The effect of Si on metal-silicate partitioning of siderophile elements and implications for the conditions of core formation

We have determined the liquid metal-liquid silicate partitioning of Ni, Co, Mo, W, V, Cr and Nb at 1.5 GPa/1923 K and 6 GPa/2123 K under conditions of constant silicate melt composition with variable amounts of Si in the Fe-rich metallic liquid. Partitioning of Ni, Co, Mo, W and V is sensitive to the Si content of the metal with, in all five cases, increasing Si tending to make the element more lithophile than for conditions where the metal is Si-free. In contrast, metal-silicate partitioning of Cr and Nb is, at constant silicate melt composition, insensitive to the Si content of the metal.The implications of our data are that if, as indicated by the Si isotopic composition of the silicate Earth ( [Georg et al., 2007] and [Fitoussi et al., 2009]), the core contains significant amounts of Si, the important siderophile elements Ni, Co, W and Mo were more lithophile during accretion and core formation than previously believed.We use our new data in conjunction with published metal-silicate partitioning results to develop a model of continuous accretion and core segregation taking explicit account of the partitioning of Si (this study) and O (from Ozawa et al., 2008) between metal and silicate and their effects on metal-silicate partitioning of siderophile elements. We find that the effect of Si on the siderophile characteristics of Ni, Co and W means that the pressures of core segregation estimated from these elements are ∼5 GPa lower than those derived from experiments in which the metal contained negligible Si (e.g., Wade and Wood, 2005). The core-mantle partitioning of Cr and Nb requires that most of Earth accretion took place under conditions which were much more reducing than those implied by the current FeO content of the mantle and that the oxidation took place late in the accretionary process. Paths of terrestrial accretion, oxidation state and partitioning which are consistent with the current mantle contents of Ni, Co, W, V, Cr and Nb lead to Si and O contents of the core of ∼4.3 wt.% and 0.15%, respectively.     

Composition and formation of metal nodules and veins in ordinary chondrites

Five large metal nodules, a composite sample of five small metal nodules, one troilite nodule and two metal veins from five ordinary chondrites were analyzed by electron microprobe and neutron activation analysis. Metal nodules and veins in H chondrites generally consist of large single crystals of kamacite, whereas L nodules contain significant taenite. Most nodules and veins are depleted by large factors ranging up to 240 in refractory siderophiles (Re, Os, Ir, Pt). Tungsten (normally a refractory siderophile) and Au, As, and Ga (volatile siderophiles) have abundance ratios similar to those of the common siderophiles Fe, Co and Ni. We propose that the metal with extremely low refractory-element contents was produced by shock-induced vaporization of chondritic material. The refractory elements condensed near the point of vaporization and were not transported with the vapor. Because the shock-generated gas was mildly oxidizing, W formed volatile oxides. The low Ni/Fe ratio and the resulting high kamacite contents may reflect dilution by Fe from dissociated FeS. Subsequent condensation of the refractory-depleted vapor into fractures and voids formed the metal veins and nodules.     

Trace element partitioning in the Fe-S-C system and its implications for planetary differentiation and the thermal history of ureilites

Element partitioning in metal-light element systems is important to our understanding of planetary differentiation processes. In this study, solid-metal/liquid-sulfide, liquid-metal/liquid-sulfide and solid-metal/troilite partition coefficients (D) were determined for 18 elements (Ag, As, Au, Co, Cr, Cu, Ge, Ir, Ni, Os, Pd, Pt, Mo, Mn, Re, Ru, Se and W) in the graphite-saturated Fe-S-C system at 1 atm. Compared at the same liquid S concentration, the solid/liquid partition coefficients are similar to those in the Fe-S system, but there are systematic differences that appear to be related to interactions with carbon dissolved in the solid metal. Elements previously shown to be “anthracophile” generally have larger solid/liquid partition coefficients in the Fe-S-C system, whereas those that are not have similar or smaller partition coefficients in the Fe-S-C system. The partitioning of trace elements between C-rich and S-rich liquids is, in most cases, broadly similar to the partitioning between solid metal and S-rich liquid. The highly siderophile elements Os, Re, Ir and W are partitioned strongly into the C-rich liquid, with D ? 100. The partition coefficients for Pt, Ge and W decrease significantly at the transition to liquid immiscibility, while the partition coefficient for Mo increases sharply. The bulk siderophile element patterns of ureilite meteorities appear to be better explained by separation of S-rich liquid from residual C-rich metallic liquid at temperatures above the silicate solidus, rather than by separation of S-rich liquid from residual solid metal at lower temperatures.     

Siderophile elements in Martian meteorites and implications for core formation in Mars

Noble metals, Mo, W, and 24 other elements were determined in six SNC meteorites of presumably Martian origin. Based on element correlations, representative siderophile element concentrations for the silicate mantle of Mars were inferred. From a comparison with experimentally determined metal/silicate partition coefficients of the moderately siderophile elements: Fe, Ni, Co, W, Mo, and Ga, it is concluded that equilibrium between core forming metal and silicates in Mars has occurred at high temperatures (around 2200°C) and low pressures (<1 GPa). This suggests that metal segregation occurred concurrently with rapid accretion of Mars, which is consistent with the inference from excess ¹⁸²W in Martian meteorites (Lee and Halliday, 1997). Concentrations of Ir, Os, Ru, Pt, and Au in the analyzed Martian meteorites, except ALH84001, are at a level of approximately 10⁻²–10⁻³ × CI. The comparatively high abundances of noble metals in Martian meteorites require the addition of chondritic material after core formation. The similarity in Au/La and Pt/Ca ratios between ALH84001 and the other Martian meteorites suggests crystallization of ALH84001 after complete accretion of Mars.     

Distribution of Ni,Ga, Ge and Ir between metal and silicate portions of H-group chondrites

Concentrations of Ni, Ga, Ge and Ir have been determined in the metal and silicate portions of 21 chondrites, including 15 H chondrites. The H-group metal shows the following concentration ranges: 7.2–9.4 per cent Ni, 2.4–18 ppm Ga, 61–70 ppm Ge and 1.6–4.6 ppm Ir, and concentrations in H-group silicates are 94–380 ppm Ni, 3.0–9.2 ppm Ga, 0.06–0.66 ppm Ge and 0.03–0.12 ppm Ir. The Ni, Ge and Ir contents in the metal are positively correlated with each other and with the Fe content of olivine, as expected from oxidation-reduction or combined metal-silicate-fractionation/oxidation-reduction models. Metal/silicate concentration ratios for Ir are lower than for Ge and Ni, despite the fact that Ir is more easily reduced to the elemental form. This may indicate that at the formation location of the H-group chondrites in the solar nebula, substantial amounts of Ir were present in condensed form at temperatures which were so high that Fe and Ni were present mainly as vapor. The metal/silicate concentration ratios of Ga and Ge are lower in type-3 ordinary chondrites than in types 4–6. Apparently appreciable fractions of these elements condensed from the nebula in oxidized form and entered the metal during later thermal events. That Ga and Ge were redistributed during recrystallization, whereas appreciable Ir remained in the silicate fraction, probably indicates that Ir faced a substantially greater diffusional barrier than did Ga and Ge.     

I-Xe dating of silicate and troilite from IAB iron meteorites

The IAB iron meteorites may be related to the chondrites: siderophile elements in the metal matrix have chondritic abundances, and the abundant silicate inclusions are chondritic both in mineralogy and in chemical composition. Silicate and troilite (FeS) from IAB irons were analyzed by the I-Xe technique. Four IAB silicate samples gave well-defined I-Xe ages [in millions of years relative to Bjurböle; the monitor error (± 2.5 Myr) is not included]: ?3.7 ± 0.3 for Woodbine, ?0.7 ± 0. 6 for Mundrabilla, +1.4 ± 0.7 for Copiapo, and +2.6 ± 0.6 for Landes. The (¹²⁹Xe/¹³²Xe)_trapped ratios are consistent with previous values for chondrites, with the exception of Landes which has an extraordinary trapped ratio of 3.5 ± 0.2. Both analyses of silicate from Pitts gave anomalous I-Xe patterns.Troilite samples were also analyzed: Pitts troilite gave a complex I-Xe pattern, which suggests an age of +17 Myr; Mundrabilla troilite defined a good I-Xe correlation, which after correction for neutron capture on ¹²⁸Te gave an age of ?10.8 ± 0.7 Myr. Thus, surprisingly, low-melting troilite substantially predates high-melting silicate in Mundrabilla.Abundances of Ga, Ge, and Ni in metal from these meteorites are correlated with I-Xe ages of the silicate; meteorites with older silicates have greater Ni contents. No model easily accounts for this result as well as other properties of IAB irons; nevertheless, these results, taken at face value, overall favor a nebular formation model (e.g. Wasson, 1970, Icarus 12, 407–423). The great age of troilite from Mundrabilla suggests that this troilite formed in a different nebular region from the silicate and metal, and was later mechanically mixed with these other phases.The correlation between the trace elements in the metal and the I-Xe ages of the silicate provides one of the first known instances in which another well-defined meteoritic property correlates with I-Xe ages. In addition, almost all the ¹²⁹Xe in Mundrabilla silicate (etched in acid) was correlated with ¹²⁸Xe. These two results further support the validity of the I-Xe dating method.     

Siderophile element constraints on the formation of metal in the metal-rich chondrites Bencubbin, Weatherford, and Gujba

Laser ablation inductively coupled plasma mass spectrometry was used to measure abundances of P, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sn, Sb, W, Re, Os, Ir, Pt, and Au in metal grains in the Bencubbin-like chondrites Bencubbin, Weatherford, and Gujba to determine the origin of large metal aggregates in bencubbinites. A strong volatility-controlled signature is observed among the metal grains. The refractory siderophiles Ru, Rh, Re, Os, Ir, and Pt are unfractionated from one another, and are present in approximately chondritic relative abundances. The less refractory elements Fe, Co, Ni, Pd, and Au are fractionated from the refractory siderophiles, with a chondritic Ni/Co ratio and a higher than chondritic Pd/Fe ratio. The moderately volatile siderophile elements Ga, Ge, As, Sn, and Sb are depleted in the metal, relative to chondritic abundances, by up to 3 orders of magnitude. The trace siderophile element data are inconsistent with the following proposed origins of Bencubbin-Weatherford-Gujba metal: (1) condensation from the canonical solar nebula, (2) oxidation of an initially chondritic metal composition, and (3) equilibration with a S-rich partial melt. A condensation model for metal-enriched (×10⁷ CI) gas is developed. Formation by condensation or evaporation in such a high-density, metal-enriched gas is consistent with the trace element measurements. The proposed model for generating such a gas is protoplanetary impact involving a metal-rich body.     

Smyer H-chondrite impact-melt breccia and evidence for sulfur vaporization

Smyer is an H-chondrite impact-melt breccia containing ∼20 vol% 0.5- to 13-mm-thick silicate-rich melt veins surrounding unmelted subrounded chondritic clasts up to 7 cm in maximum dimension. At the interface between some of the melt veins and chondritic clasts, there are troilite-rich regions consisting of unmelted, crushed 0.2- to 140-μm-size angular silicate grains and chondrule fragments surrounded by troilite and transected by thin troilite veins. Troilite fills every available fracture in the silicates, including some as thin as 0.1 μm. Little metallic Fe-Ni is present in these regions: the FeS/Fe modal ratio ranges from ∼25:1 to ∼500:1, far higher than the eutectic weight ratio of 7.5:1. The texture of these regions indicates that the sulfide formed from a fluid of very low viscosity. The moderately high viscosity (0.2 poise) and large surface tension of liquid FeS, its inability to wet silicate grain surfaces at low oxygen fugacities, and the supereutectic FeS/Fe ratios in the troilite-rich regions indicate that the fluid was a vapor. It seems likely that during the shock event that melted Smyer, many silicates adjacent to the melt veins were crushed. Upon release of shock pressure, some of the troilite evaporated and dissociated. Molecules of S₂ were transported and condensed into fractures and around tiny silicate grains; there, they combined with Fe from small adjacent metallic Fe-Ni grains to form troilite. The Ni content at the edges of some of these metal grains increased significantly; Co from these Ni-rich grains diffused into nearby kamacite. Impact-induced S volatilization may have played a major role in depleting the surface of 433 Eros (and other chondritic asteroids) in S.     

The origin of metal clasts in the Bencubbin meteoritic breccia

Bencubbin is a breccia containing metal and silicate clasts, along with occasional chondritic fragments. The breccia is cemented together by a small amount of shock-melted metal-silicate matrix. There is no evidence, however, for complete melting of either metal or silicate clasts after their incorporation within the breccia. The main metal phase occurs as rounded and angular clasts of Fe-Ni. Each clast is chemically homogeneous, but systematic chemical variations between clasts are observed with Ni concentrations varying from ? 5.3 wt% in some clasts up to 7.5 wt% in others. Cobalt concentrations vary between clasts from 0.25 to 0.35 wt% and are positively correlated with Ni. The Co and Ni concentrations are consistent with the metal condensation path (pressure ? 10^-3 atm) predicted by Grossman and Olsen (1974, Geochim. Cosmochim. Acta38, 173–187). The P vs Ni concentrations are consistent with the metal condensation path (pressure ? 10^?4atm) predicted by Wai et al. (1978, Lunar and Planetary Science IX, pp. 1193–1195). Thus we believe that Bencubbin metal clasts may record chemical information imparted during condensation of the metal from the nebula. Chromium concentrations in Bencubbin metal (0.05–0.30 wt%) greatly exceed concentrations observed in iron meteorites as predicted by Grossman and Olsen (1974, Geochim. Cosmochim. Acta38, 173–187) for metal condensates from the solar nebula. The Cr-Ni trend in Bencubbin, however, is positively correlated with Ni, in contrast to the predicted condensation trend. This unexpected correlation may be the result of subsequent redistribution of Cr between metal and micron-sized troilite blebs. The incorporation of these troilite blebs within the metal clasts is difficult to explain in terms of low temperature (? 700 K) condensation of troilite. The possible explanations for the presence of the troilite may or may not be consistent with an unaltered primitive composition for the metal clasts. High temperature equilibrium condensation of Bencubbin metal, however, is also supported by the low Ga and Ge contents reported by Kallemeynet al. (1978, Geochim. Cosmochim. Acta42, 507–515). Three of the metal clasts were found to contain ?2.3wt% Si in alloy with the metal. The compositions of these clasts are consistent with equilibrium condensation at a pressure of ? 1 atm from a gas of cosmic composition. The Si-rich clasts could also have condensed at lower pressures from a gas with a fractionated $\text{C}\text{O}$ ratio relative to cosmic abundances.     

Activities and volatilities of trace components in silicate melts: a novel use of metal–silicate partitioning data

Ian Carmichael spent 45 years thinking about and working on the activities of components in silicate melts and their use to estimate physicochemical conditions at eruption and in the source regions of igneous rocks. These interests, principally in major components such as SiO₂, led us to think about possible ways of determining the complementary activity coefficients of trace components in silicate melts. While investigating the conditions of accretion and differentiation of the Earth, a number of authors have determined the partitioning of trace elements such as Co, Ni, Mo and W between liquid Fe metal and liquid silicate. These data have the potential to provide activity information for a large number of trace components in silicate melts. In order to turn the partitioning measurements into activities, however, we need to know the activity coefficient of FeO, γ_FeO in the silicate. We obtained γ_FeO as a function of melt composition by fitting a simple model to 83 experimental data for which the authors had measured the FeO content of the silicate melt in equilibrium with metal (Fe-bearing alloy) at known f_O2. The compositional dependence of γ_FeO is weak, but, when calculated in the system Diopside–Anorthite–Forsterite, it decreases towards the Forsterite apex. A similar approach for Ni, for which twice as many data are available, leads to similar composition dependence of activity coefficient and confirms the suggestion that γ_NiO/γ_FeO is almost constant over a wide range of silicate melt composition. The activity coefficients for FeO were used in conjunction with measured Mo and W partitioning between Fe-rich metal and silicate melt to estimate activity coefficients for trace MoO₂ and WO₃ dissolved in silicate melt. When combined with data on Mo- and W-saturated silicate melts a strong dependence of activity coefficient is observed. Calculated in the system Diopside–Anorthite–Forsterite, both MoO₂ and WO₃ exhibit similar behaviour to FeO and NiO in that activity coefficients decrease as Forsterite content increases. The effect is much larger for Mo and W, however, γ_MoO2 and γ_WO3 varying by factors of 20 and nearly 100, respectively, in this system. In order to illustrate the potential applications of the metal–silicate partitioning approach to determine the activity coefficients of volatile elements, we used it to determine activity coefficients of PbO, CuO_0.5 and InO_1.5 in a silica-saturated melt at 1,650 °C. We find values of 0.22, 3.5 and 0.02, respectively, indicating a strong dependence on cation charge. The value for CuO_0.5 is in excellent agreement with experimental data of Holzheid and Lodders (Geochim Cosmochim Acta 65:1933–1951, 2001), which shows that the method is viable. When combined with thermodynamic data on the gas species, we find that Pb is the most volatile of the 3 elements under ‘normal’ terrestrial conditions of oxygen fugacity but that In should become the most volatile under strongly reducing conditions such as those of the solar nebula. The oxygen fugacity dependence of volatility has implications for the high relative abundance of In in silicate Earth. We conclude that metal–silicate partitioning experiments are a viable means for determining activities of trace components in silicate melts and are particularly useful if the metal of the element is unstable or volatile at igneous temperatures.     

The origin and history of the metal and sulfide components of chondrules

Fourteen siderophile and other non-lithophile elements determined in 31 Semarkona (LL3.0) chondrules by neutron activation analysis are severely fractionated relative to lithophile elements. Their chondrule/whole-rock abundance ratios vary by factors of up to 1000; the mean ratio is ~0.2. Non-refractory siderophile abundance patterns in Ni-rich chondrules are smooth functions of volatility and in Ni-poor chondrules patterns are more irregular. Refractory siderophile elements are often fractionated from Ni; they covary, confirming the presence of a refractory metal component. The chalcophile element Se correlates with Br and siderophile elements. Zinc is uniformly low and uncorrelated with other elements.Most metal and sulfide in chondrules was probably present in the solar nebula before chondrule formation; most siderophile and chalcophile elements were in these materials. Some Fe was also in silicates, as were minor amounts of Ni, Co, Au, Ge and possibly Se. The amount of metal formed by reduction during chondrule melting was minor. The common metal component in chondrules is similar to, and may be the same as the common component involved in the metal/silicate fractionation of the ordinary chondrite groups.Chondrules are depleted in metal chiefly because they sampled metal-poor precursor assemblages. Metal segregation during the molten period and subsequent loss was a minor process that may be responsible for most surface craters on chondrules.     

The Earth’s tungsten budget during mantle melting and crust formation

During silicate melting on Earth, W is one of the most incompatible trace elements, similar to Th, Ba or U. As W is also moderately siderophile during metal segregation, ratios of W and the lithophile Th and U in silicate rocks have therefore been used to constrain the W abundance of the Earth’s mantle and the Hf-W age of core formation. This study presents high-precision W concentration data obtained by isotope dilution for samples covering important silicate reservoirs on Earth. The data reveal significant fractionations of W from other highly incompatible lithophile elements such as Th, U, and Ta. Many arc lavas exhibit a selective enrichment of W relative to Th, U, and Nb-Ta, reflecting W enrichment in the sub-arc mantle via fluid-like components derived from subducting plates. In contrast, during enrichment by melt-like subduction components, W is generally slightly depleted relative to Th and U, but is still enriched relative to Ta. Hence, all arc rocks and the continental crust exhibit uniformly low Ta/W (ca. 1), whereas W/Th and W/U may show opposite fractionation trends, depending on the role of fluid- and melt-like subduction components. Further high-precision W data for OIBs and MORBs reveal a systematic depletion of W in both rock types relative to other HFSE, resulting in high Ta/W that are complementary to the low Ta/W observed in arc rocks and the continental crust. Similar to previous interpretations based on Nb/U and Ce/Pb systematics, our Ta/W data confirm a depletion of the depleted upper mantle (DM) in fluid mobile elements relative to the primitive mantle (PRIMA). The abundance of W in the depleted upper mantle relative to other immobile and highly incompatible elements such as Nb and Ta is therefore not representative of the bulk silicate Earth. Based on mass balance calculations using Ta-W systematics in the major silicate reservoirs, the W abundance of the Earth’s primitive mantle can be constrained to 12 ppb, resulting in revised ratios of W-U and W-Th of 0.53 and 0.14, respectively. The newly constrained Hf-W ratio of the silicate Earth is 25.8, significantly higher than previously estimated (18.7) and overlaps within error the Hf-W ratio proposed for the Moon (ca. 24.9). The ¹⁸²Hf-¹⁸²W model age for the formation of the Earth’s core that is inferred from the ¹⁸²W abundance and the Hf/W of the silicate Earth is therefore younger than previously calculated, by up to 5 Myrs after solar system formation depending on the accretion models used. The similar Hf/W ratios and ¹⁸²W compositions of the Earth and the silicate Moon suggest a strong link between the Moon forming giant impact and final metal-silicate equilibration on the Earth.     

Platinum group element and nickel sulphide ore tenors of the Mount Keith nickel deposit, Yilgarn Craton, Australia

A set of platinum group element (PGE) analyses of about 120 samples from a 250-m continuous drill core through the Mount Keith komatiite-hosted nickel orebody, combined with Ni, Cu, Co, S, and major elements, reveals a complex trend of covariance between the original cumulus components of a thick sequence of nearly pure olivine–sulphide liquid adcumulates. The intersection is divided into informal chemostratigraphic zones, defined primarily by combinations of fine-scale cyclicity in original olivine composition, defined by Mg#, and sulphide composition, defined by Pt/S and Ni/S. Contents of Ni and PGE in 100% sulphides (tenors) were determined from linear regressions of the Ni–S and PGE–S covariance for each zone. Inferred olivine compositions range from about Fo₉₂ to Fo_94.6 and show a broad decrease from bottom to top of the sequence complicated by numerous reversals, revealing crystallisation in an open conduit system. Ni and PGE tenors of Mount Keith sulphide ores have typical values similar to the type I deposits of the Kambalda Dome. Mobility of S, at least on the scale of 2-m sample composites, is evidently relatively minor. Tenors for the various zones range 12–22% Ni, 370–1540?ppb Pt, 970–3670?ppb Pd, 100–460?ppb Ir, 170–460?ppb Rh, and 710–1260?ppb Ru. Pt, Pd, and Rh tenors are very strongly correlated, but the iridium group of platinum group elements (IPGEs; Ir and Ru) less so. Tenor variations are predominantly controlled by variations in magma/sulphide ratio R (100–350), with a minor component of variance from equilibrium crystallisation trends in the parent magma. PGE depletion in the silicate melt due to sulphide liquid extraction is limited by entrainment of sulphide liquid droplets and continuous equilibration with the transporting silicate magma. Ratios of the PGEs to one another are similar to those in the host komatiite magma, with the exception of Pt, which is systematically depleted in ores, relative to Rh and Pd and relative to host magma, by a consistent factor of about 2 to 2.5. This anomalous Pt depletion relative to PGE element ratios in unmineralized komatiitic rocks matches that observed in bulk compositions of many komatiite-hosted orebodies. The highly consistent nature of this depletion, and particularly the very strong correlation between Pt, Pd, and Rh in the Mount Keith deposit, argue that this depletion is a primary magmatic signal and not an artefact of alteration. Differential diffusion rates between Pt and the other PGEs, giving rise to a low effective partition coefficient for Pt into sulphide liquid, is advanced as a possible but not definitive explanation.     

Geochemical affinities of cobalt and germanium toward metal,silicate, and sulfide phases at high temperature

Hydrothermal studies indicate that Co and Ge are strongly siderophile when metallic iron is in equilibrium with olivine at 900°C and 500 bars. If the metal is replaced by troilite (FeS), Ge is strongly lithophile whereas Co tends to concentrate in the sulfide phase. If iron meteorites were formed in a core derived from the sulfide phase, they would be depleted in Ge but retain Co.     

Occurrence, distribution and probable source of the trace elements in ghugus coals, wardha valley, districts chandrapur and yeotmal, maharashtra, India

Trace-element determinations of 15 coal samples have been made in order to know their distribution, behaviour and associations with the organic and inorganic fractions in the coal. The coal samples have been systematically collected in stratigraphic sequences so that the vertical variation of the trace-elements can be studied. The elements determined by spectographic analysis are W, V, Cr, Sc, Y, Cu, Co, Pb, Be, Ni and Ba. The results indicate that the concentration of trace elements in these coals varies greatly from bottom to top sections. The elements V and Co are extremely poor in the top and middle sections, whereas in the bottom section they are fairly distributed. Be is extremely poor in the bottom section, and fairly distributed in the middle and top sections. W, Sc, Y have poor concentration in the bottom section as compared to the middle and top sections. Ni is fairly distributed in the bottom section whereas its concentration is poor in the middle and top sections. Cr and Cu are fairly distributed in the bottom, middle and top sections. Ba has unusually high concentration in all the sections.It appears from the present study that W, Cr, Sc, Y and Be are concentrated more in silicate minerals (clay, quartz, etc.) associated with coal, and the elements like , Co, and Ni have intimate relation with organic matters in coal and are present as organometallic compounds as well as absorbed cations. Cu and Pb which are present in the coals are derived from the inorganic matter, mainly from the pyrites, whereas W has affinity with carbonate minerals in the coals. The Ba is mainly associated with the inoraanic matter of coal; its unusually high concentration indicates association with carbonates, clays and other silicate minerals.     

Deep-ocean mineral deposits as a source of critical metals for high- and green-technology applications: Comparison with land-based resources

Ferromanganese (Fe–Mn) crusts are strongly enriched relative to the Earth's lithosphere in many rare and critical metals, including Co, Te, Mo, Bi, Pt, W, Zr, Nb, Y, and rare-earth elements (REEs). Fe–Mn nodules are strongly enriched in Ni, Cu, Co, Mo, Zr, Li, Y, and REEs. Compared to Fe–Mn crusts, nodules are more enriched in Ni, Cu, and Li, with subequal amounts of Mo and crusts are more enriched in the other metals. The metal ions and complexes in seawater are sorbed onto the two major host phases, FeO(OH) with a positively charged surface and MnO₂ with a negatively charged surface. Metals are also derived from diagenetically modified sediment pore fluids and incorporated into most nodules. Seafloor massive sulfides (SMS), especially those in arc and back-arc settings, can also be enriched in rare metals and metalloids, such as Cd, Ga, Ge, In, As, Sb, and Se. Metal grades for the elements of economic interest in SMS (Cu, Zn, Au, Ag) are much greater than those in land-based volcanogenic massive sulfides. However, their tonnage throughout the global ocean is poorly known and grade/tonnage comparisons with land-based deposits would be premature.The Clarion–Clipperton Fe–Mn Nodule Zone (CCZ) in the NE Pacific and the prime Fe–Mn crust zone (PCZ) in the central Pacific are the areas of greatest economic interest for nodules and crusts and grades and tonnages for those areas are moderately well known. We compare the grades and tonnages of nodules and crusts in those two areas with the global terrestrial reserves and resources. Nodules in the CCZ have more Tl (6000 times), Mn, Te, Ni, Co, and Y than the entire global terrestrial reserve base for those metals. The CCZ nodules also contain significant amounts of Cu, Mo, W, Li, Nb, and rare earth oxides (REO) compared to the global land-based reserves. Fe–Mn crusts in the PCZ have significantly more Tl (1700 times), Te (10 times more), Co, and Y than the entire terrestrial reserve base. Other metals of significance in the PCZ crusts relative to the total global land-based reserves are Bi, REO, Nb, and W. CCZ nodules and PCZ crusts are also compared with the two largest existing land-based REE mines, Bayan Obo in China and Mountain Pass in the USA. The land-based deposits are higher grade but lower tonnage deposits. Notably, both land-based deposits have < 1% heavy REEs (HREEs), whereas the CCZ has 26% HREEs and the PCZ, 18% HREEs; the HREEs have a much greater economic value. Radioactive Th concentrations are appreciably higher in the land-based deposits than in either type of marine deposit. A discussion of the differences between terrestrial and marine impacts and mine characteristics is also presented, including the potential for rare metals and REEs in marine deposits to be recovered as byproducts of mining the main metals of economic interest in nodules and crusts.     

湖南某钨矿区花岗岩岩石化学特征

以湖南某钨矿区花岗岩类侵入岩体为研究对象,分别对花岗闪长岩及花岗岩的常量元素、微量元素进行了系统测定.研究表明,该岩体为高钾钙碱性系列;微量元素总体上都表现为贫V、Ni、Co、W、Sb、Mo,富集Cr、Pb、Bi、Sn.     

Compositions of group IVB iron meteorites and their parent melt

The concentrations of P, V, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the group IVB iron meteorites Cape of Good Hope, Hoba, Skookum, Santa Clara, Tawallah Valley, Tlacotepec, and Warburton Range have been measured by laser ablation inductively coupled plasma mass spectrometry. The data were fitted to a model of fractional crystallization of the IVB parent body core, from which the composition of the parent melt and metal/melt distribution coefficients for each element in the system were determined, for a chosen value of D(Ni). Relative to Ni and chondritic abundances, the parent melt was enriched in refractory siderophiles, with greatest enrichment of 5× chondritic in the most refractory elements, and was strongly volatile-depleted, down to 0.00014× chondritic in Ge. Comparison to an equilibrium condensation sequence from a gas of solar composition indicates that no single temperature satisfactorily explains the volatility trend in the IVB parent melt; a small (<1%) complement of ultrarefractory components added to metal that is volatile-depleted but otherwise has nearly chondritic abundances (for Fe, Co and Ni) best explains the volatility trend. In addition to this volatility processing, which probably occurred in a nebular setting, there was substantial oxidation of the metal in the IVB parent body, leading to loss of Fe and other moderately siderophile elements such as Cr, Ga, and W, and producing the high Ni contents that are observed in the IVB irons. By assuming that the entire IVB parent body underwent a similar chemical history as its core, the composition of the silicate that is complementary to the IVB parent melt was also estimated, and appears to be similar to that of the angrite parent.     

Geochemistry of trace and minor elements in sediments and manganese micronodules from the Angola Basin

Indicator role of trace elements in sedimentation and ore formation is considered for sediments from Station 2182 in the Angola Basin. It is shown that pelagic sediments were formed from two main sources: biogenic calcium carbonate and lithogenic sediment component compositionally similar to the miopelagic clay. Increase of the Mn/Al ratio, Ce anomaly in the REE composition, Co/Ni and Mo/W ratios, and anomalous accumulation of Tl, Pb, Bi and other microelements indicate that sediments from horizons 15–20 and 30–35 cm contain significant amounts of hydrogenic material as Fe-Mn oxyhydroxides. Manganese micronodules (MN) were extracted from different horizons (10–15, 15–20, and 30–35 cm) and analyzed to study the hydrogenic component. Their development is related to retardation of biogenic and lithogenic sedimentation. The studied manganese micronodules are represented by the hydrogenic-diagenetic formations >100 μm in size with Mn/Fe = 2.0–2.8, Co/Ni = 0.2–0.4, Ce an = 4.2–5.7, and Mo/W = 5.2–7.9. The MN content is too low to affect the major and trace element composition of sediments. The main part of Fe and Mn is confined to fraction <10 μm.     

Geochemical Constraints on the Origin of the Ni–Cu Sulfide Ores in the Tejadillas Prospect (Cortegana Igneous Complex,SW Spain)

After the discovery of the Aguablanca ore deposit (the unique Ni–Cu mine operating in SW Europe), a number of mafic‐ultramafic intrusions bearing Ni–Cu magmatic sulfides have been found in the Ossa–Morena Zone of the Iberian Massif (SW Iberian Peninsula). The Tejadillas prospect is one of these intrusions, situated close to the border between the Ossa–Morena Zone and the South Portuguese Zone of the Iberian Massif. This prospect contains an average grade of 0.16 wt % Ni and 0.08 wt % Cu with peaks of 1.2 wt % Ni and 0.2 wt % Cu. It forms part of the Cortegana Igneous Complex, a group of small mafic‐ultramafic igneous bodies located 65 km west of the Aguablanca deposit. In spite of good initial results, exploration work has revealed that sulfide mineralization is much less abundant than in Aguablanca. A comparative study using whole‐rock geochemical data between Aguablanca and Tejadillas shows that the Tejadillas igneous rocks present a lower degree of crustal contamination than those of Aguablanca. The low crustal contamination of the Tejadillas magmas inhibited the assimilation of significant amounts of crustal sulfur to the silicate magmas, resulting in the sparse formation of sulfides. In addition, Tejadillas sulfides are strongly depleted in PGE, with total PGE contents ranging from 14 to 81 ppb, the sum of Pd and Pt, since Os, Ir, Ru and Rh are usually below or close to the detection limit (2 ppb). High Cu/Pd ratios (9700–146,000) and depleted mantle‐normalized PGE patterns suggest that the Tejadillas sulfides formed from PGE‐depleted silicate magmas. Modeling has led us to establish that these sulfides segregated under R‐factors between 1000 and 10,000 from a silicate melt that previously experienced 0.015% of sulfide extraction. All these results highlight the importance of contamination processes with S‐rich crustal rocks and multiple episodes of sulfide segregations in the genesis of high‐tenor Ni–Cu–PGE ore deposits in mafic‐ultramafic intrusions of the region.