Redox state of deep off-craton lithospheric mantle: new data from garnet and spinel peridotites from Vitim, southern Siberia

Oxygen fugacity (fO₂) affects melting, metasomatism, speciation of C–O–H fluids and carbon-rich phases in the upper mantle. fO₂ of deep off-craton mantle is poorly known because garnet-peridotite xenoliths are rare in alkali basalts. We examine the redox and thermal state of the lithospheric mantle between the Siberian and North China cratons using new Fe³⁺/ΣFe ratios in garnet and spinel obtained by M?ssbauer spectroscopy, major element data and P–T estimates for 22 peridotite xenoliths as well as published data for 15 xenoliths from Vitim, Russia. Shallow spinel-facies mantle is more oxidized than deep garnet peridotites (average, ?0.1 vs. ?2.5 ΔlogfO₂(FMQ)). For intermediate garnet–spinel peridotites, fO₂ estimates from spinel-based oxybarometers are 1.5–3.2 ΔlogfO₂(FMQ) lower than those from garnet-based oxybarometers. These rocks may be out of phase and chemical inter-mineral equilibrium because the spinel–garnet reaction and concomitant changes in mineral chemistry do not keep up with P–T changes (e.g., lithospheric heating by recent volcanism) due to slow diffusion of trivalent cations and because gar-, gar-spl and spl-facies rocks may coexist on centimeter–meter scale. The spinel-based fO₂ estimates may not be correct while garnet-based fO₂ values provide conditions before the heating. The T (780–1,100?°C) and fO₂ ranges of the Vitim xenoliths overlap those of coarse garnet and spinel cratonic peridotites. However, because of a higher geothermal gradient, the deepest Vitim garnet peridotites are more reduced (by 0.5–2.0 ΔlogfO₂(FMQ)) than cratonic garnet peridotites at similar depths, and the “water maximum” conditions (>80?% H₂O) in the off-craton mantle exist in a more shallow and narrow depth range (60–85?km) than in cratonic roots (100–170?km). The base of the off-craton lithospheric mantle (≥90?km) at 2.5?GPa and 1,150?°C has fO₂ of ?3.0 ?logfO₂(FMQ), with dominant CH₄ and H₂O and minor H₂ in the fluid. Melting near the base of off-craton mantle lithosphere may be induced by increasing water share in migrating fluids due to oxidation of methane.     

Distribution of gold and rhenium between nickel-iron and silicate melts: implications for the abundance of siderophile elements on the Earth and Moon

The distribution equilibrium of Au and Re between nickel-iron and basaltic melts was studied at 1400–1600°C, using radioactive tracers. Metal/silicate distribution coefficients were 1–3 orders of magnitude higher than earlier estimates, as follows. Mauna Loa basalt—Fe₁₀Ni₉₀: D_Au = 3.3 × 10⁴, D_Re = (2.4?89) × 10⁴. Gorda Ridge basalt—Fe₁₀Ni₉₀: D_Au = (18?75) × 10⁴. Synthetic lunar basalt—Fe₇₀ Ni₃₀: D_Au≥ 2 × 10⁴, D_Re ≥ 2 × 10³. The experimental ΔG₁₈₀₀^° for the distribution of Au between nickel-iron and Mauna Loa basalt is ?40 kcal/mole, compared to a calculated value of about ?110 kcal/mole for a reaction involving simple Au³⁺ ions. Presumably the difference represents stabilization of Au(III) by complex formation with ligands such as Cl^?, H₂O, etc.Gold abundances in lunar basalts are roughly consistent with the measured D_Au, but those in terrestrial basalts are two orders of magnitude too high. This discrepancy may reflect complexing by volatiles in the Earth's upper lithosphere, as well as oxidative destruction of metal in the final stages of accretion. In the absence of a metal phase, siderophile trace elements would remain trapped in the upper mantle and crust.     

Apatite as a probe of halogen and water fugacities in the terrestrial planets

Apatite preserves a record of the halogen and water fugacities that existed during the waning stages of crystallization of planetary magmas, when they became saturated in phosphates. We develop a thermodynamic formalism based on apatite-merrillite equilibria that makes it possible to compare the relative values of halogen and water fugacities in Martian, lunar and terrestrial basalts, accounting for possible differences in pressure, temperature and oxygen fugacities among the planets. We show that each of these planetary bodies has distinctive ratios among volatile fugacities at apatite saturation and that these fugacities are in some cases related in a consistent way to volatile fugacities in the mantle magma sources. Our analysis shows that the Martian mantle parental to basaltic SNC meteorites was dry and poor in both fluorine and chlorine compared to the terrestrial mantle. The limited data available from Mars show no secular variation in mantle halogen and water fugacities from ∼4 Ga to ∼180 Ma. The water and halogens found in present-day Martian surface rocks have thus resided in the planet’s surficial systems since at least 4 Ga, and may have been degassed from the planet’s interior during a primordial crust-forming event. In comparison to the Earth and Mars, the Moon, and possibly the eucrite parent body too, appear to be strongly depleted not only in H₂O but also in Cl₂ relative to H₂O. Chlorine depletion is strongest in mare basalts, perhaps reflecting an eruptive process characteristic of large-scale lunar magmatism.     

U-Pb and Lu-Hf isotope record of detrital zircon grains from the Limpopo Belt - Evidence for crustal recycling at the Hadean to early-Archean transition

Detrital zircon grains from Beit Bridge Group quartzite from the Central Zone of the Limpopo Belt near Musina yield mostly ages of 3.35-3.15 Ga, minor 3.15-2.51 Ga components, and numerous older grains grouped at approximately 3.4, 3.5 and 3.6 Ga. Two grains yielded concordant Late Hadean U-Pb ages of 3881 ± 11 Ma and 3909 ± 26 Ma, which are the oldest zircon grains so far found in Africa. The combined U-Pb and Lu-Hf datasets and field relationships provide evidence that the sedimentary protolith of the Beit Bridge Group quartzite was deposited after the emplacement of the Sand River Gneisses (3.35-3.15 Ga), but prior to the Neoarchean magmatic-metamorphic events at 2.65-2.60 Ga. The finding of abundant magmatic zircon detritus with concordant U-Pb ages of 3.35-3.15 Ga, and ¹⁷⁶Hf/¹⁷⁷Hf of 0.28066 ± 0.00004 indicate that the Sand River Gneiss-type rocks were a predominant source. In contrast, detrital zircon grains older than approximately 3.35 Ga were derived from the hinterland of the Limpopo Belt; either from a so far unknown crustal source in southern Africa, possibly from the Zimbabwe Craton and/or a source, which was similar but not necessarily identical to the one that supplied the Hadean zircons to Jack Hills, Western Australia. The Beit Bridge Group zircon population at >3.35 Ga shows a general εHf_t increase with decreasing age from εHf_3.9Ga = −6.3 to εHf_3.3-3.1Ga = −0.2, indicating that Hadean crust older than 4.0 Ga (T_DM = 4.45-4.36 Ga) was rejuvenated during magmatic events between >3.9 and 3.1 Ga, due to a successive mixing of crustal rocks with mantle derived magmas. The existence of a depleted mantle reservoir in the Limpopo’s hinterland is reflected by the ∼3.6 Ga zircon population, which shows εHf_3.6Ga between −4.6 and +3.2. In a global context, our data suggest that a long-lived, mafic Hadean protocrust with some tonalite-trondhjemite-granodiorite constituents was destroyed and partly recycled at the Hadean/Archean transition, perhaps due to the onset of modern-style plate tectonics.     

Aluminous enstatites of lunar meteorites and deep-seated lunar rocks

Fragments of aluminous enstatite from lunar meteorites of highland origin were investigated. It was found that such fragments usually occur in impact breccias of troctolitic composition. The aluminous enstatite contains up to 12 wt % Al₂O₃ and shows low CaO (<1 wt %) and almost constant high Mg/(Mg + Fe) ratio (89.5 ± 1.4 at %) identical to that of the Earth’s mantle. With respect to these parameters, the aluminous enstatites are distinctly different from common orthopyroxene of lunar rocks. The aluminous enstatite associates with spinel (pleonaste), olivine, anorthite (clinopyroxene was never found), and accessory minerals: rutile, Ti-Zr oxides, troilite, and Fe-Ni metal. The same assemblage was described in rare fragments of spinel cataclasites from the samples of the Apollo missions. Thermobarometry and the analysis of phase equilibria showed that the rocks hosting aluminous enstatite are of deep origin and occurred at depths from 25 km to 130–200 km at T from 800 to 1300°C, i.e., at least in the lower crust and, possibly, in the upper mantle of the Moon. These rocks could form individual plutons or dominate the composition of the lower crust. The most probable source of aluminous enstatite is troctolitic magnesian rocks and, especially, spinel troctolites with low Ca/Al and Ca/Si ratios. The decompression of such rocks must produce cordierite-bearing assemblages. The almost complete absence of such assemblages in the surficial rocks of lunar highlands implies that vertical tectonic movements were practically absent in the lunar crust. The transport of deep-seated materials to the lunar surface was probably related to impact events during the intense meteorite bombardments >3.9 Ga ago.     

Experimental investigation of the partitioning of phosphorus between metal and silicate phases: implications for the Earth,Moon and Eucrite Parent Body

The solid metal/silicate melt partition coefficient for P, D(P), has been determined experimentally at 1190°C and 1300°C. The dependence of the partition coefficient on oxygen fugacity has been investigated, and is consistent with a valence state of 5 for P in the silicate melt. The experimental partition coefficients are given by: $\text{log D(P) = ?1.21 log ?O}{}_2\text{? 15.95 at 1190°C}$$\text{log D(P) = ?1.53 log ?O}{}_2\text{? 17.73 at 1300°C}$The experimentally determined partition coefficients may be used to interpret the low $\text{P}\text{La}$ ratios of the Earth, Moon and eucrites relative to C1 chondrites. The low $\text{P}\text{La}$ ratios in the eucrites may be explained by partitioning of P into 5% to 25% of a sulfur-bearing metallic liquid assuming equilibration and separation of the liquid metal from the silicates at low degrees of partial melting of the silicates. The low $\text{W}\text{La}$ ratios in the eucrites compared to C1 chondrites require the separation of an additional 2% to 10% solid metal.The lowering of both $\text{P}\text{La}$ and $\text{W}\text{La}$ ratios in the Moon may be explained by partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. The $\text{W}\text{La}$ ratios in the Earth and Moon are virtually indistinguishable, while $\text{P}\text{La}$ ratios differ by a factor of two. The concentrations of FeO also appear to be different. These observations are difficult to reconcile with the hypothesis of a terrestrial origin of the Moon following formation of the Earth's core, but are consistent with independent formation of the Earth and Moon.     

Enriched crustal and mantle components and the role of the lithosphere in generating Paleoproterozoic dyke swarms of the Ungava Peninsula,Canada

Paleoproterozoic mafic dyke swarms (2.5–2.0 Ga) of the Ungava Peninsula can be divided in three chemical groups. The main group has a wide range of Fe (10–18 wt.% Fe₂O₃) and Ti (0.8–2.0 wt.% TiO₂) contents, and the most magnesian samples have compositions consistent with melting of a fertile lherzolitic mantle at ~ 1.5 GPa. Dykes of a low-LREE (light rare earth element) subgroup (La/Yb ≤ 4) display decreasing Zr/Nb with increasing La/Yb ratios and positive εNd_2.0 Ga values (+ 3.9 to + 0.2) that trend from primitive mantle towards the composition of Paleoproterozoic alkaline rocks. In contrast, dykes of a high-LREE subgroup (La/Yb ≥4) display increasing Zr/Nb ratios and negative εNd_2.0 Ga values (? 2.3 to ? 6.4) that trend towards the composition of Archean crust. A low Fe–Ti group has low Fe (< 11 wt.% Fe₂O₃), Ti (< 0.8 wt.% TiO₂), high field strength elements (HFSE; < 6 ppm Nb) and heavy rare earth elements (HREE; < 2 ppm Yb) contents, but are enriched in large ion lithophile elements (LILE; K/Ti = 0.7–3) and LREE (La/Yb > 4). These dykes are interpreted as melts of a depleted harzburgitic mantle that has experienced metasomatic enrichment. A positive correlation of Zr/Nb ratio and La/Yb ratio, negative εNd_2.0 Ga values (? 14 to ? 6), and the presence of inherited Archean zircons further suggest the incorporation of a crustal component. A high Fe–Ti group has high Fe (> 14 wt.% Fe₂O₃) and Ti (> 1.4 wt.% TiO₂) contents, along with higher Na contents relative to the main group dykes. Dykes of a high-Al subgroup (> 12 wt.% Al₂O₃) share Fe contents, εNd_2.0 Ga values (? 2.3 to ? 3.4), La/Yb and Th/Nb ratios with Archean ferropicrites, and may represent evolved ferropicrite melts. A low-Al subgroup (< 12 wt.% Al₂O₃) has relatively lower Yb contents (< 2 ppm) and fractionated HREE patterns that indicate the presence of garnet in their melting residue. A comparison with ~ 5 GPa experimentally-derived melts suggests that these dykes may be derived from garnet-bearing pyroxenite or peridotite. The εNd_2.0 Ga values (? 0.3 to ? 2.0) of these dykes lie between the compositions of Archean granitoids and Paleoproterozoic alkaline rocks, signifying their petrogenesis involved both crustal and mantle components.Paleoproterozoic dykes containing a crustal component occur within, or close to, an isotopically enriched Archean terrane (T_DM 4.3–3.1 Ga), whereas dykes without this component occur in an isotopically juvenile terrane (T_DM < 3.1 Ga). The lack of a crustal component and the positive εNd_2.0 Ga values of dykes intruding the latter suggest that the crust they intruded was either too cold to be assimilated, or that its lower crust and/or lithosphere were Paleoproterozoic in age. In contrast, the ubiquitous presence of a crustal component and the diversity of mantle sources for dykes intruding the enriched terrane (lherzolite, harzburgite, pyroxenite) suggest a warmer crust with underlying heterogeneous lithospheric mantle.     

Moon and Earth : compositional differences inferred from siderophiles,volatiles, and alkalis in basalts

We have compared RNAA analyses of 18 trace elements in 25 low-Ti lunar and 10 terrestrial oceanic basalts. According to Ringwood and Kesson, the abundance ratio in basalts for most of these elements approximates the ratio in the two planets.Volatiles (Ag, Bi, Br, Cd, In, Sb, Sn, Tl, Zn) are depleted in lunar basalts by a nearly constant factor of 0.026 ± 0.013, relative to terrestrial basalts. Given the differences in volatility among these elements, this constancy is not consistent with models that derive the Moon's volatiles from partial recondensation of the Earth's mantle or from partial degassing of a captured body. It is consistent with models that derive planetary volatiles from a thin veneer (or a residuum) of C-chondrite material; apparently the Moon received only 2.6% of the Earth's endowment of such material per unit mass.Chalcogens (Se and Te) have virtually constant and identical abundances in lunar and terrestrial basalts, probably reflecting saturation with Fe(S, Se, Te) in the source regions.Siderophiles show diverse trends. Ni is relatively abundant in lunar basalts (4 × 10^?3 × Cl-chondrites), whereas Ir, Re, Ge, Au are depleted to 10^?4?10^?5× Cl. Except for Ir, these elements are consistently enriched in terrestrial basalts: Ni 3 × , Re 370 ×, Ge 330 × , Au 9 × . This difference apparently reflects the presence of nickel-iron phase in the lunar mantle, which sequesters these metals. On Earth, where such metal is absent, these elements partition into the crust to a greater degree. Though no lunar mantle rock is known, an analogue is provided by the siderophile-rich dunite 72417 (~0.1% metal) and the complementary, siderophile-poor troctolite 76535. The implied metal-siderophile distribution coefficients range from 10⁴ to 10⁶, and are consistent with available laboratory data.The evidence does not support the alternative explanation advanced by Ringwood—that Re was volatilized during the Moon's formation, and is an incompatible element (like La or W⁴⁺) in igneous processes. Re is much more depleted than elements of far greater volatility: (Re/U)_Cl～- 4 × 10^?6 vs (T1/U)_Cl = 1.3 × 10^?4, and Re does not correlate with La or other incompatibles.Heavy alkalis (K, Rb, Cs) show increasing depletion with atomic number. Cs/Rb ratios in lunar basalts, eucrites, and shergottites are 0.44, 0.36, and 0.65 × Cl, whereas the value for the bulk Earth is 0.15–0.26. These ratios fall within the range observed in LL and E6 chondrites. supporting the suggestion that the alkali depletion in planets, as in chondrites, was caused by localized remelting of nebular dust (= chondrule formation). Indeed, the small fractionation of K, Rb and Cs, despite their great differences in volatility, suggests that the planets, like the chondrites, formed from a mixture of depleted and undepleted material, not from a single, partially devolatilized material.     

Comparative Scavenging of Yttrium and the Rare Earth Elements in Seawater: Competitive Influences of Solution and Surface Chemistry

Distribution coefficients were obtained for yttrium and the rare earth elements (YREEs) in aqueous solutions containing freshly precipitated hydroxides of trivalent cations (Fe³⁺, Al³⁺, Ga³⁺, and In³⁺). Observed patterns of log _i K _S–, where _i K _S = [MS _i ][M³⁺]^?1[S _i ]^?1, [MS _i ] is the concentration of a sorbed YREE, [M³⁺] is the concentration of a free hydrated YREE ion, and [S _i] is the concentration of a sorptive solid substrate (Fe(III), Al, Ga, In)– exhibited similarities to patterns of YREE solution complexation constants with hydroxide (_OH β ₁) and fluoride (_F β ₁), but also distinct differences. The log _i K _S pattern for YREE sorption on Al hydroxide precipitates is very similar to the pattern of YREE hydroxide stability constants (log_OH β ₁) in solution. Linear free-energy relationships between log _i K _S and log_OH β ₁ showed excellent correlation for YREE sorption on Al hydroxide precipitates, good correlation for YREE sorption on Ga or In hydroxide precipitates, yet poor correlation for YREE sorption on Fe(III) hydroxide precipitates. Whereas the correlation between log _i K _S and log_F β ₁ was generally poor, patterns of log( _i K _S/_F β ₁) displayed substantially increased smoothness compared to patterns of log _i K _S. This indicates that the conspicuous sequence of inflections along the YREE series in the patterns of log _i K _S and log_F β ₁ is very similar, particularly for In and Fe(III) hydroxide precipitates. While the log _i K _S patterns obtained with Fe(III) hydroxide precipitates in this work are quite distinct from those obtained with Al, Ga, and In hydroxide precipitates, they are in good agreement with patterns of YREE sorption on ferric oxyhydroxide precipitates reported by others. Furthermore, our log _i K _S patterns for Fe(III) hydroxide precipitates bear a striking resemblance to predicted log _i K _S patterns for natural surfaces that are based on YREE solution chemistry and shale-normalized YREE concentrations in seawater. Yttrium exhibits an itinerant behavior among the REEs: sorption of Y on Fe(III) hydroxide precipitates is intermediate to that of La and Ce, while for Al hydroxide precipitates Y sorption is similar to that of Eu. This behavior of Y can be rationalized from the propensities of different YREEs for covalent vs. ionic interactions. The relatively high shale-normalized concentration of Y in seawater can be explained in terms of primarily covalent YREE interactions with scavenging particulate matter, whereby Y behaves as a light REE, and primarily ionic interactions with solution ligands, whereby Y behaves as a heavy REE.     

Highly siderophile elements in the Earth, Moon and Mars: Update and implications for planetary accretion and differentiation

The highly siderophile elements (HSE) pose a challenge for planetary geochemistry. They are normally strongly partitioned into metal relative to silicate. Consequently, planetary core segregation might be expected to essentially quantitatively remove these elements from planetary mantles. Yet the abundances of these elements estimated for Earth's primitive upper mantle (PUM) and the martian mantle are broadly similar, and only about 200 times lower than those of chondritic meteorites. In contrast, although problematic to estimate, abundances in the lunar mantle may be more than twenty times lower than in the terrestrial PUM. The generally chondritic Os isotopic compositions estimated for the terrestrial, lunar and martian mantles require that their long-term Re/Os ratios were within the range of chondritic meteorites. Further, most HSE in the terrestrial PUM also appear to be present in chondritic relative abundances, although Ru/Ir and Pd/Ir ratios are slightly suprachondritic. Similarly suprachondritic Ru/Ir and Pd/Ir ratios have also been reported for some lunar impact melt breccias that were created via large basin forming events.Numerous hypotheses have been proposed to account for the HSE present in Earth's mantle. These hypotheses include inefficient core formation, lowered metal-silicate D values resulting from metal segregation at elevated temperatures and pressures (as may occur at the base of a deep magma ocean), and late accretion of materials with chondritic bulk compositions after the cessation of core segregation. Synthesis of the large database now available for HSE in the terrestrial mantle, lunar samples, and martian meteorites reveals that each of the main hypotheses has flaws. Most difficult to explain is the similarity between HSE in the Earth's PUM and estimates for the martian mantle, coupled with the striking differences between the PUM and estimates for the lunar mantle. More complex, hybrid models that may include aspects of inefficient core formation, HSE partitioning at elevated temperatures and pressures, and late accretion may ultimately be necessary to account for all of the observed HSE characteristics. Participation of aspects of each process may not be surprising as it is difficult to envision the growth of a planet, like Earth, without the involvement of each.     

Systematics of metal-silicate partitioning for many siderophile elements applied to Earth’s core formation

Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO₂ conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO₂ yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO₂ conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.     

Experimental studies of metal-silicate partitioning of Sb: Implications for the terrestrial and lunar mantles

The terrestrial mantle has a well defined Sb depletion of ∼7 ± 1 (Jochum and Hofmann, 1997), and the lunar mantle is depleted relative to the Earth by a factor of ∼50 ± 5 (Wolf and Anders, 1980). Despite these well defined depletions, there are few data upon which to evaluate their origin—whether due to volatility or core formation. We have carried out a series of experiments to isolate several variables such as oxygen fugacity, temperature, pressure, and silicate and metallic melt compositions, on the magnitude of . The activity of Sb in FeNi metal is strongly composition dependent such that solubility of Sb as a function of fO₂ must be corrected for the metal composition. When the correction is applied, Sb solubility is consistent with 3+ valence. Temperature series (at 1.5 GPa) shows that decreases by a factor of 100 over 400 °C, and a pressure series exhibits an additional decrease between ambient pressure (100 MPa) and 13 GPa. A strong dependence upon silicate melt composition is evident from a factor of 100 decrease in between nbo/t values of 0.3 and 1.7. Consideration of all these variables indicates that the small Sb depletion for the Earth’s mantle can be explained by high PT equilibrium partitioning between metal and silicate melt . The relatively large lunar Sb depletion can also be explained by segregation of a small metallic core, at lower pressure conditions where is much higher (2500).     

Conditions of formation of the Mavrokoryfi high-sulfidation epithermal Cu�CAg�CAu�CTe mineralization (Petrota Graben, NE Greece)

The Mavrokoryfi Cu?CAg?CAu?CTe prospect, northeastern Greece, consists of atypical, high-sulfidation mineralization where precious metals were introduced contemporaneously with advanced argillic alteration from magmatic vapors. It occurs as veins of massive sulfides in zones of silicic and advanced argillic alteration spatially associated with an andesitic lava dome and hyaloclastites. Mineralogical data demonstrate an unusual ore and gangue mineralogy that is compatible with formation under very oxidizing conditions (logfO₂ values of >?31.8) at temperatures of 200°C to 250°C. Oxidizing conditions favored the formation of hypogene lead sulfates (anglesite and barian celestite) instead of galena. Selenian acanthite, cadmian freibergite, and argentian goldfieldite are the main carriers of silver in the deposit and are reported in Greece for the first time. They were deposited at logfS₂ of ?9 to ?7 and logfTe₂ values of ?9 to ?12.5 (250°C). Ag-poor goldfieldite at Mavrokoryfi has up to 3.7 apfu Te and is the most Te-rich goldfieldite yet reported. The mineralization is accompanied by aluminum?Cphosphate?Csulfate minerals of magmatic-hydrothermal origin and an unusual Pb-enrichment. Ore-forming components were likely derived from andesite porphyries.     

Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene,olivine, armalcolite,ilmenite, and silicate glass during mare basalt petrogenesis

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO₂) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (>?100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti³⁺ under fO₂ conditions relevant to lunar magmatism (IW ??1.5 to ??1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% ^[IV]Ti⁴⁺ in the pyroxene. In addition, our results can help to better constrain the Ti³⁺/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.     

Coupled Ce-Nd isotope systematics and rare earth elements differentiation of the moon

¹³⁸Ce/¹⁴²Ce and ¹⁴³Nd/¹⁴⁴Nd isotope ratios of lunar samples are determined to constrain the petrogenetic differentiation and evolution of the moon. High-precision Ce-Nd isotope data, well-defined Rb-Sr isochrons, and rare earth elements (REE) abundances of lunar samples show that unexpectedly low La/Ce ratios of evolved lunar highland samples are preserved from at least 3.9 Ga. Precise analysis of REE abundances indicates that the low La/Ce ratio results from a depletion of La relative to other REE. This depletion can be seen in pristine KREEP basalts and Mg-suite rocks from 3.85 to 4.46 Ga. As REE abundances of all these samples are controlled by the presence of a KREEP component, the depletion was probably inherited from a late crystallization sequence of the lunar magma ocean related to the production of the original KREEP component.     

Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ¹⁸O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO₂, Al₂O₃). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ⁵⁶Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ¹⁸O and δ⁵⁶Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ⁵⁶Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ¹⁸O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ¹⁸O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ¹⁸O and δ⁵⁶Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).     

The origin of geochemical diversity of lunar mantle sources inferred from the combined U-Pb, Rb-Sr, and Sm-Nd isotope systematics of mare basalt 10017

The results of our combined U-Pb, Rb-Sr, and Sm-Nd isotope study of mare basalt 10017 contribute to the understanding of the petrogenetic processes involved in the origin of geochemical diversity in lunar mare basalt sources, as well as the U-Pb isotope systematics of the Moon. The Rb-Sr, Sm-Nd, and ²³⁸U-²⁰⁶Pb isotope systems yield concordant crystallization ages of 3.633 ± 0.057 Ga, 3.678 ± 0.069 Ga, and 3.616 ± 0.098 Ga, respectively. The ²³⁵U-²⁰⁷Pb isochron yields an older, though still concordant, age of 3.80 ± 0.12 Ga. Neither the ²⁰⁶Pb-²⁰⁷Pb system nor U-Pb concordia system yields an age for 10017 that is concordant with the age determined from the Sm-Nd, Rb-Sr, and ²³⁸U-²⁰⁶Pb systems. The initial ⁸⁷Sr/⁸⁶Sr of 10017 is 0.69941 ± 7 and the initial ε_Nd is +3.2 ± 0.4. Initial Pb isotopic compositions, determined from the U-Pb isochrons, are ²⁰⁶Pb/²⁰⁴Pb_i = 31 ± 11 and ²⁰⁷Pb/²⁰⁴Pb_i = 34 ± 15. Together, these initial Pb compositions constrain the μ value of the 10017 source to be 70 ± 30, assuming a single-stage Pb growth model. This is considerably lower than μ values typically estimated for mare basalt sources (∼100-600). Regardless, the μ values calculated for the sources of mare basalts, as well as other lunar samples, show a range that is larger than can be explained by fractionation of U from Pb solely by crystallization of silicate phases and ilmenite during magma ocean solidification and formation of lunar mantle sources. The U-Pb isotope systematics may reflect late-stage formation of a sulfide phase, which strongly fractionates Pb from U but has minimal effect on Rb/Sr or Sm/Nd compositions, during crystallization of the lunar magma ocean.     

Distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid equilibria in oceanic ridge basalt: an experimental study

The distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid pairs as a function of temperature and oxygen fugacity were experimentally investigated using an oceanic ridge basalt enriched with Eu and Sr as the starting material. Experiments were conducted between 1190° and 1140°C over a range of oxygen fugacities between 10^?8 and 10^?14 atm.The molar distribution coefficients are given by the equations: log^PL_Sr = 7320/T ? 4.62logK^CPX_Sr = 18020/T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logD^PL_Sr = 6570/T ? 4.30logD^CPX_Sr = 18434/T ? 13.62.Although the mole fraction distribution coefficients have a smaller dependence on bulk composition than do the weight fraction distribution coefficients, they are not independent of bulk composition, thereby restricting the application of these experimental results to rocks similar to oceanic ridge basalts in bulk composition.Because the Sr distribution coefficients are independent of oxygen fugacity, they may be used as geothermometers. If the temperature can be determined independently — for example, with the Sr distribution coefficients, the Eu distribution coefficients may be used as oxygen geobarometers. Throughout the range of oxygen fugacities ascribed to terrestrial and lunar basalts, plagioclase concentrates Eu but clinopyroxene rejects Eu.     

The Neoproterozoic-early Paleozoic metamorphic and magmatic evolution of the Eastern Sierras Pampeanas: an overview

The Eastern Sierras Pampeanas were structured by three main events: the Ediacaran to early Cambrian (580?C510?Ma) Pampean, the late Cambrian?COrdovician (500?C440?Ma) Famatinian and the Devonian-Carboniferous (400?C350?Ma) Achalian orogenies. Geochronological and Sm?CNd isotopic evidence combined with petrological and structural features allow to speculate for a major rift event (Ediacaran) dividing into two Mesoproterozoic major crustal blocks (source of the Grenvillian age peaks in the metaclastic rocks).This event would be coeval with the development of arc magmatism along the eastern margin of the eastern block. Closure of this eastern margin led to a Cambrian active margin (Sierra Norte arc) along the western margin of the eastern block in which magmatism reworked the same crustal block. Consumption of a ridge segment (input of OIB signature mafic magmas) which controlled granulite-facies metamorphism led to a final collision (Pampean orogeny) with the western Mesoprotrozoic block. Sm?CNd results for the metamorphic basement suggest that the T _DM age interval of 1.8?C1.7?Ga, which is associated with the less radiogenic values of ??Nd₍₅₄₀₎ (?6 to ?8), can be considered as the mean average crustal composition for the Eastern Sierras Pampeanas. Increasing metamorphic grade in rocks with similar detrital sources and metamorphic ages like in the Sierras de Córdoba is associated with a younger T _DM age and a more positive ??Nd₍₅₄₀₎ value. Pampean pre-540?Ma granitoids form two clusters, one with T _DM ages between 2.0 and 1.75?Ga and another between 1.6 and 1.5?Ga. Pampean post-540?Ma granitoids exhibit more homogenous T _DM ages ranging from 2.0 to 1.75?Ga. Ordovician re-activation of active margin along the western part of the block that collided in the Cambrian led to arc magmatism (Famatinian orogeny) and related ensialic back-arc basin in which high-grade metamorphism is related to mid-crustal felsic plutonism and mafic magmatism with significant contamination of continental crust. T _DM values for the Ordovician Famatinian granitoids define a main interval of 1.8?C1.6, except for the Ordovician TTG suites of the Sierras de Córdoba, which show younger T _DM ages ranging from 1.3 to 1.0?Ga. In Devonian times (Achalian orogeny), a new subduction regime installed west of the Eastern Sierras Pampeanas. Devonian magmatism in the Sierras exhibit process of mixing/assimilation of depleted mantle signature melts and continental crust. Achalian magmatism exhibits more radiogenic ??Nd₍₅₄₀₎ values that range between 0.5 and ?4 and T _DM ages younger than 1.3?Ga. In pre-Devonian times, crustal reworking is dominant, whereas processes during Devonian times involved different geochemical and isotopic signatures that reflect a major input of juvenile magmatism.     

An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.