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

Meteoritic Bismuth and ^(208)Pb Microdistributions

Certain types of meteorites are believed to be the most primitive solar system objects available. Bismuth and lead microdistributions in these are of interest because (a) predictions for the condensation of these elements are available from thermodynamic calculations for equilibrium, gas-to-solid condensation in a cooling nebula of solar composition; (b) based on this theory, bulk bismuth contents have been used for inferring the temperatures at which solids in the solar nebula accreted, as well as the extant nebular pressures; and (c) due to their volatility, these elements are easily mobilized in metamorphic (reheating) events and are thus sensitive indicators of planetary processing of the meteoritic material. With the idea of testing, where possible, the equilibrium condensation theory (a) and its ramifications (b) and of assessing the nature and evolution of early bodies in the solar system (c), we have been studying the bismuth and ^(208)Pb microdistributions in unequilibrated chondritic meteorites

Metal and Bi/Pb microdistribution studies of an L3 chondrite: their implications for a meteorite parent body

We find strong localizations (relative to bulk) of Bi and to a lesser extent Pb. in some of the kamacite grains in Khohar. Other kamacite grains show no such enrichments. There are distinctive and correlated differences in the Ni contents of the two kamacite populations, with the Bi/Pb-rich kamacite grains having consistently lower Ni levels (sometimes unusually low. ~ 2% Ni) than the Bi/Pb-poor kamacite, which typically have ~ 6–7% Ni. The Bi/Pb-rich kamacite grains are also distinguished on the basis of their etching behavior, exhibiting a highly reactive attack, which has not been observed previously and which we believe may be due to the fact that the Bi/Pb-rich kamacite is finely polycrystalline. We conclude that the trace element microdistributions were not established in the nebula. Nor is it likely that the enrichments occurred with slow cooling in the presence of a vapor phase during the kamacite-taenite phase transition. Rather, the Bi/Pb-rich kamacite most likely reflect the occurrence of a brief reheating episode (or episodes), which may have been shock-induced and which was followed by rapid cooling. We find fine-grained metal-sulfide intergrowths which testify to such a reheating event, and one likely candidate for the site of this event is a hot ejecta blanket at the parent body surface. Iron oxides are found in our Khohar sections. We believe that they are not due to terrestrial alteration, that they are magnetite and that the magnetite probably originated in the same dynamic event in which the Bi/Pb distributions were established. The present data do not allow us to confidently determine whether the event occurred prior to, during, or after the compaction of this meteorite, although the simplest interpretation of the data would indicate the first alternative. Bulk Bi data for Khohar has been used for inferring accretion temperatures and this now appears inappropriate

Bismuth and ^(208)Pb microdistributions in enstatite chondrites

Polished sections of 5 enstatite chondrites have been irradiated with 30 MeV ^4He ions to produce the alpha-radioactive nuclei ^(211)At and ^(210)Po from ^(209)Bi and ^(208)Pb, respectively. The distribution of alpha activity can be mapped, using cellulose nitrate as an alpha track detector, to give the corresponding Bi or Pb distributions in the meteorite. No strong localization of Bi or ^(208)Pb was found; relatively uniform track distributions were observed. In particular, metal or sulfide grains are not enriched in Bi or Pb (relative to bulk), which is in agreement with the predictions of nebular condensation calculations. While the track distributions appear uniform, the results of detailed, track-by-track mappings of the Bi detectors indicate that the Bi is not totally randomly distributed; the statistical fluctuations in the observed track density are different for the cases where the Bi is totally randomly distributed and where the Bi is localized in point sources. Assuming that the Bi in a given sample is localized in identical point sources which are uniformly distributed throughout the sample, the observed relative population densities of clusters (‘stars’) of small numbers of tracks (2–5) corresponds to Bi being localized, with ~90% in grains with about 10^(−16)g-Bi (~3 × 10^5 Bi atoms), and with ~10% in 4 × 10^(−14) g-Bi sources. If these are elemental Bi, as predicted theoretically, they are ~ 10^2 Å and 10^3 Å in size, respectively