Engineering topics
Publications and source records attributed to Bunch, T. E..
Evidence for impact-generated hydrothermal activity is reported from the Haughton crater, Canada. Two distinct settings have been found: (1) pipe structures with marcasite, pyrite and minor chalcopyrite; (2) cavity and fracture fillings with marcasite predominant.
In this work we have searched for extraterrestrial (ET) helium (He) in fullerenes isolated from several K/T boundary (KTB) sediments. Measurements of He in these KTB fullerene residues revealed He-3/He-4 ratios that can only be explained as ET in origin.
In this paper, we confirm our earlier observations of fullerenes (C60 and C70) in the Allende meteorite (Becker et al., 1994a, 1995). Fullerene C60 was also detected in two separate C-rich (approximately 0.5-1.0%) dark inclusions (Heymann et al., 1987) that were hand picked from the Allende sample. The amounts of C60 detected were approximately 5 and approximately 10 ppb, respectively, which is considerably less than what was detected in the Allende 15/21 sample (approximately 100 ppb; Becker et al., 1994a, 1995). This suggests that fullerenes are heterogeneously distributed in the meteorite. In addition, we present evidence for fulleranes, (C60Hx), detected in separate samples by laser desorption (reflectron) time-of-flight (TOF) mass spectrometry (LDMS). The LDMS spectra for the Allende extracts were remarkably similar to the spectra generated for the synthetic fullerane mixtures. Several fullerane products were synthesized using a Rh catalyst (Becker et al., 1993a) and separated using high-performance liquid chromatography (HPLC). Polycyclic aromatic hydrocarbons (PAHs) were also observed ppm levels) that included benzofluoranthene and corannulene, a cup-shaped molecule that has been proposed as a precursor molecule to the formation of fullerenes in the gas phase (Pope et al., 1993).
Fullerenes (C60 and C70) have recently been identified in a shock-produced breccia (Onaping Formation) associated with the 1.85-Ga Sudbury Impact Crater. The presence of parts-per-million levels of fullerenes in this impact structure raises interesting questions about the processes that led to the formation of fullerenes and the potential for delivery of intact organic material to the Earth by a large bolide (e.g., asteroid or comet). Two possible scenarios for the presence of fullerenes in the Sudbury impact deposits are that (1) fullerenes are synthesized within the impact plume from the C contained in the bolide; or (2) fullerenes are already present in the bolide and survived the impact event. The correlation of C and trapped noble gas atoms in meteorites is well established. Primitive meteorites contain several trapped noble gas components that have anomalous isotopic compositions, some of which may have a presolar origin. Several C-bearing phases, including SiC, graphite, and diamond, have been recognized as carriers of trapped noble gases. It has also been suggested that fullerenes (C60 and C70) might be a carrier of noble gas components in carbonaceous chondrites. Recently, fullerenes have been detected in separate samples in the Allende meteorite. Carbon-60 is large enough to enclose the noble gases He, Ne, Ar, Kr, and Xe, but it is too small to contain diatomic gases such as N2 or triatomic gases such as CO2. Recent experimental work has demonstrated that noble gases of a specific isotopic composition can be introduced into synthetic fullerenes at high temperatures and pressures; these encapsulated gases can then be released by the breaking of one or more C bonds during step-heating under vacuum. These thermal-release patterns for He encapsulated within the C60 molecule (He@C60) are similar to the patterns for acid residues of carbonaceous chondrites, suggesting that fullerenes could be an additional carrier of trapped noble gases in acid residues of meteorites. Analysis and Results: In order to characterize the noble gas compositions of the Sudbury fullerenes, we undertook a systematic study of acid-resistant residues throughout the C-rich layer (Black member) of the Onaping Formation. Samples were demineralized and extracted using standard techniques. The Onaping extracts were analyzed using several techniques, including UV-Vis adsorption, electro spray mass spectrometry, and laser desorption (linear and reflectron) time-of-flight (TOF) mass spectrometry (LDMS). The Sudbury fullerenes were then separated and purified using HPLC coupled with a photo diode array detector. The HPLC extracts containing the purified fullerenes were loaded into a metal tube furnace within a glove box under a N atmosphere in preparation for noble gas analyses. The 3-He and 4-He content of the fullerene extracts was measured using previously reported standard techniques . Discussion: Fullerenes (C60 and C70) in the Sudbury Impact Structure have been found to contain trapped He with a 3-He/4-He ratio greater than 5 x 10(exp -4). The 3-He/4-He ratio exceeds the accepted solar value by more than 30% and is more than 10x higher than the maximum reported mantle value. Terrestrial nuclear reactions or cosmic-my bombardment are not sufficient to generate such a high ratio. The 3-He/4-He ratios in the Sudbury fullerenes are similar to those determined for interplanetary dust particles. The greater-than-solar ratios of 3-He/4-He in the Sudbury fullerenes may indicate a presolar origin, although alternative mechanisms occurring in the ISM to explain these high ratios (e.g., spallation reactions, selective He implantation, etc.) cannot be entirely ruled out. We are currently attempting to isolate enough fullerene material to measure anomalous Ne (or Kr or Xe) contained within the C60 (e.g., the "pure" 22-Ne component) and thus determine whether the Sudbury fullerenes are indeed presolar in origin.
One intriguing and important issue of the Sudbury Structure concerns the source of the relatively large amount of C in the Onaping Formation Black member. This dilemma was recently addressed, and the conclusion was reached that an impactor could not have delivered all of the requisite C. Becker et al. have suggested that much of the C came from the impactor and reported the presence of interstellar He "caged" inside some fullerenes that may have survived the impact. So, conceivably, the C inventory in the Sudbury Structure comes from both target and impactor materials, although the known target rocks have little C. We discuss here the possibility of two terrestrial sources for at least some of the C: (1) impact evaporation/dissociation of C from carbonate target rocks and (2) the presence of heretofore-unrecognized C-rich (up to 26 wt%) siliceous "shale," fragments, which are found in the upper, reworked Black member. Experimental: Hypervelocity impact of a 0.635-diameter Al projectile into dolomite at 5.03 km/s (performed at the Ames Research Center vertical gun range) produced a thin, black layer (= 0.05 mm thick) that partially lined the crater and coated impactor remnants. Scanning electronic microscope (SEM) imagery shows this layer to be spongelike on a submicron scale and Auger spectroscopic analyses yield: 33% C, 22% Mg, 19% 0, and 9% Al (from the projectile). Elemental mapping shows that all of the available 0 is combined with Ca and Mg, Al is not oxidized, and C is in elemental form. Dissociation efficiency of C from CO2 is estimated to be <10% of crater volume. Raman spectroscopy indicates that the C is highly disorganized graphite. Another impact experiment [4] also produced highly disordered graphite from a limestone target (reducing collector), in addition to small amounts of diamond/lonsdaleite/chaoite (oxidizing collector). These experiments confirm the reduction of C from carbonates in impact vapor plumes. Observational: SEM observations and microprobe analyses of small, black shalelike inclusions in the upper Black Onaping indicate high C contents (7-26 wt% avg. = 16%). They contain mostly quartz and carbonaceous matter with small amounts of altered K-feldspar, clays, Fe oxide, and a sulfide. No evidence of shock is seen in quartz, and overall characteristics indicate a natural, lightly metamorphosed carbonaceous shale or mudstone that probably existed as a preimpact rock in the target region and distal fragments washed in during early crater filling. Fragments range in size from tens of microns to cm and increase in abundance in the upper Black toward the Onwatin contact, although their distribution is highly irregular. This increase corresponds to an increase in "organic" C with increasingly negative delta-13 C values and S, together with a decrease in fullerene abundance. In addition, we have found soot in acid-demineralized residues of the Onwatin but not in the Onaping samples. These data could be consistent with impact plume and atmospheric chemical processes, with possible diageneric ovedays. We are analyzing carbonaceous fractions of the Onaping and Onwatin to determine diagnostic C isotopic signatures Analyses by Whitehead et al. on bulk samples revealed no definitive source or processes, although delta-13 C values for "organic" C overlapped those for some meteorites. Discussion: If impact evaporation of Sudbury target carbonates did occur, then where are the carbonates? Distal carbonate (limestone/dolostone) exposures of the Espanola Formation (Huronian Supergroup) are generally thin-bedded, although remnants that partially encompass the Sudbury Crater are variable in thickness and may locally reach 250 m . If a carbonate thickness of 100-200 in existed at the target site, then copious amounts of C could have been reduced by impact processing of carbonates and also C-shale, depending on the efficiency of the processing and the amount of postimpact oxidation. Conclusion: The Sudbury crater offers a unique opportunity to study preserved characteristics of immediate carbonaceous fallback matter and particles of short-term residency in the impact plume as well as dust/aerosols from postimpact atmospheric processing.
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.
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.
The detection of fullerenes in deposits from meteor impacts has led to renewed interest in the possibility that fullerenes are present in meteorites. Although fullerenes have not previously been detected in the Murchison and Allende meteorites, the Allende meteorite is known to contain several well-ordered graphite particles which are remarkably similar in size and appearance to the fullerene-related structures carbon onions and nanotubes. We report that fullerenes are in fact present in trace amounts in the Allende meteorite. In addition to fullerenes, we detected many polycyclic aromatic hydrocarbons (PAHs) in the Allende meteorite, consistent with previous reports. In particular, we detected benzofluoranthene and corannulene (C20H10), five-membered ring structures which have been proposed as precursors to the formation of fullerene synthesis, perhaps within circumstellar envelopes or other sites in the interstellar medium.
We wish to draw attention to a major controversy that has arisen in the area of CM-chondrite petrology. The problem is important because its resolution will have profound implications for ideas concerning nebular dynamics, gas-solid interactions in the nebula, and accretionary processes in the nebula, among other issues. On the one hand, cogent arguments have been presented that 'accretionary dust mantles,' were formed in the solar nebula prior to accretion of the CM parent asteroid(s). On the other hand, no-less-powerful arguments have been advanced that a significant fraction of the CM lithology is secondary, produced by aqueous alteration in the near-surface regions of an asteroid-sized object. Because most, if not all, CM chondrites are breccias, these two views could coexist harmoniously, were it not for the fact that some of the coarse-grained lithologies surrounded by 'accretion dust mantles' are themselves of apparently secondary origin. Such an observation must clearly force a reassessment of one or both of the present schools of thought. Our objective here is to stimulate such a reassessment. Four possible resolutions of this conflict may be postulated. First, perhaps nature found a way of permitting such secondary alteration to take place in the nebula. Second, maybe dust mantles could form in a regolith, rather than a nebular, environment. Third, it is possible that dust mantles around secondary lithologies are different from those around primary lithologies. Finally, perhaps formation of CM chondrites involved a more complex sequence of events than visualized so far, so that some apparently 'primary' processes postdated certain 'secondary' processes.
The fullerenes C60 and C70 have been found to occur naturally on Earth and have also been invoked to explain features in the absorption spectra of interstellar clouds. But no definitive spectroscopic evidence exists for fullerenes in space and attempts to find fullerenes in carbonaceous chondrites have been unsuccessful. Here we report the observation of fullerenes associated with carbonaceous impact residue in a crater on the Long Duration Exposure Facility (LDEF) spacecraft. Laser ionization mass spectrometry and Raman spectroscopy indicate the presence of fullerenes in the crater and in adjacent ejecta. Man-made fullerenes survive experimental hypervelocity (approximately 6.1 km s-1) impacts into aluminium targets, suggesting that space fullerenes contained in a carbonaceous micrometeorite could have survived the LDEF impact at velocities towards the lower end of the natural particle encounter range (<13 km s-1). We also demonstrate that the fullerenes were unlikely to have formed as instrumental artefacts, nor are they present as contaminants. Although we cannot specify the origin of the fullerenes with certainty, the most plausible source is the chondritic impactor. If, alternatively, the impact produced the fullerenes in situ on LDEF, then this suggests a viable mechanism for fullerene production in space.
Evidence of shock metamorphism in the Dutch Peak diamictite in the Sheeprock Mountains, Utah, is reported. The Dutch Peak diamictite is of Proterozoic age and is a minor part of the Dutch Peak formation. A shocked sample, specimen A250, was collected during a brief visit of the Harker Canyon area of the Sheeprock Mountains. This sample consists of equant, anhedral grains of quartz, K-feldspar, and plagioclase. The crystallographic orientation of 244 lamellae systems in 106 grains was measured. It is presently difficult to evaluate the significance of this single specimen. Without additional and substantial field work, and petrographic characterization of this formation, a number of scenarios for the presence of a shocked clast and the emplacement of the entire formation remain viable.
The Small Particles Intact Capture Experiment (SPICE) will develop technologies and engineering techniques necessary to capture nearly intact, uncontaminated cosmic and interplanetary dust particles (IDP's). Successful capture of such particles will benefit the exobiology and planetary science communities by providing particulate samples that may have survived unaltered since the formation of the solar system. Characterization of these particles may contribute fundamental data to our knowledge of how these particles could have formed into our planet Earth and, perhaps, contributed to the beginnings of life. The term 'uncontaminated' means that captured cosmic and IDP particles are free of organic contamination from the capture process and the term 'nearly intact capture' means that their chemical and elemental components are not materially altered during capture. The key to capturing cosmic and IDP particles that are organic-contamination free and nearly intact is the capture medium. Initial screening of capture media included organic foams, multiple thin foil layers, and aerogel (a silica gel); but, with the exception of aerogel, the requirements of no contamination or nearly intact capture were not met. To ensure no contamination of particles in the capture process, high-purity aerogel was chosen. High-purity aerogel results in high clarity (visual clearness), a useful quality in detection and recovery of embedded captured particles from the aerogel. P. Tsou at the Jet Propulsion Laboratory (JPL) originally described the use of aerogel for this purpose and reported laboratory test results. He has flown aerogel as a 'GAS-can Lid' payload on STS-47 and is evaluating the results. The Timeband Capture Cell Experiment (TICCE), a Eureca 1 experiment, is also flying aerogel and is scheduled for recovery in late April.
Refractory inclusions or Ca-Al-rich inclusions (CAI's) from carbonaceous chondrites span a wide range of bulk compositions that cannot be explained either by segregation from a gas of solar composition at different points in the condensation sequence or by fractional crystallization from a parent liquid. CAI's are commonly rimmed by Wark-Lovering (W-L) rims, a series of nearly monomineralic layers that have been a source of controversy since the variety of rim sequences occurring on different types of CAI's from Allende were described. The origin of these distinctive features has not yet been resolved, with proponents of accretion, condensation, flash heating, ablation, evaporation, etc. Rims have generated considerable interest because they potentially contain clues to conditions experienced by CAI's after the formation of the inclusion and prior to incorporation into the parent body. Ceramic bricks in contact with hot steel slag may produce reaction products in rimlike fashion similar to those found in CAI's. The similarity between the mineralogy of blast furnace slags and CAI's has long been recognized, with both containing unusual phases not found in terrestrial materials. We provide here a comparison between a ceramic brick/slag multiple-layered interface and a multiple-layered interface between a melilite-perovskite object and a melilite-spinel object in the Allende inclusion USNM 4691-1. These results have implications in interpreting the origin of rims and the textures and compositions of CAI's.
In order to gain knowledge about the potential contributions of comets and cosmic dust to the origin of life on Earth, we need to explore the survivability of their potential organic compounds on impact and the formation of secondary products that may have arisen from the chaotic events sustained by the carriers as they fell to Earth. We have performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, kerogens, PAH crystals, and Murchison and Nogoya meteorites) into Al plate targets at velocities - 6 km/s. Estimated peak shock pressures probably did not exceed 120 GPa and peak shock temperatures were probably less than 4000 K for times of nano- to microsecs. Nominal crater dia. are less than one mm. The most significant results of these experiments are the preservation of the higher mass PAHs (e. g., pyrene relative to napthalene) and the formation of additional alkylated PAHs. We have also examined the residues of polystyrene projectiles impacted by a microparticle accelerator into targets at velocities up to 15 km/s. This talk will discuss the results of these experiments and their implications with respect to the survival of carbonaceous deliverables to early Earth. The prospects of survivability of organic molecules on "intact" capture of cosmic dust in space via soft: and hard cosmic dust collectors will also be discussed.
Results of calculations performed to determine the conditions necessary for producing the opaque rims on chondrules and CAI rims by high-speed entry into the transient atmosphere of an accreting meteorite parent body are presented. The sensitivity of these results to variations in critical parameters is investigated. The range of entry velocities which can produce such rims is shown to depend on the size, melting temperature, and thermal conductivity of the particles. For particles greater than 2 mm in radius, with thermal conductivities of 20,000 ergs/sm s K or lower, entry velocities of about 3 km/s suffice. For particle sizes less than 1 mm in radius, the range of encounter velocities that can produce rims is narrow or vanishing, regardless of the thermal conductivity, unless the melting temperature in the outer part of the chondrule has been reduced by compositional heterogeneity.
We performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, fullerenes, phthalic acid crystals, and Murchison meteorite) into Al plate at velocities between 4.2 and 6.1 km/s. These tests were made to do the following: (1) determine the survivability of carbon forms and organize molecules in low hypervelocity impact; (2) characterize carbonaceous impactor residues; and (3) determine whether or not fullerenes could form from carbonaceous impactors, under our experimental conditions, or survive as impactors. An analytical protocol of field emission SEM imagery, SEM-EDX, laser Raman spectroscopy, single and 2-stage laser mass spectrometry, and laser induced fluorescence (LIF) found the following: (1) diamonds did not survive impact at 4.8 km/s, but were transformed into various forms of disordered graphite; (2) intact, well-ordered graphite impactors did survive impact at 5.9 km/sec, but were only found in the crater bottom centers; the degree of impact-induced disorder in the graphite increases outward (walls, rims, ejecta); (3) phthalic acid crystals were destroyed on impact (at 4.2 km/s, although a large proportion of phthalic acid molecules did survive impact); (4) fullerenes did not form as products of carbonaceous impactors (5.9 - 6.1 km/s, fullerene impactor molecules mostly survived impact at 5.9 km/s; and (5) two Murchison meteorite samples (launched at 4.8 and 5.9 km/s) show preservation of some higher mass polycyclic aromatic hydrocarbons (PAHs) compared with the non-impacted sample. Each impactor type shows unique impactor residue morphologies produced at a given impact velocity. An expanded methodology is presented to announce relatively new analytical techniques together with innovative modifications to other methods that can be used to characterize small impact residues in LDEF craters, in addition to other acquired extraterrestrial samples.
Initial analyses of the geologic setting, petrology, and geochemistry of glasses recovered from within and around the elongate Rio Cuarto (RC) craters in Argentina focused on selected samples in order to document the general similarity with impactites around other terrestrial impact craters and to establish their origin. Continued analysis has surveyed the diversity in compositions for a range of samples, examined further evidence for temperature and pressure history, and compared the results with experimentally fused loess from oblique hypervelocity impacts. These new results not only firmly establish their impact origin but provide new insight on the impact process.
Experiments dedicated to the detection of interplanetary dust particles (IDP's) were exposed within the FRECOPA payload, installed on the face of the LDEF directly opposed to the velocity vector (west facing direction, location B3). We were mainly interested in the analysis of hypervelocity impact features of sizes less than or = 10 microns, found in thick Al targets devoted to the research of impact features. In the 15 craters found in the scanned area (approximately 4 sq. cm), the chemical analysis suggests an extraterrestrial origin for the impacting particles. The main elements we identified are usually refered to as chondrite elements: Na, Mg, Si, S, Ca, and Fe are found in various proportions, intrinsic Al being masked by the Al target; we notice a strong depletion in Ni, never observed in our samples. Furthermore, C and O are present in 90 percent of the cases; the C/O peak height ratio varies from 0.1 to 3. Impactor simulations by light gas gun hypervelocity impact experiments have shown that meaningful biogenic element and compound information maybe obtained from IDP residues below impacts of critical velocities, that are less than or = 4 km/sec for particles larger than 100 microns in diameter. Our results obtained for the smaller size fraction IDP's suggest that at such sizes, the critical velocity could be higher by a factor of 2 or 3, as chemical analysis of the remnants were possible in all the identified impact craters, performed on targets possibly hit at velocities greater than or = 7.5 km/s, which is the spacecraft velocity. These samples are now subjected to an imagery and analytical protocol that includes FESEM (field emission scanning electron microscopy) and LIMS (laser ionization mass spectrometry). The LIMS analyses were performed using the LIMA-ZA instrument. Results are presented, clearly indicating that such small events show crater features analogous to what is observed at larger sizes; our first analytical results, obtained for 2 events (P6 and P10) suggest that N is present in the IDP's remnants in which C and O were identified by EDX analysis. In one case (P6), enrichment in K and P is observed. Surface contamination by NaCl is evident on the FRECOPA surfaces.