Siderophile elements in the upper mantle of the Earth: New clues from metal-silicate partition coefficients

New, precise data on the solubilities of Ni, Co, and Mo in silicate melts at 1400 C and fO2 from IW to IW-2 are presented. The results suggest NiO, CoO as stable species in the melt. No evidence for metallic Ni or Co was found. Equilibrium was ensured by reversals with initially high Ni and Co in the glass. Mo appears to change oxidation state at IW-1, from MoO3 to MoO2. Metal-silicate partition coefficients calculated from these data and recent data on Pd indicate similar partition coefficients for Pd and Mo at the conditions of core formation. This unexpected result constrains models of core formation in the Earth

Die Nominalkomposita in der Iliasuebersetzung von N. I. Gnedič

In der Reihe Slavistische Beiträge werden vor allem slavistische Dissertationen des deutschsprachigen Raums sowie vereinzelt auch amerikanische, englische und russische publiziert. Darüber hinaus stellt die Reihe ein Forum für Sammelbände und Monographien etablierter Wissenschafter/innen dar.</P

Mechanisms and Geochemical Models of Core Formation

The formation of the Earth's core is a consequence of planetary accretion and processes in the Earth's interior. The mechanical process of planetary differentiation is likely to occur in large, if not global, magma oceans created by the collisions of planetary embryos. Metal-silicate segregation in magma oceans occurs rapidly and efficiently unlike grain scale percolation according to laboratory experiments and calculations. Geochemical models of the core formation process as planetary accretion proceeds are becoming increasingly realistic. Single stage and continuous core formation models have evolved into multi-stage models that are couple to the output of dynamical models of the giant impact phase of planet formation. The models that are most successful in matching the chemical composition of the Earth's mantle, based on experimentally-derived element partition coefficients, show that the temperature and pressure of metal-silicate equilibration must increase as a function of time and mass accreted and so must the oxygen fugacity of the equilibrating material. The latter can occur if silicon partitions into the core and through the late delivery of oxidized material. Coupled dynamical accretion and multi-stage core formation models predict the evolving mantle and core compositions of all the terrestrial planets simultaneously and also place strong constraints on the bulk compositions and oxidation states of primitive bodies in the protoplanetary disk.Comment: Accepted in Fischer, R., Terasaki, H. (eds), Deep Earth: Physics and Chemistry of the Lower Mantle and Core, AGU Monograp

Late Accretion and the Late Veneer

The concept of Late Veneer has been introduced by the geochemical community to explain the abundance of highly siderophile elements in the Earth's mantle and their chondritic proportions relative to each other. However, in the complex scenario of Earth accretion, involving both planetesimal bombardment and giant impacts from chondritic and differentiated projectiles, it is not obvious what the "Late Veneer" actually corresponds to. In fact, the process of differentiation of the Earth was probably intermittent and there was presumably no well-defined transition between an earlier phase where all metal sunk into the core and a later phase in which the core was a closed entity separated from the mantle. In addition, the modellers of Earth accretion have introduced the concept of "Late Accretion", which refers to the material accreted by our planet after the Moon-forming event. Characterising Late Veneer, Late Accretion and the relationship between the two is the major goal of this chapter.Comment: In press as a review chapter of the AGU Monograph "The Early Earth", J. Badro and M. Walter Ed

Paradoxical co-existing base metal sulphides in the mantle: The multi-event record preserved in Loch Roag peridotite xenoliths, North Atlantic Craton

The role of the subcontinental lithospheric mantle as a source of precious metals for mafic magmas is contentious and, given the chalcophile (and siderophile) character of metals such as the platinum-group elements (PGE), Se, Te, Re, Cu and Au, the mobility of these metals is intimately linked with that of sulphur. Hence the nature of the host phase(s), and their age and stability in the subcontinental lithospheric mantle may be of critical importance. We investigate the sulphide mineralogy and sulphide in situ trace element compositions in base metal sulphides (BMS) in a suite of spinel lherzolite mantle xenoliths from northwest Scotland (Loch Roag, Isle of Lewis). This area is situated on the margin of the North Atlantic Craton which has been overprinted by a Palaeoproterozoic orogenic belt, and occurs in a region which has undergone magmatic events from the Palaeoproterozoic to the Eocene. We identify two populations of co-existing BMS within a single spinel lherzolite xenolith (LR80) and which can also be recognised in the peridotite xenolith suite as a whole. Both populations consist of a mixture of Fe-Ni-Cu sulphide minerals, and we distinguished between these according to BMS texture, petrographic setting (i.e., location within the xenolith in terms of ‘interstitial’ or within feldspar-spinel symplectites, as demonstrated by X-ray Computed Microtomography) and in situ trace element composition. Group A BMS are coarse, metasomatic, have low concentrations of total PGE (&lt; 40 ppm) and high (Re/Os)N (ranging 1 to 400). Group B BMS strictly occur within symplectites of spinel and feldspar, are finer-grained rounded droplets, with micron-scale PtS (cooperite), high overall total PGE concentrations (15–800 ppm) and low (Re/Os)N ranging 0.04 to 2. Group B BMS sometimes coexist with apatite, and both the Group B BMS and apatite can preserve rounded micron-scale Ca-carbonate inclusions indicative of sulphide-carbonate-phosphate immiscibility. This carbonate-phosphate metasomatic association appears to be important in forming PGE-rich sulphide liquids, although the precise mechanism for this remains obscure. As a consequence of their position within the symplectites, Group B BMS are particularly vulnerable to being incorporated in ascending mantle-derived magmas (either by melting or physical entrainment). Based on the cross-cutting relationships of the symplectites, it is possible to infer the relative ages of each metasomatic BMS population. We tally these with major tectono-magmatic events for the North Atlantic region by making comparisons to carbonatite events recorded in crustal and mantle rocks, and we suggest that the Pt-enrichment was associated with a pre-Carboniferous carbonatite episode. This method of mantle xenolith base metal sulphide documentation may ultimately permit the temporal and spatial mapping of the chalcophile metallogenic budget of the lithospheric mantle, providing a blueprint for assessing regional metallogenic potential. Abbreviations: NAC, North Atlantic Craton; GGF, Great Glen Fault; NAIP, North Atlantic Igneous Province; BPIP, British Palaeogene Igneous Province; SCLM, subcontinental lithospheric mantle; PGE, platinum-group elements; HSE, highly siderophile elements; BMS, base metal sulphid

The effects of melt depletion and metasomatism on highly siderophile and strongly chalcophile elements: S–Se–Te–Re–PGE systematics of peridotite xenoliths from Kilbourne Hole, New Mexico

The composition of the Earth’s upper mantle is a function of melt depletion and subsequent metasomatism; the latter obscuring many of the key characteristics of the former, and potentially making predictions of Primitive Upper Mantle (PUM) composition problematic. To date, estimates of PUM abundances of highly siderophile element (HSE = platinum group elements (PGE) and Re) and the strongly chalcophile elements Se and Te, have been the subject of less scrutiny than the lithophile elements. Critically, estimates of HSE and strongly chalcophile element abundances in PUM may have been derived by including a large number of metasomatized and refertilized samples whose HSE and chalcophile element abundances may not be representative of melt depletion alone. Unravelling the effects of metasomatism on the S–Se–Te–HSE abundances in peridotite xenoliths from Kilbourne Hole, New Mexico, USA, potentially provides valuable insights into the abundances of HSE and strongly chalcophile element abundances in PUM. Superimposed upon the effects of melt depletion is the addition of metasomatic sulfide in approximately half of the xenoliths from this study, while the remaining half have lost sulfide to a late S-undersaturated melt. Despite these observations, the Kilbourne Hole peridotite xenoliths have HSE systematics that are, in general, indistinguishable from orogenic peridotites and peridotite xenoliths used for determination of PUM HSE abundances. This study represents the first instance where Se-Te-HSE systematics in peridotite xenoliths are scrutinized in detail in order to test their usefulness for PUM estimates. Despite earlier studies attesting to the relative immobility of Se during supergene weathering, low S, Se, Os and Se/Te in peridotite xenoliths suggests that Se may be more mobile than originally thought, and for this reason, peridotite xenoliths may not be suitable for making predictions of the abundance of these elements in PUM. Removal of Se, in turn, lowers the Se/Te in basalt-borne xenolithic peridotites to subchondritic values. This is in contrast to what has been recently reported in kimberlite-borne peridotite xenoliths. Moreover, Te added to melt depleted peridotite in metasomatic sulfide is more difficult to remove in a S-undersaturated melt than the HSE and Se due to the generation of micron-scale tellurides. The effects of these processes in orogenic peridotites and xenoliths, from which PUM abundances have been calculated, require further scrutiny before unequivocal Se-Te-Re-PGE values for PUM can be derived

Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): Influence of hydrothermal and magmatic processes

Highly depleted harzburgites and dunites were recovered from ODP Hole 1274A, near the intersection between the Mid-Atlantic Ocean Ridge and the 15°20′N Fracture Zone. In addition to high degrees of partial melting, these peridotites underwent multiple episodes of melt-rock reaction and intense serpentinization and seawater alteration close to the seafloor. Low concentrations of Se, Cu and platinum-group elements (PGE) in harzburgites drilled at around 35-85 m below seafloor are consistent with the consumption of mantle sulfides after high degrees (>15-20 %) of partial melting and redistribution of chalcophile and siderophile elements into PGE-rich residual microphases. Higher concentrations of Cu, Se, Ru, Rh and Pd in harzburgites from the uppermost and lowest cores testify to late reaction with a sulfide melt. Dunites were formed by percolation of silica- and sulfur-undersaturated melts into low-Se harzburgites. Platinum-group and chalcophile elements were not mobilized during dunite formation and mostly preserve the signature of precursor harzburgites, except for higher Ru and lower Pt contents caused by precipitation and removal of platinum-group minerals. During serpentinization at low temperature (<250 °C) and reducing conditions, mantle sulfides experienced desulfurization to S-poor sulfides (mainly heazlewoodite) and awaruite. Contrary to Se and Cu, sulfur does not record the magmatic evolution of peridotites but was mostly added in hydrothermal sulfides and sulfate from seawater. Platinum-group elements were unaffected by post-magmatic low-temperature processes, except Pt and Pd that may have been slightly remobilized during oxidative seawater alteration

Composition, crystallization conditions and genesis of sulfide-saturated parental melts of olivine-phyric rocks from Kamchatsky Mys (Kamchatka, Russia)

Highlights • Parental melts of sulfide-bearing KM rocks have near primary MORB-like composition. • Crystallization of these S-saturated melts occurred in near-surface conditions. • Extensive fractionation and crustal assimilation are not the causes of S-saturation. • S content in melts can be restored by accounting for daughter sulfide globules. Abstract Sulfide liquids that immiscibly separate from silicate melts in different magmatic processes accumulate chalcophile metals and may represent important sources of the metals in Earth's crust for the formation of ore deposits. Sulfide phases commonly found in some primitive mid-ocean ridge basalts (MORB) may support the occurrence of sulfide immiscibility in the crust without requiring magma contamination and/or extensive fractionation. However, the records of incipient sulfide melts in equilibrium with primitive high-Mg olivine and Cr-spinel are scarce. Sulfide globules in olivine phenocrysts in picritic rocks of MORB-affinity at Kamchatsky Mys (Eastern Kamchatka, Russia) represent a well-documented example of natural immiscibility in primitive oceanic magmas. Our study examines the conditions of silicate-sulfide immiscibility in these magmas by reporting high precision data on the compositions of Cr-spinel and silicate melt inclusions, hosted in Mg-rich olivine (86.9–90 mol% Fo), which also contain globules of magmatic sulfide melt. Major and trace element contents of reconstructed parental silicate melts, redox conditions (ΔQFM = +0.1 ± 0.16 (1σ) log. units) and crystallization temperature (1200–1285 °C), as well as mantle potential temperatures (~1350 °C), correspond to typical MORB values. We show that nearly 50% of sulfur could be captured in daughter sulfide globules even in reheated melt inclusions, which could lead to a significant underestimation of sulfur content in reconstructed silicate melts. The saturation of these melts in sulfur appears to be unrelated to the effects of melt crystallization and crustal assimilation, so we discuss the reasons for the S variations in reconstructed melts and the influence of pressure and other parameters on the SCSS (Sulfur Content at Sulfide Saturation)