Engineering topics
Publications and source records attributed to Zinner, Ernst.
Below we summarize the results of the research carried out under the above-mentioned grant, which was funded from May 1, 2003 through April 30, 2004. A list of publications resulting from this work is to be found at the end of this document.
We have determined major (Si, Zr, Hf), minor (Al, Y, Fe, P), and trace element (Ca, Sc, Ti, Ba, REE, Th, U) concentrations and Raman spectra of a zoned, 200 microns zircon grain in lunar sample 14161,7069, a quartz monzodiorite breccia collected at the Apollo 14 site. Analyses were obtained on a thin section in situ with an ion microprobe, an electron microprobe, and a laser Raman microprobe. The zircon grain is optically zoned in birefringence, a reflection of variable (incomplete) metamictization resulting from zo- nation in U and Th concentrations. Variations in the concentrations of U and Th correlate strongly with those of other high-field-strength trace elements and with changes in Raman spectral parameters. Concentrations of U and Th range from 21 to 55 ppm and 6 to 31 ppm, respectively, and correlate with lower Raman peak intensities, wider Raman peaks, and shifted Si-O peak positions. Concentrations of heavy rare earth elements range over a factor of three to four and correlate with intensities of fluorescence peaks. Correlated variations in trace element concentrations reflect the original magmatic differentiation of the parental melt approx. 4 b.y. ago. Degradation of the zircon structure, as reflected by the observed Raman spectral parameters, has occurred in this sample over a range of alpha-decay event dose from approx. 5.2 x 10(exp 14) to 1.4 x 10(exp 15) decay events per milligram of zircon, as calculated from the U and Th concentrations. This dose is well below the approx. 10(exp 16) events per milligram cumulative dose that causes complete metamictization and indicates that laser Raman microprobe spectroscopy is an analytical technique that is very sensitive to the radiation-induced damage in zircon.
Previous secondary ion mass spectrometry (SIMS) studies of extended impact features from LDEF capture cell experiment AO187-2 showed that it is possible to distinguish natural and man-made particle impacts based on the chemical composition of projectile residues. The same measurement technique has now been applied to specially prepared gold target impacts from experiment AO187-1 in order to identify the origins of projectiles that left deposits too thin to be analyzed by conventional energy-dispersive x-ray (EDX) spectroscopy. The results indicate that SIMS may be the method of choice for the analysis of impact deposits on a variety of sample surfaces. SIMS was also used to determine the isotopic compositions of impact residues from several natural projectiles. Within the precision of the measurements all analyzed residues show isotopically normal compositions.
#Experiment AO187-2, that was flown on board the Long Duration Exposure Facility(LDEF), was designed to measure the chemical and isotopic compositions of interplanetary dust impinging on the spacecraft from outer space. Information on the nature and composition of orbital debris was also anticipated. The spacecraft maintained a constant orientation with respect to its velocity vector thereby defining leading and trailing edges that faced respectively into and away from the direction of motion. Arrays of individual capture cells each 80.8 sq cm in size and totaling 237 in number were exposed on both the leading and trailing edges of LDEF. Each cell consisted of a pure Ge target surface slightly separated from a thin (2.5 micrometers) metallized plastic 'entrance foil.' The basic concept was that incoming projectiles would penetrate the foil, strike the Ge target plate at high velocity producing a vapor-liquid cloud that would re-deposit material on the underside of the plastic foil. This material would then be analyzed using the sensitive surface analysis technique of Secondary Ion Mass Spectrometry (SIMS). In practice, most of the plastic entrance foils failed during the extended period of orbital exposure probably due to a combination of UV embrittlement, large densities of impact events and (for the leading edge) the effects of atomic oxygen erosion in orbit. However the foils failed gradually and most remained in place on the capture cells for a significant fraction of the duration of the flight . Because most of the impactors were small (less than 10 micrometers) they were heated and dispersed in traversing the entrance foils producing clouds of molten droplets and vapor that produced easily identifiable 'extended impacts' on the Ge target plates. Fortunately, it proved possible to make ion probe measurements of projectile compositions from material deposited on the Ge in the extended impact structures.
We have tried to deconvolve Solar-System carbon into its sources, on the basis of C-12/C-13 ratios (equivalent to R). Interstellar SiC in meteorites, representing greater than 4.6-Ga-old stardust from carbon stars, is isotopically heavier (bar R = 38 +/- 2) than Solar-System carbon (89), implying that the latter contains an additional, light component. A likely source are massive stars, mainly Type II supernovae and Wolf-Rayet stars, which, being O-rich, eject their C largely as CO rather than carbonaceous dust. The fraction of such light C in the Solar System depends on R(sub light) in the source. For R(sub light) = 180-1025 (as in 'Group 4' meteoritic graphite spherules, which apparently came from massive stars greater than 4.6 Ga ago), the fraction of light C is 0.79-0.61. Similar results are obtained for present-day data on red giants and interstellar gas. Although both have become enriched in C-13 due to galactic evolution (to bar-R = 20 and 57), the fraction of the light component in interstellar gas again is near 0.7. (Here bar R represents the mean of a mixture calculated via atom fractions; it is not identical to the arithmetic mean R). Interstellar graphite, unlike SiC, shows a large peak at R approximately equal 90, near the solar value. Although some of the grains may be of local origin, others show anomalies in other elements and hence are exotic. Microdiamonds, with R = 93, also are exotic on the basis of their Xe and N. Apparently R approximately 90 was a fairly common composition 4.6 Ga ago, of stars as well as the ISM.
Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources. The C- and N-isotopic compositions of most grains are consistent with H-burning in the CNO cycle. These and s-process Kr, Xe, Ba, and Nd suggest asymptotic giant branch (AGB) or Wolf-Rayet stars as likely sources for the grains, but existing models of nucleosynthesis in these stellar sites fail to account in detail for all the observed isotopic compositions. Special problems are posed by grains with C-12/C-13 less than 10 and almost normal and heavy N-isotopic compositions. Also the Si- and Ti-isotopic compositions, with excesses in Si-29 and Si-30 relative to Si-28 and excesses in all Ti isotopes relative to Ti-48, do not precisely conform with the compositions predicted for slow neutron capture. Additional theoretical efforts are needed to achieve an understanding of the isotopic composition of the SiC grains and their stellar sources.
The Ca isotopic compositions of 32 oldhamite (CaS) grains from the Qingzhen (EH3), MAC88136 (EL3), and Indarch (EH4) enstatite chondrites were determined by ion microprobe mass spectrometry. Also measured were the S isotopic compositions of eight oldhamite, two niningerite (MgS), and seven troilite (FeS) grains. The S isotopic compositions of all minerals are normal, but oldhamite grains of the first two meteorites exhibit apparent small Ca-48 excesses and deficits that are correlated with isotopic mass fractionation as determined from the Ca-40-Ca-44 pair. The interpretation of these results is complicated by the fact that none of the established mass fractionation laws can account for the data in the Norton County oldhamite standard. The method of analysis is carefully scrutinized for experimental artifacts. Neither interferences nor any known mass frationation effect can satisfactorily explain the observed small deviations from normal isotopic composition. If these are truly isotopic anomalies, they are much smaller than those observed in hibonite. The nucleosynthetic origin of Ca isotopes is discussed.
Primitive meteorites contain a few parts per million (ppm) of pristine interstellar grains that provide information on nuclear and chemical processes in stars. Their interstellar origin is proven by highly anomalous isotopic ratios, varying more than 1000-fold for elements such as C and N. Most grains isolated thus far are stable only under highly reducing conditions (C/O greater than 1), and apparently are 'stardust' formed in stellar atmospheres. Microdiamonds, of median size about 10 A, are most abundant (about 400-1800 ppm) but least understood. They contain anomalous noble gases including Xe-HL, which shows the signature of the r- and p-processes. Silicon carbide, of grain size 0.2-10 microns and abundance about 6 ppm, shows the signature of the s-process and apparently comes mainly from red giant carbon (AGB) stars of 1-3 solar masses. Some grains appear to be not less than 10 exp 9 a older than the solar system. Graphite spherules of grain size 0.8-7 microns and abundance less than 2 ppm contain highly anomalous C and noble gases, as well as large amounts of fossil Mg-26 from the decay of extinct Al-26. They seem to come from at least three sources, probably AGB stars, novae, and Wolf-Rayet stars.
A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.
We have measured C-, N-, and O-isotopic ratios of individual graphite grains from the Murchison density fractions KFB1 (2.1-2.15 g/cc) and KFC1 (2.15 -2.20 g/cc). According to the C-isotopic composition, KFC1 consists of two populations: one has light C while the other has heavy C. In addition to these two populations, KFB1 also contains grains whose C-isotopic ratios are approximately normal. In view of these isotopic distributions, it is difficult to understand why the Kr-isotopic compositions of these two separates are so different. In contrast to the lighter density fractions KE1 (1.6-2.05 g/cc) and KFA1 (2.05-2.10 g/cc), the separates KFB1 and KFC1 do not seem to contain many grains with significant O-18 excess.
Results are presented from an ion microprobe mass spectrometric analyses of five SiC grains from the Murchison carbonaceous meteorite. Unlike most interstellar SiC grains from primitive meteorites, the five grains from the Murchison meteorite show large excesses of C-12 (up to 28 times solar) and N-15 (up to 22 times solar), depletion in Si-29 and Si-30 (up to 59 percent), Al-26/Al-27 ratios between 0.1 and 0.6, and Ti-49 excesses up to 95 percent; in addition, one grain has a large Ca-44 excess (300 percent). The Ca and Ti anomalies point toward explosive nucleosynthesis in supernovae and the in situ decay of the radioactive precursors Ti-44 and V-49 in SiC grains formed in supernova ejecta. However, there is no simple formation scenario that can give a consistent explanation for the isotopic compositions of these grains.
Ion probe mass spectrometry is used to analyze 41 large SiC grains from the Murchison CM2 chondrite, ranging up to 15 x 26 microns, for the isotopic compositions of C, N, Mg, and Si, and the concentrations of Al, Ti, V, Fe, Zr, and Ba. The majority were found to have large isotopic anomalies. Only two grains, characterized by extremely heavy carbon, give evidence for fossil Mg-26. On the basis of C and Si isotopic composition, 29 of the grains fall into three compact clusters, presumably from three discrete sources. The clustering of coarse-grained SiC stands in sharp contrast to the quasi-continuous distribution of finer-grained SiC and suggests that the top 0.1 percent of the mass distribution is a distinct population. The C and N isotopic compositions of the anomalous grains are not very diagnostic, being consistent with H-burning in the CNO cycle. The Si-isotopic compositions qualitatively show the signature of neutron capture in He-burning shells of highly evolved stars.
One hundred capture cells from the trailing edge, which had lost their cover foils during flight, were optically scanned for extended impact features caused by high velocity projectiles impinging on the cells while the foils were still intact. Of the 53 candidates, 24 impacts were analyzed by secondary ion mass spectroscopy for the chemical composition of the deposits. Projectile material was found in all impacts, and at least 75 percent of them appear to be caused by interplanetary dust particles. Elemental ratios are fractionated, with refractory elements enriched in the impacts relative to interplanetary dust particles collected in the stratosphere. Although this could be due to systematic differences in the compositions, a more likely explanation is volatility fractionation during the impact process.
Ion microprobe isotopic measurements of Ba, Nd, and Sm in the K-series SiC size separates on which noble gas measurements were made by Lewis et al. (1990) are reported. All elements show isotopic abundance patterns characteristic for the s-process. The Ba-134/Ba-136 ratios are distinct from solar, indicating that s-Ba in SiC is different from that in the solar system. Ba-138/Ba-136 ratios decrease with grain size; if interpreted as being due to different neutron exposures, this trend is opposite of that shown by the Kr-86/Kr-82 ratios. Although other isotropic ratios for Ba and those for Nd and Sm differ in detail from theoretical predictions, the disagreements probably being due to uncertainties in the n-capture cross sections and simplifications in the models, the general agreement of the data with models of s-process nucleosynthesis support an AGB star origin for the relatively fine-grain SiC under consideration. Ba-136 in SiC is up to 85 percent pure s-process.
Results are presented from measurements of O, Mg, and Ti isotopes and the abundances of Mg, Ca, Sc, Ti, V, Sr, Y, Zr, La, and Ce in 26 individual corundum grains from the Murchison CM2 chondrite. The results provide further evidence for live Al-26 in the early solar system and set strict upper limits on the amounts of fossil Mg-26. The analyses suggest that corundum in this chondrite formed from two components with live Al-26 and a mass fraction of 43 percent dead Al.
The study focuses on 26 Al2O3 grains up to 20 micron in size recovered from the Murchison C2 chrondite. It is observed that Mg-26/Mg-24 ranges up to 56 times the solar system ratio, but the initial Al-26/Al-27 ratios do not exceed the canonical maximum of 0.00005 in other meteoritic samples. It is concluded that this ratio represents the abundance of live Al-26 in the early solar system, not fossil radiogenic Mg-26 surviving from presolar times. The grains are shown to divide into three groups on the basis of Al-26, O-16, Ti, and V content, and distinctive correlations are found for Al-26 and O-16. An origin from at least three discrete components is suggested, two of which contained live Al-26.
A survey of microanalytical measurements on interplanetary dust particles (IDPs) and interstellar dust grains from primitive meteorites is presented. Ion-microprobe mass spectrometry with its capability to determine isotopic compositions of many elements on a micron spatial scale has played a special role. Examples are measurements of H, N, and O isotopes and refractory trace elements in IDPs; C, N, Mg, and Si isotopes in interstellar SiC grains; and C and N isotopes and H, N, Al, and Si concentrations in interstellar graphite grains.
It is reported here that interstellar graphite and SiC grains recovered from the Murchison CM2 chondritic meteorite have large abundances of Mg-26 from the decay of extinct Al-26. The deduced initial Al-26/Al-27 ratios range up to 0.06 in graphite and 0.2 in SiC. This is 1200 to 4000 times the maximum values found in refractory inclusions in primitive meteorites. All proposed stellar sources of carbonaceous dust also produced Al-26, but the highest Al-26/Al-27 ratios found in these grains seem to rule out Wolf-Rayet stars and supernovae. The aluminum abundance correlates with that of nitrogen, suggesting that the aluminum condensed as aluminum nitride.