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NASA NTRS1989

Platinum group elements in a 3.5 Ga nickel-iron occurrence - Possible evidence of a deep mantle origin

This paper reports the results of new field observations and the geochemical analyses for the area of the Bon Accord (BA) (the Kaapvaal craton, South Africa) Ni-Fe deposit, with particular consideration given to the trace element, platinum-group element, and isotopic (Pb, Nd, and Os) compositions. On the basis of these data, an interpretation of BA is suggested, according to which the BA deposit is a siderophile-rich heterogeneity remaining in the deep mantle after a process of incomplete core formation. The implications of such a model for the study of core-mantle segregation and the geochemistry of the lowermost mantle are discussed.

Tredoux, Marian↗

NASA NTRS2005

Osmium-Isotope and Platinum-Group-Element Systematics of Impact-Melt Rocks, Chesapeake Bay Impact Structure, Virginia, USA

Osmium (Os) isotopes and platinum-group elements (PGEs) are useful for geochemically identifying a meteoritic component within impact structures, because meteorites are typically characterized by low (187)Os/(188)Os ratios and high PGE concentrations. In contrast, most types of crustal target rocks have high radiogenic Os and very low PGE concentrations. We have examined Os isotope and PGE systematics of impact-melt rocks and pre-impact target rocks from a 2004 test hole in the late Eocene Chesapeake Bay impact structure and from nearby coreholes. Our goal is to determine the proportion of the projectile component in the melt rock Additional information is included in the original extended abstract.

Lee, Seung Ryeol↗

NASA NTRS2003

Platinum-group elements (PGE) and Rhenium in Marine Sediments across the Cretaceous-Tertiary Boundary: Constraints on Re-PGE Transport in the Marine Environment

The nature of Re-platinum-group element (PGE; Pt, Pd, Ir, Os, Ru) transport in the marine environment was investigated by means of marine sediments at and across the Cretaceous-Tertiary boundary (KTB) at two hemipelagic sites in Europe and two pelagic sites in the North and South Pacific. A traverse across the KTB in the South Pacific pelagic clay core found elevated levels of Re, Pt, Ir, Os, and Ru, each of which is approximately symmetrically distributed over a distance of approx. 1.8 m across the KTB. The Re-PGE abundance patterns are fractionated from chondritic relative abundances: Ru, Pt, Pd, and Re contents are slightly subchondritic relative to Ir, and Os is depleted by approx. 95% relative to chondritic Ir proportions. A similar depletion in Os (approx. 90%) was found in a sample of the pelagic KTB in the North Pacific, but it is enriched in Ru, Pt, Pd, and Re relative to Ir. The two hemipelagic KTB clays have near-chondritic abundance patterns. The approx. 1.8-m-wide Re-PGE peak in the pelagic South Pacific section cannot be reconciled with the fallout of a single impactor, indicating that postdepositional redistribution has occurred. The elemental profiles appear to fit diffusion profiles, although bioturbation could have also played a role. If diffusion had occurred over approx. 65 Ma, the effective diffusivities are approx. 10(exp -13)sq cm/s, much smaller than that of soluble cations in pore waters (approx. 10(exp -5) sq cm/s). The coupling of Re and the PGEs during redistribution indicates that postdepositional processes did not significantly fractionate their relative abundances. If redistribution was caused by diffusion, then the effective diffusivities are the same. Fractionation of Os from Ir during the KTB interval must therefore have occurred during aqueous transport in the marine environment. Distinctly subchondritic Os/Ir ratios throughout the Cenozoic in the South Pacific core further suggest that fractionation of Os from Ir in the marine environment is a general process throughout geologic time because most of the inputs of Os and Ir into the ocean have OsAr ratios greater than or = 1. Mass balance calculations show that Os and Re burial fluxes in pelagic sediments account for only a small fraction of the riverine Os (less than 10%) and Re (less than 0.1%) inputs into the oceans. In contrast, burial of Ir in pelagic sediments is similar to the riverine Ir input, indicating that pelagic sediments are a much larger repository for Ir than for Os and Re. If all of the missing Os and Re is assumed to reside in anoxic sediments in oceanic margins, the calculated burial fluxes in anoxic sediments are similar to observed burial fluxes. However, putting all of the missing Os and Re into estuarine sediments would require high concentrations to balance the riverine input and would also fail to explain the depletion of Os at pelagic KTB sites, where at most approx. 25% of the K-T impactor's Os could have passed through estuaries. If Os is preferentially sequestered in anoxic marine environments, it follows that the OsAr ratio of pelagic sediments should be sensitive to changes in the rates of anoxic sediment deposition. There is thus a clear fractionation of Os and Re from Ir in precipitation out of sea water in pelagic sections. Accordingly, it is inferred here that Re and Os are removed from sea water in anoxic marine depositional regimes.

Lee, Cin-Ty Aeolus↗

NASA NTRS1992

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↗

NASA NTRS2000

Comparison of Os and Cr Isotopic Methods for the Detection of Meteoritic Components in Impact Melt Rocks from the Morokweng and Vredefort Impact Structures, South Africa

The verification of an extraterrestrial component in impact-derived melt rocks or breccias can be of diagnostic value to provide confirming evidence for an impact origin of a geological structure. Geochemical methods are used to determine the presence of the traces of such a component. In the absence of actual meteorite fragments, it is necessary to search for traces of meteoritic material that is mixed in with the target rocks in breccias and melt rocks. Meteoritic components have been identified for just over 40 impact structures (out of more than 160 known on Earth), which reflects also the detail in which these structures were studied. The identification of a meteoritic component can be achieved by determining the concentrations and interelement ratios of siderophile elements, especially the platinum group elements (PGE), which are several orders of magnitude more abundant in meteorites than in terrestrial upper crustal rocks. The usage of platinum group element abundances and ratios avoids some of the ambiguities that may result if only common siderophile elements (e.g., Cr, Co, Ni) are considered. However, problems may arise if the target rocks have high abundances of siderophile elements, or if the siderophile element concentrations in the impactites are very low. In such cases, the Os and Cr isotopic systems have recently been used for establishing the presence of a meteoritic component in a number of impact melt rocks and breccias. In the past it was attempted to use PGE data to determine the type or class of meteorite for the impactor, but these attempts were not always successful. It is difficult to decide between chondrite types based on PGE abundances, which has led to conflicting identifications for a number of impact structures. Clearly, the identification of a meteoritic component in impactites is not a trivial problem. In this study, we are using a combination of trace element (PGE) analyses and the results from both, Os and Cr isotopic studies, to illustrate the pros and cons of each method on two case studies, namely the Vredefort and Morokweng impact structures. Additional information is contained in the original extended abstract.

Koeberl, Christian↗

NASA NTRS1989

Rhenium-osmium and samarium-neodymium isotopic systematics of the Stillwater complex

The role of magma mixing in the formation of strategic platinum-group element ore deposits is examined using isotopic data from the Stillwater Complex, Montana. Nd and Os isotopic data show that the intrusion formed from at least two distinct magmas: ultramafic (U-type) affinity magmas and anorthositic (A-type) affinity magmas. The U-type magmas formed from a lithospheric mantle source containing recycled crustal materials and the A-type magmas originated either by crustal contamination of basaltic magmas or by partial melting of basalt in the lower crust. The results also suggest that the platinum-group element ore deposits were derived from A-type magmas which were injected into the U-type magma chamber at several stages during the development of the ultramafic series.

Lambert, David D.↗

NASA NTRS2003

Tracers of the Extraterrestrial Component in Sediments and Inferences for Earth's Accretion History

The study of extraterrestrial matter in sediments began with the discovery of cosmic spherules during the HMS Challenger Expedition (1873-1876), but has evolved into a multidisciplinary study of the chemical, physical, and isotopic study of sediments. Extraterrestrial matter in sediments comes mainly from dust and large impactors from the asteroid belt and comets. What we know of the nature of these source materials comes from the study of stratospheric dust particles, cosmic spherules, micrometeorites, meteorites, and astronomical observations. The most common chemical tracers of extraterrestrial matter in sediments are the siderophile elements, most commonly iridium and other platinum group elements. Physical tracers include cosmic and impact spherules, Ni-rich spinels, meteorites, fossil meteorites, and ocean-impact melt debris. Three types of isotopic systems have been used to trace extraterrestrial matter. Osmium isotopes cannot distinguish chondritic from mantle sources, but provide a useful tool in modeling long-term accretion rates. Helium isotopes can be used to trace the long-term flux of the fine fraction of the interplanetary dust complex. Chromium isotopes can provide unequivocal evidence of an extraterrestrial source for sediments with high concentrations of meteoritic Cr. The terrestrial history of impacts, as recorded in sediments, is still poorly understood. Helium isotopes, multiple Ir anomalies, spherule beds, and craters all indicate a comet shower in the late Eocene. The Cretaceous-Tertiary boundary impact event appears to have been caused by a single carbonaceous chondrite projectile, most likely of asteroid origin. Little is known of the impact record in sediments from the rest of the Phanerozoic. Several impact deposits are known in the Precambrian, including several possible mega-impacts in the Early Archean.

Kyte, Frank T.↗

NASA NTRS2007

Partitioning of Pd Between Fe-S-C and Mantle Liquids at High Pressure and Temperature: Implications for Core Formation

One of the most elusive geochemical aspects of the early Earth has been explaining the near chondritic relative abundances of the highly siderophile elements (HSE; Au, Re and the platinum group elements) in Earth's primitive upper mantle (PUM). Perhaps they were delivered to the Earth after core formation, by late addition of carbonaceous chondrite material. However, the recognition that many moderately siderophile elements can be explained by high pressure and temperature (PT) metal-silicate equilibrium, leads to the question whether high PT equilibrium can also explain the HSE concentrations. Answers to this question have been slowed by experimental difficulties (nugget effect and very low solubilities). But two different perspectives have emerged from recent studies. One perspective is that D(M/S) for HSE at high PT are not low enough to explain terrestrial mantle depletions of these elements (for Pd and Pt). A second perspective is D(M/S) are reduced substantially at high PT and even low enough to explain terrestrial mantle depletions (for Au and Pt). Issues complicating interpretation of all experiments include use of MgO- and FeO-free silicate melts, and S-free and FeNi metal-free systems. In addition, conclusions for Pt rest on an interpretation that the tiny metallic nuggets plaguing many such experiments, were formed upon quench. There is not agreement on this issue, and the general question of HSE solubility at high PT remains unresolved

Righter, K.↗

NASA NTRS2009

Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation during late fractional crystallization. These results show that shergottite HSE contents are controlled by silicates, oxides, and sulfides. In addition, the mantle producing the most primitive shergottites did not contain near chondritic relative ratios of the HSEs like the terrestrial mantle, and did not experience a late chondritic veneer.

Righter, Kevin↗

NASA NTRS2011

High Pressure and Temperature Core Formation as an Alternative to the "Late Veneer" Hypothesis

The highly siderophile elements (HSE; Re, Au and the Platinum Group Elements - Pd Pt, Rh, Ru, Ir, Os) are commonly utilized to constrain accretion processes in terrestrial differentiated bodies due to their affinity for FeNi metal [1]. These eight elements exhibit highly siderophile behavior, but nonetheless have highly diverse metal-silicate partition coefficients [2]. Therefore the near chondritic relative concentrations of HSEs in the terrestrial and lunar mantles, as well as some other bodies, are attributed to late accretion rather than core formation [1]. Evaluation of competing theories, such as high pressure metal-silicate partitioning or magma ocean hypotheses has been hindered by a lack of relevant partitioning data for this group of eight elements. In particular, systematic studies isolating the effect of one variable (e.g. temperature or melt compositions) are lacking. Here we undertake new experiments on all eight elements, using Fe metal and FeO-bearing silicate melts at fixed pressure, but variable temperatures. These experiments, as well as some additional planned experiments should allow partition coefficients to be more accurately calculated or estimated at the PT conditions and compositions at which core formation is thought to have occurred.

Righter, Kevin↗

NASA NTRS1989

Abundances of ultraheavy elements in the cosmic radiation - Results from HEAO 3

An analysis is presented that, for the first time, systematically normalizes the data from the HEAO 3 heavy nuclei experiment on the cosmic-ray abundances of all the elements heavier than germanium to that of iron. In the range of atomic number Z from 33 to 60, the analysis yields abundances of odd-even element pairs. The abundances are consistent with a cosmic-ray source having a composition similar to that of the solar system, but subject to source fractionation correlated with the first ionization potential (FIP) of each element. For Z greater than 60, the analysis yields abundances of element groups. For these heaviest nuclei, we find an enhancement of the abundance of the platinum group, elements with Z of 74-80, relative to that in propagated solar system source, and a corresponding increase in the abundance of the largely secondary elements in the 62-73 range. These abundances suggest that there is an enhancement of the r-process contribution to the source nuclei in the Z greater than 60 charge region. Over the entire region of charge, standard leaky box models of propagation satisfactorily model secondary production.

Binns, W. R.↗

NASA NTRS1991

Asteroid 1986 DA: Radar evidence for a metallic composition

Radar observations of the near-Earth asteroid 1986 DA were carried out at the Arecibo Observatory in April 1986, two months after its discovery. Radar results are consistent with the hypothesis that 1986 HA is a piece of NiFe metal derived from the interior of a much larger object that melted, differentiated, cooled and subsequently was disrupted in a catastrophic collision. This 2-km asteroid might be (or have been part of) the parent body of some iron meteorites. Or 1986 DA might share the parentage and/or part of the dynamical history of some meteorites without ever having contributed any of its own ejecta to our meteorite sample. Analysis of the samples returned from 1986 DA might ultimately involve economic considerations. Meteoritic metal is mostly iron with about 8 percent nickel, but also contains substantial concentrations of precious and strategic metals, including approx. 1 ppm of gold and approx. 10 ppm of platinum group elements. If these abundances apply to 1986 DA, it contains some 10(exp 16) g of iron, 10 (exp 15) g of nickel, 10(exp 11) g of platinum group metals, and 10(exp 10) g of gold.

Ostro, Steven J.↗

NASA NTRS1988

Geochemical comparison of K-T boundaries from the Northern and Southern Hemispheres

Closely spaced (cm-scale) traverses through the K-T boundary at Stevns Klint (Denmark), Woodside Creek (New Zealand) and a new Southern Hemisphere site at Richards Bay (South Africa) were subjected to trace element and isotopic (C, O, Sr) investigation. Intercomparison between these data-sets, and correlation with the broad K-T database available in the literature, indicate that the chemistry of the boundary clays is not globally constant. Variations are more common than similarities, both of absolute concentrations, and interelement ratios. For example, the chondrite normalized platinum-group elements (PGE) patterns of Stevns Klint are not like those of Woodside Creek, with the Pt/Os ratios showing the biggest variation. These differences in PGE patterns are difficult to explain by secondary alteration of a layer that was originally chemically homogeneous, especially for elements of such dubious crustal mobility as Os and Ir. The data also show that enhanced PGE concentrations, with similar trends to those of the boundary layers, occur in the Cretaceous sediments below the actual boundary at Stevns Klint and all three the New Zealand localities. This confirms the observations of others that the geochemistry of the boundary layers apparently does not record a unique component. It is suggested that terrestrial processes, eg. an extended period of Late Cretaceous volcanism can offer a satisfactory explanation for the features of the K-T geochemical anomaly. Such models would probably be more consistent with the observed stepwise, or gradual, palaeontological changes across this boundary, than the instant catastrophe predicated by the impact theory.

Tredous, M.↗

NASA NTRS1984

Extraterrestrial platinum group nuggets in deep-sea sediments

A previously unrecognized property of iron cosmic spheres is reported. The most common spheres larger than 300 microns do not, in fact, contain FeNi metal cores, but instead contain a micrometer-sized nugget composed almost entirely of platinum group elements. These elements appear to have been concentrated by the oxidation of molten meteoritic metal during atmospheric entry. This process is critically dependent on the relative abundance of oxygen in the atmosphere, and the first appearance of the nuggets in the geological record may provide a marker indicating when the oxygen abundance attained half of its present level.

Brownlee, D. E.↗

NASA NTRS1988

Deccan volcanism at the Cretaceous-Tertiary boundary

The accuracy with which one can claim that Deccan trap volcanism occurred at the Cretaceous-Tertiary boundary (KTB) over a very short time interval is of key importance in deciding whether a volcanic origin of the KTB events should be taken seriously. In the two years since paleomagnetic, paleontological and geodynamic evidence was published, further data have become available and the case now appears to be well constrained. The Ar-40/Ar-39 results from six labs have yielded some 24 reliable plateau ages that narrow the age range to 65 to 69 Ma. Moreover, it appears that a significant part of this range results from inter-lab spread and possible minor alteration. Paleontology demonstrates that volcanism started in the Maestrichtian, more precisely in the A. mayaroensis zone. Paleomagnetism shows that volcanism spanned only 3 chrons and only one correlation remains possible, that of the main central reversed chron with 29R. Therefore, whereas Ar-40/Ar-39 is able only to restrict the duration of volcanism to some 4 Ma, paleomagnetism restricts it to 0.5 Ma. Using some geochemical indicators such as C-13 as proxy, it is suggested that volcanism actually consists of a few shorter events of unequal magnitude. Extrusion rates may be as high as 100 cu km/yr and fissure lengths as long as several 100 km. Such a scenario appears to be at least as successful as others in accounting for most anomalies observed at the KTB. Particularly important are Iridium and other platinum group elements (PGE) profiles, Sr-87/Sr-86, C-13, 0-18, other exotic geochemical signatures, spherules, soot, shocked minerals, selective and stepwise extinctions. The environmental impact of CO2 possibly released during explosive phases of volcanism, and SO2 released during effusive phases, and the ability of volcanism to ensure worldwide distribution of KTB products are now all addressed. In conclusion, the case for a causal link between internal hotspot activity, birth of the Reunion hotspot itself as the Deccan and KTB events appears to rest on an increasingly stronger basis.

Courtillot, V.↗

NASA NTRS1988

Noble metals in mid-ocean ridge volcanism: A significant fractionation of gold with respect to platinum group metals

Hydrothermal precipitates, black smoker particulate, and massive sulphide dredge samples from the Explorer Ridge on the Juan de Fuca Plate and the TAG hydrothermal area on the Mid-Atlantic Ridge were analyzed for selected noble metals including Au, Ir and Pd by radiochemical neutron activation analysis. The preliminary results indicate that gold contents may reach the ppm range although values in the neighborhood of 100 to 200 ppb are more typical. The platinum group elements (PGE) represented by Ir and Pd are typically less than 0.02 ppb and less than 2 ppb respectively. These abundances represent a significant enrichment of gold relative to the PGE in comparison with average noble metal abundances in mid-ocean ridge basalts (MORB). A partial explanation of this distinctive fractionation can be found in the concepts of sulfur-saturation of basic magma in mid-ocean ridge (MOR) settings, and the origin of MOR hydrothermal fluids. Experimental and petrological data suggest that MORBs are sulfur-saturated at the time of magma generation and that an immiscible sulfide component remains in the mantle residue. Hence, MORBs are noble metal-poor, particularly with respect to PGE. Consequently, black smoker fluids can be expected to reflect the low Ir and Pd contents of the rock column. The average Au content of MORB is 1.3 ppb, and so the rock column is not significantly enriched in Au. The generation of fluids which precipitate solids with 200 ppb Au is apparently dependent on highly efficient fluid chemistry to mobilize Au from the rock column, high Au solubility in seawater hydrothermal fluids and efficient precipitation mechanisms to coprecipitate Au on Fe, Zn and Cu sulfides. Significant differences in these parameters appear to be the ultimate cause of the strong Au-PGE fractionation in the MOR setting. It does not appear from the current data base that MOR hydrothermal fluids are significant contributors to the Ir enrichment seen in Cretaceous-Tertiary boundary sediments.

Crocket, James H.↗

NASA NTRS1988

Environmental effects of large impacts on the earth; relation to extinction mechanisms

Since Alvarez et al., discovered a worldwide approx. cm-thick layer of fine sediments laden with platinum group elements in approximately chondritic proportions exactly at the Cretaceous-Tertiary (C-T) boundary, and proposed bolide-impact as triggering mass extinctions, many have studied this hypothesis and the layer itself with its associated spherules and shocked quartz. At issue is whether the mass extinctions, and this horizon has an impact versus volcanic origin. A critical feature of the Alvarez hypothesis is the suggestion that the bolide or possibly a shower of objects delivered to the earth approx. 0.6 x 10 to the 18th power g of material which resulted in aerosol-sized ejecta such that global insolation was drastically reduced for significant periods. Such an event would lower temperatures on continents and halt photosynthesis in the upper 200 m of th eocean. The latter would strangle the marine food chain and thus produce the major marine faunal extinctions which mark the C-T boundary. Crucial issues examined include: What are the dynamics of atmospheric flow occurring upon impact of a large bolide with the earth; What is the size distributions of the very fine impact ejecta and how do these compare to the models of ejecta which are used to model the earth's radiative thermal balance. The flow field due to passage of a 10 km diameter bolide through an exponential atmosphere and the interaction of the gas flow and bolide with the solid ear was calculated. The CO2 released upon impact onto shallow marine carbonate sections was modeled and found that the mass of CO2 released exceeds the present 10 to the 18th power g CO2 budget of the earth's atmosphere by several times. Using the calculations of Kasting and Toon it was found that to compute the temperature rise of the earth's surface as a function of CO2 content, it was found that sudden and prolonged global increases are induced from impact of 20 to 50 km radius projectiles and propose that sudden terrestrial greenhouse-induced heating, not cooling, produced the highly variable extinctions seen at the C-T boundary.

Okeefe, John D.↗

NASA NTRS1989

Geological and geochemical record of 3400-million-year-old terrestrial meteorite impacts

Beds of sand-sized spherules in the 3400-million-year-old Fig Tree Group, Barberton Greenstone belt, South Africa, formed by the fall of quenched liquid silicate droplets into a range of shallow- to deep-water depositional environments. The regional extent of the layers, their compositional complexity, and lack of included volcanic debris suggest that they are not products of volcanic activity. The layers are greatly enriched in iridium and other platinum group elements in roughly chondritic proportions. Geochemical modeling based on immobile element abundances suggests that the original average spherule composition can be approximated by a mixture of fractionated tholeiitic basalt, komatiite, and CI carbonaceous chondrite. The spherules are thought to be the products of large meteorite impacts on the Archean earth.

Lowe, Donald R.↗