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NASA NTRS1992

Ruthenium/Iridium Ratios in the Cretaceous-tertiary Boundary Clay: Implications for Global Dispersal and Fractionation Within the Ejecta Cloud

Ruthenium (Ru) and iridium (Ir) are the least mobile platinum group elements (PGE's) within the Cretaceous-Tertiary (K-T) boundary clay (BC). The Ru/Ir ratio is, therefore, the most useful PGE interelement ratio for distinguishing terrestrial and extraterrestrial contributions to the BC. The Ru/Ir ratio of marine K-T sections (1.77 +/- 0.53) is statistically different from that of the continental sections (0.93 +/- 0.28). The marine Ru/Ir ratios are chondritic (C1 = 1.48 +/- 0.09), but the continental ratios are not. We discovered an inverse correlation of shocked quartz size (or distance from the impact site) and Ru/Ir ratio. This correlation may arise from the difference in Ru and Ir vaporization temperature and/or fractionation during condensation from the ejecta cloud. Postsedimentary alteration, remobilization, or terrestrial PGE input may be responsible for the Ru/Ir ratio variations within the groups of marine and continental sites studied. The marine ratios could also be attained if approximately 15 percent of the boundary metals were contributed by Deccan Trap emissions. However, volcanic emissions could not have been the principal source of the PGE's in the BC because mantle PGE ratios and abundances are inconsistent with those measured in the clay. The Ru/Ir values for pristine Tertiary mantle xenoliths (2.6 +/- 0.48), picrites (4.1 +/- 1.8), and Deccan Trap basalt (3.42 +/- 1.96) are all statistically distinct from those measured in the K-T BC.

Evans, Noreen Joyce↗

NASA NTRS1992

Impact origin of the Sudbury structure: Evolution of a theory

This paper reviews the origin, development, and present status of the widely accepted theory, proposed by Robert S. Dietz in 1962, that the Sudbury structure was formed by meteoritic or asteroidal impact. The impact theory for the origin of the Sudbury structure seems supported by a nearly conclusive body of evidence. However, even assuming an impact origin to be correct, at least three major questions require further study: (1) the original size and shape of the crater, before tectonic deformation and erosion; (2) the source of the melt now forming the Sudbury Igneous Complex; and (3) the degree, if any, to which the Ni-Cu-platinum group elements are meteoritic. The history of the impact theory illustrates several under-appreciated aspects of scientific research: (1) the importance of cross-fertilization between space research and terrestrial geology; (2) the role of the outsider in stimulating thinking by insiders; (3) the value of small science, at least in the initial stages of an investigation, Dietz's first field work having been at his own expense; and (4) the value of analogies (here, between the Sudbury Igneous Complex and the maria), which although incorrect in major aspects, may trigger research on totally new lines. Finally, the Sudbury story illustrates the totally unpredictable and, by implication, unplannable nature of basic research, in that insight to the origin of the world's then-greatest Ni deposit came from the study of tektites and the Moon.

Lowman, Paul D., Jr.↗

NASA NTRS1997

Large Meteorite Impacts and Planetary Evolution

Topics considered include: Petrography, geochemistry and geochronology; impact-induced hydrothermal base metal mineralization; nickel-and platinum group element -enriched quartz norite in the latest jurassic morokweng impact structure, south Africa; extraterrestrial helium trapped in fullerenes in the sudbury; synthetic aperture radar characteristics of a glacially modified meltsheet; the chicxulub seismic experiment; chemical compositions of chicxulub impact breccias; experimental investigation of the chemistry of vaporization of targets in relation to the chicxulub impact; artificial ozone hole generation following a large meteoroid impact into an oceanic site; three dimensional modeling of impactite bodies of popigai impact crater, Russia.

Source record↗

NASA NTRS2003

The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary

The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0.07-0.15) and slightly enriched in Pd and Pt relative to Ir.

Lee, Cin-Ty↗

NASA NTRS2000

Early Archean Spherule Beds-Confirmation of Impact Origin

The oldest record of major impact events on Earth may be a number of early Archean (3.5 to 3.2 Ga) spherule beds that have been identified in the Barberton Greenstone Belt, South Africa. Several field, petrographic, and geochemical criteria distinguish these beds from typical volcanic and clastic sediments. These criteria include the wide geographic distribution of two beds in a variety of depositional environments, the presence of relict quench textures, absence of juvenile volcaniclastic debris within the beds, and extreme enrichment of Ir and other platinum group elements (PGE) as compared to surrounding sediments. Some researchers, however, argued for a terrestrial origin for spherule bed formation, possibly related to volcanism and gold mineralization.

Shukolyukov, A.↗

NASA NTRS2004

Mars chronology: assessing techniques for quantifying surficial processes

Currently, the absolute chronology of Martian rocks, deposits and events is based mainly on crater counting and remains highly imprecise with epoch boundary uncertainties in excess of 2 billion years. Answers to key questions concerning the comparative origin and evolution of Mars and Earth will not be forthcoming without a rigid Martian chronology, enabling the construction of a time scale comparable to Earth's. Priorities for exploration include calibration of the cratering rate, dating major volcanic and fluvial events and establishing chronology of the polar layered deposits. If extinct andor extant life is discovered, the chronology of the biosphere will be of paramount importance. Many radiometric and cosmogenic techniques applicable on Earth and the Moon will apply to Mars after certain baselines (e.g. composition of the atmosphere, trace species, chemical and physical characteristics of Martian dust) are established. The high radiation regime may pose a problem for dosimetry-based techniques (e.g. luminescence). The unique isotopic composition of nitrogen in the Martian atmosphere may permit a Mars-specific chronometer for tracing the time-evolution of the atmosphere and of lithic phases with trapped atmospheric gases. Other Mars-specific chronometers include measurement of gas fluxes and accumulation of platinum group elements (PGE) in the regolith. Putting collected samples into geologic context is deemed essential, as is using multiple techniques on multiple samples. If in situ measurements are restricted to a single technique it must be shown to give consistent results on multiple samples, but in all cases, using two or more techniques (e.g. on the same lander) will reduce error. While there is no question that returned samples will yield the best ages, in situ techniques have the potential to be flown on multiple missions providing a larger data set and broader context in which to place the more accurate dates.

Doran, Peter T.↗

NASA NTRS2003

Early Archean Spherule Beds: Chromium Isotopes Confirm Origin through Multiple Impacts of Projectiles of Carbonaceous Chondrite Type: Comment and Reply

This is a exchange in the form of a comment and a reply in regards to an earlier article. The authors of the original article, consider it likely that virtually all of the projectile will condense with the silicate fraction, resulting in very little platinum group element fractionation in the final ejecta deposit. Further, we find no evidence in the commentator's, (i.e., Glikson), comment to support vapor fractionation. We note that the Pd/Ir ratios of published data on 2.56 Ga Hamersley Basin spherules are all greater than in chondrites, contrary to the assertion by Glikson. This is consistent with relatively high Pd concentrations (and Pd/Ir ratios) in crustal rocks.

Kyte, Frank T.↗

NASA NTRS2020

Isotopic and Microstructural Analyses of Opaque Mineral Assemblages and Their Alteration Products Hosted in a Refractory Inclusion

Calcium-aluminum-rich inclusions (CAIs) hosted in primitive meteorites are the oldest solids formed in the Solar System. Some CAIs contain metal nuggets that are complex assemblages of Fe-Ni alloys, along with rare ultra-refractory metals such as platinum group elements (PGEs), and their alteration products such as magnetite, sulfides, and phosphates. Three possible mechanisms proposed to explain the origin of these metal nuggets include condensation in circumstellar settings, condensation in the solar nebula within the CAI-forming region, or crystallization from immiscible metal-silicate melt. However, secondary alteration processes may have also affected some of these assemblages. Additionally, similar metal assemblages observed in chondrules and chondritic matrix indicate that all of these metal nuggets could share common high-temperature origins. These metal assemblages record early Solar System conditions that are reflected in their distinctive chemical composition, mineralogy and microstructures. Here we report a detailed mineralogical, microstructural and oxygen isotopic study of one such metal assemblage hosted in a CAI to understand the physical and chemical settings in which it formed.

Mane, P.↗

NASA NTRS1986

Lead, platinum and other heavy elements in the primary cosmic radiation: HEAO-3 results

An observation of the abundances of cosmic-ray lead and platinum-group nuclei using data from the HEAO-3 Heavy Nuclei Experiment (HNE) which consisted of ion chambers mounted on both sides of a plastic Cherenkov counter (Binns et al., 1981) is reported. Further analysis with more stringent selections, inclusion of additional data, and a calibration at the LBL Bevalac, have allowed the determination of the abundance ratio of lead and the platinum group of elements for particles that had a cutoff rigidity R(c) 5 GV. The observed ratio for Pb/Pt is distinctly lower than that predicted by any of the standard models for cosmic ray sources. It is possible that the difference is not an indication that the cosmic ray source composition is greatly different from that of the solar system, but rather that there is less Pb in the solar system and in the r-process than is assumed in the standard models.

Waddington, C. J.↗

NASA NTRS1985

Lead, platinum, and other heavy elements in the primary cosmic radiation: HEAO-3 results ssc wg032961 cb553097

Waddington, C. J.↗

NASA NTRS1982

The abundance of the actinides in the cosmic radiation as measured on HEAO 3

The HEAO 3 detector of heavy cosmic-ray nuclei has observed one possible actinide nucleus and some 100 nuclei of the platinum-lead group of elements. The resulting upper limit of 3% for the abundance ratio of actinides to platinum-lead nuclides is significantly lower than previous results from other observations. This new limit is inconsistent with freshly synthesized, pure r-process sources for cosmic-ray nuclei in this charge interval but is consistent with a source having a composition similar to the solar system, or to aged r-process material. We observe no events with a charge greater than 96.

Binns, W. R.↗

NASA NTRS1988

Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components

Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary.

Margolis, S. V.↗

NASA NTRS1985

Lead, platinum, and other heavy elements in the primary cosmic radiation - HEAO 3 results

An observation of the abundances of cosmic-ray lead-group and platinum-group nuclei is reported, using data from the HEAO 3 Heavy Nuclei Experiment. From an analysis of 580 days of exposure, 322 nuclei were selected with reasonable charge resolution, E at least 1.3 GeV/nucleon and Z at least 50. The data show a defined abundance peak in the 'platinum' region (Z from 74 to 80), a small abundance of 'lead' (Z from 81 to 83), and a significant number of 'secondary' nuclei in the range of Z between 62 and 73. Possible explanations are offered for the deduced ratio in space of 0.25 plus or minus 0.09 for 'Pb/Pt' being distinctly lower than that predicted by any of the standard models for cosmic-ray sources and propagation effects.

Binns, W. R.↗

NASA NTRS1960

Oxidation Behavior of Binary Niobium Alloys

This investigation concludes a study to determine the effects of up to 25 atomic percent of 55 alloying additions on the oxidation characteristics of niobium. The alloys were evaluated by oxidizing in an air atmosphere for 4 hours at 1000 C and 2 hours at 1200 C. Titanium and chromium improved oxidation resistance at both evaluation conditions. Vanadium and aluminum improved oxidation resistance at 1000 C, even though the V scale tended to liquefy and the Al specimens became brittle and the scale powdery. Copper, cobalt, iron, and iridium improved oxidation resistance at 1200 C. Other investigations report tungsten and molybdenum are protective up to about 1000 C, and tantalum at 1100 C. The most important factor influencing the rate of oxidation was the ion size of the alloy additions. Ions slightly smaller than the Nb(5+) ion are soluble in the oxide lattice and tend to lower the compressive stresses in the bulk scale that lead to cracking. The solubility of the alloying addition also depends on the valence to some extent. All of the elements mentioned that improve the oxidation resistance of Nb fit this size criterion with the possible exception of Al, whose extremely small size in large concentrations would probably lead to the formation of a powdery scale. Maintenance of a crack-free bulk scale for as long as possible may contribute to the formation of a dark subscale that ultimately is rate- controlling in the oxidation process. The platinum-group metals, especially Ir, appear to protect by entrapment of the finely dispersed alloying element by the incoming Nb2O5 metal-oxide interface. This inert metallic Ir when alloyed in a sufficient amount with Yb appears to give a ductile phase dispersed in the brittle oxide. This scale would then flow more easily to relieve the large compressive stresses to delay cracking. Complex oxide formation (which both Ti and Zr tend to initiate) and valence effects, which probably change the vacancy concentration in the scale, are masked by the overriding tendency for a porous scale.

Barrett, Charles A.↗

NASA NTRS2016

Platinum Partitioning at Low Oxygen Fugacity: Implications for Core Formation Processes

Highly siderophile elements (HSE = Au, Re, and the Pt-group elements) are tracers of silicate / metal interactions during planetary processes. Since most core-formation models involve some state of equilibrium between liquid silicate and liquid metal, understanding the partioning of highly siderophile elements (HSE) between silicate and metallic melts is a key issue for models of core / mantle equilibria and for core formation scenarios. However, partitioning models for HSE are still inaccurate due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variable like temperature, pressure, and oxygen fugacity. In this abstract, we describe a self-consistent set of experiments aimed at determining the valence of platinum, one of the HSE, in silicate melts. This is a key information required to parameterize the evolution of platinum partitioning with oxygen fugacity.

Medard, E.↗

NASA NTRS1990

Heavy Nucleus Collector (HNC) project for the NASA Long Duration Exposure Facility (LDEF)

The primary goal of the heavy nucleus collector (HNC) experiment was to obtain high resolution composition measurements for cosmic ray nuclei in the platinum-lead and actinide region of the periodic table. Secondary objectives include studies of selected groups of elements of lower charge. These goals were to be realized by orbiting a large area array of dielectric nuclear track detectors in space for several years. In this time sufficient actinide nuclei would be collected to determine the nucleosynthetic age of the cosmic radiation and the relative mix of r- and s-process elements in the cosmic ray source. The detector consists of approximately 50 trays assembled in pressurized canisters. Each tray would contain 8 half-stacks (4 stacks total) and an event thermometer which would record the temperature of each event at the time of exposure. Each stack would contain 7 layers of Rodyne-P, CR-39 and Cronar plastic track detectors interleaved with copper stripping foils. Upon return to Earth, detectors would be removed for analysis. Ultraheavy nuclei would have left tracks through the detector sheets that would be made visible after etching in a hot sodium hydroxide solution.

Tarle, Gregory↗

NASA NTRS2023

Galvanic Protected Anode Materials for Molten Regolith Electrolysis

This effort aimed to explore the use of refractory alloys as long-lifetime electrode materials for use in a molten regolith electrolysis (MRE) reactor, a technology that can produce oxygen (O2) from regolith. To find a material capable of withstanding the high temperatures and corrosive nature of molten regolith, first-principles thermodynamic calculations were performed on platinum group metals in the presence of iron (Fe) and silicon (Si) to determine favorable compositions for resisting unwanted secondary phases that could form on the surface of the material. As a result of these first-principles calculations, the kinetic properties of elements such as aluminum (Al), Fe, and Si can be more easily derived, which would provide insight into the longevity of such a material when used in an MRE reactor. The effort funded by this CIF project mapped the entire phase diagram of platinum group metals, which is beneficial not only to MRE where high temperatures and molten material are present, but also aerospace applications like turbine materials, terrestrial metal processing techniques, and energy storage applications. This project narrowed a broad spectrum of refractory metals down to a small list of alloys that would be able to survive not only the high temperatures of an MRE reactor, but also the thermodynamic forces that would cause inferior alloys to form secondary phases, which would ultimately consume the electrodes of the reactor. This research needs to be followed up with experimental demonstrations of these alloys in an MRE environment.

Kevin Grossman↗

NASA NTRS1984

Platinum group nuggets in deep sea sediments

The existence of iron meteor oblation spheres in deep sea sediments was known for over a century. These spheres generally were believed to be composed of either pure magnetite and wustite or an oxide shell surrounding a NiFe metal core. A large number of 300 micron to 600 micron spheres found were pure oxide spheres, usually containing a solitary 10 micron platinum group nugget (pgn) composed almost entirely of group VIII metals. Twelve PGN's were analyzed and most had chondritic abundances with some depletions that correlate with element volatility. PGN formation by oxidation of a molten metal sphere entering the atmosphere cannot occur if the oxygen abundance in the atmosphere is less than half of its present value. The first appearance of PGN's in the geological record should mark when, in the Earth's history, oxygen rose to this level.

Brownlee, D. E.↗