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Negative thermal ion mass spectrometry of osmium, rhenium, and iridium

This paper describes a technique for obtaining, in a conventional surface ionization mass spectrometer, intense ion beams of negatively charged oxides of Os, Re, and Ir by thermal ionization. It is shown that the principal ion species of these ions are OsO3(-), ReO4(-), and IrO2(-), respectively. For Re-187/Os-187 studies, this technique offers the advantage of isotopic analyses without prior chemical separation of Re from Os.

Creaser, R. A.↗

Diffusion mechanisms in chemical vapor-deposited iridium coated on chemical vapor-deposited rhenium

Radiation-cooled rocket thruster chambers have been developed which use CVD Re coated with CVD Ir on the interior surface that is exposed to hot combustion gases. The Ir serves as an oxidation barrier which protects the structural integrity-maintaining Re at elevated temperatures. The diffusion kinetics of CVD materials at elevated temperatures is presently studied with a view to the prediction and extension of these thrusters' performance limits. Line scans for Ir and Re were fit on the basis of a diffusion model, in order to extract relevant diffusion constants; the fastest diffusion process is grain-boundary diffusion, where Re diffuses down grain boundaries in the Ir overlayer.

Hamilton, J. C.↗

Mobilization of the platinum group elements by low-temperature fluids: Implications for mineralization and the iridium controversy

Geochemical investigations on the widely dispersed Late Proterozoic Acraman impact ejecta horizon and its host marine shales in the Adelaide Geosyncline provide strong evidence for low-temperature mobilization of the platinum group elements (PGE), including Ir. The ejecta horizon was formed when the middle Proterozoic dacitic volcanics in the Gawler Ranges, central South Australia, were impacted by a very large (ca. 4 km) meteorite. The resulting structure, now represented by Lake Acraman, is Australia's largest meteorite impact structure. Debris from the impact was blasted for many hundreds of kilometers, some falling into the shallow sea of the Adelaide Geosyncline, some 300 km to the east of the impact site.

Dowling, Kim↗

Iridium in sediments containing large abundances of Australasian microtektites from DSDP hole 758B in the Eastern Indian Ocean and from DSDP hole 769A in the Sulu Sea

Excess Ir found in sediments at the Cretaceous/Tertiary (K/T) boundary and in other (e.g., Pliocene) sediments from deep sea drilling cores is widely interpreted as evidence of major impact events. The Australasian tektites originated in an impact event approximately 0.77 Ma ago; microtektites have been found in deep-sea sediment cores from throughout the Indian Ocean, the Philippine Sea, and western Pacific Ocean, but Ir has not been previously reported in these horizons. The deep-sea record of tektites is of particular interest, because in contrast to most continental occurrences, the stratigraphy preserves the original depositional position. Recently several cores having exceptionally high contents of Australasian microtektites have been investigated, Glass and Wu found shocked quartz associated with the microtektites. We used neutron activation to determine concentrations of Ir and other elements in two cores bearing microtektites, one from Deep Sea Drilling Project (DSDP) hole 758B in the Eastern Indian Ocean and one from DSDP hole 769A in the Sulu Sea (near Mindanao, Philippines). The sedimentation age for the microtektite layers in core 758B lies between 0.73 - 0.78 Ma and agrees well with the mean laser-fusion Ar-40/Ar-39 age of Australasian tektites of 0.77 +/- 0.02 Ma by Izett et al. We are able to resolve a small positive Ir enhancement in 758B. Core 769A shows too much scatter to allow resolution of an Ir peak.

Schmidt, Gerhard↗

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗

Anomalous Iridium Enrichment at the Triassic-Jurassic Boundary, Blomidon Formation, Fundy Basin, Canada

We present new analyses that confirm Ir enrichment (up to 0.31 ng/g) in close proximity to the palynological Triassic-Jurassic boundary in strata near the top of the Blomidon Formation at Partridge Island, Nova Scotia. High Ir concentrations have been found in at least two samples within the uppermost 70 cm of the formation. Ratios of other PGEs and Au to Ir are generally higher by an order of magnitude than in ordinary chondrites. No impact-related materials have been identified at #is horizon in the Blomidon Formation, therefore we cannot confirm an extraterrestrial source for the anomalous Ir levels. We consider, however, the possibility that regional basaltic volcanism is a potential source for the Ir in these sediments. The elevated Ir concentrations are found in reduced, grey colored mudstones, so redox concentration is a possible explanation for the distribution of Ir in these strata.

Kyte, Frank T.↗

Studies of noble-metal thermocouple stability at high temperatures

Two investigatory studies on performance characteristics of noble-metal thermocouples are described. (1) thermoelectric stability as affected by preferential oxidation of iridium in the system iridium-40% rhodium versus iridium, and (2) the effects of temperature gradients on the emf stability of the systems platinum-13% rhodium versus platinum and iridium-40% rhodium versus iridium, operating in air. The stability investigation was carried out at three temperatures - 1700, 1850, and 2000 C - by comparing the output of the test thermocouple in air with the output of an identically constructed reference thermocouple in nitrogen. The results show that no calibration shift was observed producing a change in output greater than that corresponding to a 2.0% change in the indicated temperature for all samples tested. The investigation of gradient effects was carried out by subjecting test thermocouples to both severe and mild gradients for periods up to 200 hours. For the platinum system, the operating temperature was 1500 C with gradients of 1475 and 700 C/cm; for the iridium system, 2000 C with gradients of 700, 1500, and 1975 C/cm. Exposure to temperature gradients was found to introduce significant changes in calibration for both systems. In both investigations, the thermoelements were examined by means of electron-probe analysis and by metallographic methods to detect chemical and structural changes. Data and micrographs are presented.

Freeze, P.↗

High-Pressure Lightweight Thrusters

Returning samples of Martian soil and rock to Earth is of great interest to scientists. There were numerous studies to evaluate Mars Sample Return (MSR) mission architectures, technology needs, development plans, and requirements. The largest propulsion risk element of the MSR mission is the Mars Ascent Vehicle (MAV). Along with the baseline solid-propellant vehicle, liquid propellants have been considered. Similar requirements apply to other lander ascent engines and reaction control systems. The performance of current state-ofthe- art liquid propellant engines can be significantly improved by increasing both combustion temperature and pressure. Pump-fed propulsion is suggested for a single-stage bipropellant MAV. Achieving a 90-percent stage propellant fraction is thought to be possible on a 100-kg scale, including sufficient thrust for lifting off Mars. To increase the performance of storable bipropellant rocket engines, a high-pressure, lightweight combustion chamber was designed. Iridium liner electrodeposition was investigated on complex-shaped thrust chamber mandrels. Dense, uniform iridium liners were produced on chamber and cylindrical mandrels. Carbon/carbon composite (C/C) structures were braided over iridium-lined mandrels and densified by chemical vapor infiltration. Niobium deposition was evaluated for forming a metallic attachment flange on the carbon/ carbon structure. The new thrust chamber was designed to exceed state-of-the-art performance, and was manufactured with an 83-percent weight savings. High-performance C/Cs possess a unique set of properties that make them desirable materials for high-temperature structures used in rocket propulsion components, hypersonic vehicles, and aircraft brakes. In particular, more attention is focused on 3D braided C/Cs due to their mesh-work structure. Research on the properties of C/Cs has shown that the strength of composites is strongly affected by the fiber-matrix interfacial bonding, and that weakening interface realizes pseudo-plastic behavior with significant increase in the tensile strength. The investigation of high-temperature strength of C/Cs under high-rate heating (critical for thrust chambers) shows that tensile and compression strength increases from 70 MPa at room temperature to 110 MPa at 1,773 K, and up to 125 MPa at 2,473 K. Despite these unique properties, the use of C/Cs is limited by its high oxidation rate at elevated temperatures. Lining carbon/carbon chambers with a thin layer of iridium or iridium and rhenium is an innovative way to use proven refractory metals and provide the oxidation barrier necessary to enable the use of carbon/ carbon composites. Due to the lower density of C/Cs as compared to SiC/SiC composites, an iridium liner can be added to the C/C structure and still be below the overall thruster weight. Weight calculations show that C/C, C/C with 50 microns of Ir, and C/C with 100 microns of Ir are of less weight than alternative materials for the same construction.

Holmes, Richard↗

Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

Jang, Q.↗

Space Based Communications

Current space lift launches on the Eastern and Western Range require extensive ground-based real-time tracking, communications and command/control systems. These are expensive to maintain and operate and cover only limited geographical areas. Future spaceports will require new technologies to provide greater launch and landing opportunities, support simultaneous missions, and offer enhanced decision support models and simulation capabilities. These ranges must also have lower costs and reduced complexity while continuing to provide unsurpassed safety to the public, flight crew, personnel, vehicles and facilities. Commercial and government space-based assets for tracking and communications offer many attractive possibilities to help achieve these goals. This paper describes two NASA proof-of-concept projects that seek-to exploit the advantages of a space-based range: Iridium Flight Modem and Space-Based Telemetry and Range Safety (STARS). Iridium Flight Modem uses the commercial satellite system Iridium for extremely low cost, low rate two-way communications and has been successfully tested on four aircraft flights. A sister project at Goddard Space Flight Center's (GSFC) Wallops Flight Facility (WFF) using the Globalstar system has been tested on one rocket. The basic Iridium Flight Modem system consists of a L1 carrier Coarse/Acquisition (C/A)-Code Global Positioning System (GPS) receiver, an on-board computer, and a standard commercial satellite modem and antennas. STARS uses the much higher data rate NASA owned Tracking and Data Relay Satellite System (TDRSS), a C/A-Code GPS receiver, an experimental low-power transceiver, custom built command and data handler processor, and digitized flight termination system (FTS) commands. STARS is scheduled to fly on an F-15 at Dryden Flight Research Center in the spring of 2003, with follow-on tests over the next several years.

Simpson, James↗

Software Tool for Tracking & Mapping the NASA Orion AA-2 Test Flight Ejectable Data Recorders in Real Time

On 2 July 2019, the NASA Ascent Abort 2 flight took place off the Florida coast to test the emergency systems to separate the Orion Crew Module (CM) from the future Space Launch System rocket in the event of a malfunction. During this high-altitude test, instrumentation data was recorded on twelve customized buoyant Ejectable Data Recorders (EDRs) and subsequently jettisoned from the CM in mid-air. Upon release, the EDRs activated their GPS-Iridium beacon systems and began transmitting Short Burst Data (SBD) messages via the Iridium satellite network to relay their individual location and system health information. To locate, track and retrieve each EDR from the ocean surface in real-time, multiple open-source programming tools (Python and Linux shells) were developed for parsing the incoming Iridium binary SBD messages. For this, a Linux laptop was used to receive the Iridium-generated emails containing the SBD messages and autonomously execute the parsing tools. The received SBD data contained location, timestamp and health status information that was translated, saved, and subsequently used for simultaneously generating a continuously updated color-coded tabular display summary and unique KML files used with Google Earth to track their locations. Once their locations were known, dedicated recovery vessels retrieved all EDRs from the ocean. An additional tool was also developed in order to generate 5- and 10-minute geolocation predictions for each EDR by deriving the displacement distance, elapsed time, displacement heading and velocity based on the latest known information available. The recovery vessels were also tracked with the use of a separate commercial GPS beacon system. After jettison, 67% of the EDRs transmitted valid data by the time they were retrieved from the ocean. However, the real-time information presented by the plotting tool allowed for the ready depiction of EDR dispersal patterns and reference drift trajectories, which contributed to the recovery of all twelve EDRs and the AA-2 flight data. Lastly, the available data showed that the distance between the software’s reported drift/predicted locations and the recovery locations did not exceed 38 meters, therefore demonstrating the advantages of this software tool for supporting real-time tracking and recovery efforts of beacon devices.

Moxey, Lucas↗

Extraterrestrial cause for the Cretaceous-Tertiary extinction

Direct physical evidence is presented for an unusual event at exactly the time of extinctions in the planktonic realm. Deep-sea limestones exposed in Italy, Denmark, and New Zealand indicate iridium increases of about 30, 160, and 20 times, respectively, above the background level at precisely the time of the Cretaceous-Tertiary extinctions, 65 million years ago. Reasons are given that this iridium is of extraterrestrial origin, but did not come from a nearby supernova. A hypothesis is set forth which accounts for the extinctions and the iridium observations. One prediction of this hypothesis is verified, that the chemical composition of the boundary clay, which is thought to come from the stratospheric dust, is markedly different from that of clay mixed with the chemically similar Cretaceous and Tertiary limestones.

Alvarez, L. W.↗

High-temperature oxidation of a rapidly solidified amorphous Ta-Ir alloy

The oxidation products formed at 500 and 700 C on an amorphous Ta-44.5 at. pct Ir alloy in an Ar-0.1 percent O2 gas mixture were characterized using SEM, XRD, EPMA, TEM, STEM, AES, and XPS. Initially, a thin (3-4 nm) layer of Ta2O5 formed at the surface of the alloy. Continued growth of the Ta2O5, which occurred very rapidly, involved diffusion of oxygen anions from the Ta2O5/gas interface to the alloy/Ta2O5 interface, where tantalum was selectively oxidized. Because the oxide grew more quickly than iridium could diffuse back into the alloy, the iridium coalesced into platelets of crystalline iridium-rich alloy that were oriented approximately parallel to the oxide/alloy interface, and which became embedded in a matrix of Ta2O5. The unoxidized core remained in the glassy state. The oxidation process and/or the dissolution of oxygen into the unoxidized alloy caused the alloy to become embrittled.

Cotell, Catherine M.↗

Geochemistry of K/T boundaries in India and contributions of Deccan volcanism

Three possible Cretaceous/Tertiary (K/T) boundary sections in the Indian subcontinent were studied for their geochemical and fossil characteristics. These include two marine sections of Meghalaya and Zanskar and one continental section of Nagpur. The Um Sohryngkew river section of Meghalaya shows a high iridium, osmium, iron, cobalt, nickel and chromium concentration in a 1.5 cm thick limonitic layer about 30 cm below the planktonic Cretaceous-Palaeocene boundary identified by the characteristic fossils. The Bottaccione and Contessa sections at Gubbio were also analyzed for these elements. The geochemical pattern at the boundary at the Um Sohryngkew river and Gubbio sections are similar but the peak concentrations and the enrichment factors are different. The biological boundary is not as sharp as the geochemical boundary and the extinction appears to be a prolonged process. The Zanskar section shows, in general, similar concentration of the siderophile, lithophile and rare earth elements but no evidence of enrichment of siderophiles has so far been observed. The Takli section is a shallow inter-trappean deposit within the Deccan province, sandwiched between flow 1 and flow 2. The geochemical stratigraphy of the inter-trappeans is presented. The various horizons of ash, clay and marl show concentration of Fe and Co, generally lower than the adjacent basalts. Two horizons of slight enrichment of iridium are found within the ash layers, one near the contact of flow 1 and other near the contact of flow 2, where iridium occurs at 170 and 260 pg/g. These levels are lower by a factor of 30 compared to Ir concentration in the K/T boundary in Meghalaya section. If the enhanced level of some elements in a few horizons of the ash layer are considered as volcanic contribution by some fractionation processes than the only elements for which it occurs are REE, Ir and possibly Cr.

Bhandari, N.↗

Search for the Tunguska event in the Antarctic snow

The Tunguska explosion in 1908 is supposed to have been produced by the impact of a small celestial body. The absence of any identifiable crater together with the huge energy released by the event suggest that the impactor exploded in midair and that its material was widely spread over the Earth. The short term contribution of such exceptional events to the total accretion rate of extraterrestrial material by the Earth could be significant. Samples were chosen in a core electromechanically drilled in 1984 near South Pole Station. There, the low temperatures, preventing melting all year long, and the nearly regular snow fall rate provide good conditions for a reliable continuous record of any infalling material. In many samples Ir was below the detection limit of the instrumentation. The iridium infall averaged over 45 samples is given. In a few samples the iridium content is significantly higher than the average: the frequency and amplitude of such fluctuations can be explained by the presence on some filters of finite size cosmic particles. No significant systematic increase above the average level is observed in the part of the core corresponding to the Tunguska event. The two major results of this study are: (1) The presence of Tunguska explosion debris in the Antarctic snow is not confirmed; and (2) The estimate of the average iridium infall, is an order of magnitude lower than the Ganapathy's background but is close to the values measured in Antarctic snow and atmospheric samples by Takahashi et al. The results are also consistent with the flux of micrometeoroids deduced from optical and radar observations or derived from the study of Greenland cosmic dust collection but are lower than the flux at mid-latitude measured in paleocene-oligocene sediments from the central part of the Pacific Ocean.

Rocchia, R.↗