Pallasites and Trace Element Measurements

Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~100 µg g⁻¹ level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g⁻¹. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine; but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio

Electron Microprobe/SIMS Determinations of Al in Olivine: Applications to Solar Wind, Pallasites and Trace Element Measurements

Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~100 µg g⁻¹ level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g⁻¹. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine; but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio

Ion Implants as Matrix-Appropriate Calibrators for Geochemical Ion Probe Analyses

Ion microprobe elemental and isotopic determinations can be precise but difficult to quantify. Error is introduced when the reference material and the sample to be analysed have different compositions. Mitigation of such “matrix effects” is possible using ion implants. If a compositionally homogeneous reference material is available which is “matrix-appropriate,” i.e., close in major element composition to the sample to be analysed, but having an unknown concentration of the element, E, to be determined, ion implantation can be used to introduce a known amount of an E isotope, calibrating the E concentration and producing a matrix-appropriate calibrator. Nominal implant fluences (ions cm^(−2)) are inaccurate by amounts up to approximately 30%. However, ion implantation gives uniform fluences over large areas, thus it is possible to “co-implant” an additional reference material of any bulk composition having known amounts of E, independently calibrating the implant fluence. Isotope-ratio measurement standards can be produced by implanting two different isotopes, but permil level precision requires post-implant calibration of the implant isotopic ratio. Examples discussed include: (1) standardising Li in melilite; (2) calibrating a ^(25)Mg implant fluence using NIST SRM 617 glass; and (3) using Si co-implanted with ^(25)Mg alongside NIST SRM 617 to produce a calibrated measurement of Mg in Si

Crystallization sequences of Ca-AI-rich inclusions from Allende: The effects of cooling rate and maximum temperature

We have studied the crystallization sequences, mineral chemistries, and textures that develop when an average Type B Ca-Al-rich inclusion composition is cooled in air from 1275–1580° C to below 1000°C at rates between 0.5 and 1000°C/hr. Crystallization sequences, the textures of all the major phases, pyroxene chemistry, and melilite zoning patterns are functions of both the cooling rate and the temperature from which cooling begins. Determination of the order of pyroxene and plagioclase crystallization has been identified as an important goal for petrographic studies of CAIs because it can be used to set constraints on the cooling rate experienced by an individual inclusion. Overall textures plus melilite zoning patterns and pyroxene chemistry can give important clues as to whether pyroxene or plagioclase began to crystallize first. Melilite texture and chemistry appear to yield the most valuable information on the maximum temperature to which an inclusion was raised prior to cooling. Comparison of our experimental results with petrographic observations of Type B CAIs suggests that most inclusions were partially melted and then cooled at rates on the order of a few tenths to tens of degrees per hour. Maximum temperatures of about 1400°C appear most likely for intermediate Type B Allende inclusions. Our results do not support the suggestion that the textures observed in these inclusions formed by crystallization of supercooled, metastable melt droplets condensed from nebular gas. The slow cooling rates we infer for CAIs are difficult to reconcile with models for their origin that imply simple radiative cooling of individual molten or partially molten droplets in a cold, low density environment. On the other hand, cooling rates of the nebular cloud are believed to have been much slower than those we have inferred for Type B CAIs. Scenarios that could be reconciled with the thermal history that we have inferred include drag heating of particles falling through nebular gas, heating by intense radiation (e.g., via flares) from the early sun, heating in nebular shock fronts, or other thermal heterogeneities in the early nebula allowing time scales for cooling (and heating) of CAIs much shorter than those for the nebular cloud as a whole. Successful models for the origin of Type B CAIs must account for the fact that most Type B CAIs cooled relatively slowly from a partially molten state

A new titanium-bearing calcium aluminosilicate phase: II. Crystallography and crystal chemistry of grains formed in slowly cooled melts with bulk compositions of calcium-aluminum-rich inclusions

The crystallography and crystal chemistry of a new calcium- titanium-aluminosilicate mineral (UNK) observed in synthetic analogs to calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites was studied by electron diffraction techniques. The unit cell is primitive hexagonal or trigonal, with a = 0.790 ± 0.02 nm and c = 0.492 ± 0.002 nm, similar to the lattice parameters of melilite and consistent with cell dimensions for crystals in a mixer furnace slag described by Barber and Agrell (1994). The phase frequently displays an epitactic relationship in which melilite acts as the host, with (0001)_(UNK) || (001)_(mel) and _(UNK) || _mel. If one of the two space groups determined by Barber and Agrell (1994) for their sample of UNK is applicable (P3ml or P31m), then the structure is probably characterized by puckered sheets of octahedra and tetrahedra perpendicular to the c-axis with successive sheets coordinated by planar arrays of Ca. In this likely structure, each unit cell contains three Ca sites located in mirror planes, one octahedrally coordinated cation located along a three-fold axis and five tetrahedrally coordinated cations, three in mirrors and two along triads. The octahedron contains Ti but, because there are 1.3-1.9 cations of Ti/formula unit, some of the Ti must also be in tetrahedral coordination, an unusual but not unprecedented situation for a silicate. Tetrahedral sites in mirror planes would contain mostly Si, with lesser amounts of Al while those along the triads correspondingly contain mostly Al with subordinate Ti. The structural formula, therefore, can be expressed as Ca^(VIII)_3(Ti,Al)^(VI)(Al,Ti,Si)^(IV)_2(Si,Al)^(IV)_3O_(14) with Si + Ti = 4. Compositions of meteoritic and synthetic Ti-bearing samples of the phase can be described in terms of a binary solid solution between the end-members Ca_3TiAl_2Si_3O_14 and Ca_3Ti(AlTi)(AlSi_2)O_14. A Ti-free analog with a formula of Ca_3Al_2Si_4O_14 synthesized by Paque et al. (1994) is thought to be related structurally but with the octahedral site being occupied by Al, that is, Ca^(VIII)_3Al^(VI)(Al,Si)^(IV)_2(Si)^(IV)_3O_14

A new titanium-bearing calcium aluminosilicate phase: I. Meteoritic occurrences and formation in synthetic systems

A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed “UNK,” is Ca_3Ti(Al, Ti)_2(Si, Al)_3O_(14), and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystals oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 °C/h from maximum (initial) temperatures of 1375 to 1580 °C. Only below 1190 °C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic UNK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti (7–13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAIs, although glass, which is typically associated with synthetic UNK, is not observed in meteoritic occurrences. A low Ti end-member of UNK (“Si-UNK”) with a composition near that of Ca_3Al_2Si_4O_(14) was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions