Distribution of siderophile and chalcophile elements in serpentinites of the oceanic lithosphere as an insight into the magmatic and crustal evolution of mantle peridotites

The paper reports result of comparative analysis of the distribution of siderophile (Au, Pt, Pd, Co, Ni, and Cr) and chalcophile (Ag, Cd, Sb, Pb, Zn, Cu, As, and S) elements in ultramafic rock samples of various types of abyssal peridotites. One of the objectives of this research was to obtain reference estimates for the concentrations of siderophile and chalcophile elements in the two end members defining the geochemical evolutionary trends of the material of the suboceanic mantle: a sample of insignificantly depleted mantle material (spinel lherzolite) and extensively carbonated serpentinite after harzburgite, which was formed at the “endpoint” of the ascent of mantle material to the seafloor surface. The distribution of siderophile and chalcophile elements is proved to record information on the whole compositional evolution of abyssal peridotites corresponding to the trajectory of their exhumation from mantle depth levels to seafloor outcrops. These data indicate that the bulk-rock compositional parameters of abyssal peridotites can be utilized to estimate the contribution of magmatic and hydrothermal process to the distribution of siderophile and chalcophile elements.     

Precious metals in magnesian low-Ti lavas: Implications for metallogenesis and sulfur saturation in primary magmas

Boninites and related magnesian low-Ti magmas are generally regarded as partial melts of a moderately to severely depleted peridotite source. Incompatible lithophile element abundances indicate that this source was variably enriched in LREE, Zr, Sr, Ba and alkalis by some mantle metasomatic process. Low-Ti lavas from the Bonin-Mariana arc system, Cape Vogel, New Caledonia, Cyprus, Newfoundland and SE Australia have been analysed for Pd, Ir, Au, Cu, S and Se. Comparison of fresh glassy material with variably altered samples suggests sporadic loss of Au and Cu and essentially inert behaviour for Pd, Ir and Se during seawater and subsequent alteration. They are uniformly enriched in Pd (mean 15 ppb) and depleted in Cu (mean 20 ppm), S (mean < 54 ppm) and Se (mean 53 ppb) compared to average MORB (<0.8 ppb Pd, 72 ppm Cu, 800 ppm S and 196 ppb Se) and exhibit incompatible-like behaviour for these elements and Au.The data are compatible with fractionation of the chalcophile elements during multi-stage mantle melting. Primary MORB liquids are S-saturated in their mantle source and an immiscible sulfide component is retained in the mantle residue. This results in the preferential removal of metals having low D^S/L- values (base metals) and concentration of those metals with high D^S/L values (precious metals) in the residual mantle sulfide fraction. Subsequent remelting of this refractory source produces S-deficient precious metal-enriched magmas, as exemplified by boninites. The absence of correlation between incompatible lithophile element enrichment and chalcophile element abundances suggests that the latter were not added to the source during mantle metasomatism.The constraints imposed by the nature of the source region result in two fundamentally contrasting patterns of behaviour for exclusively chalcophile elements. Magmas generated in mildly depleted to undepleted source regions by low to moderate degrees of partial melting (e.g. MORB) are S-saturated and become rapidly impoverished in precious metals during the early stages of silicate fractionation, owing to the co-precipitation of an immiscible sulfide component. Magmas generated from a strongly depleted source are initially S-undersaturated and concentrate chalcophile metals in their liquid residua.The contrasting behaviour of chalcophile metals during the early crystallisation stage of MORB and low-Ti magmas lead to divergent predictions concerning the primary distribution of these metals in oceanic crust generated by these magmas. The similarity in composition of early Bushveld magmas and boninites suggests that these S-deficient, PGE-enriched magmas may be essential to the formation of platiniferous horizons in layered intrusions.     

Residual platinum-group minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle

In order to constrain the highly siderophile elements (HSE: Re and platinum group elements (PGE: Os, Ir, Ru, Pt and Pd)) host mineral(s) in refractory, base metal sulfide-free mantle residues, four very depleted spinel-harzburgites from the Lherz massif (France) have been analyzed for HSE in whole-rock and in major mineral separates (olivine, orthopyroxene, clinopyroxene and spinel) by isotope dilution. In addition, HSE host minerals have been separated and analyzed with a scanning electron microscope. Olivine and spinel show the highest HSE concentration especially for Os, Ir, Ru and Pt (up to 10 ppb) among the modally-major minerals, while the pyroxenes are 1-2 orders of magnitude poorer in HSE. The major minerals account for less than 30% of the whole-rock platinum group element budget. On the other hand, rare, micron to submicron platinum group minerals (PGM), such as Ru-Os ± Ir sulfides and Pt-Ir ± Os alloys, likely located in the intergranular spaces of the refractory depleted harzburgite, account for 50-100% of the HSE budget. The PGM grains are interpreted to be residual, having formed in response to the complete consumption of the base-metal sulfides by the high degree of partial melting (i.e. 23-24%) experienced by these samples. As they sequester the compatible platinum group elements (Os, Ir, Ru and Pt) in the mantle residue, these PGM provide key constraints for the modelling of PGE contents in terrestrial basalts (e.g. the solid/liquid partition coefficients needed to account for the compatible behavior of these elements in the mantle residue) and for understanding the long-lived Os isotope heterogeneities of the upper mantle, especially the old Re-Os ages found in young oceanic mantle. In fact, because of their Os-rich compositions and high melting temperatures, these microphases are likely to preserve their initial Os isotopic compositions unmodified over multiple events of mantle melting and mixing, and therefore generate, through recycling, heterogeneous Os isotopic signatures at different scales in the convecting mantle.     

Trace elements in ocean ridge basalt glasses: implications for fractionations during mantle evolution and petrogenesis

Seven well-documented and fresh glassy selvages from ocean floor basalt pillows were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Os, Pd, Rb, Re, Sb, Se, Te, Tl, U and Zn. The samples came from active spreading centers in the Indian and Atlantic Ocean. Glasses from DSDP Leg 24, site 238 (Indian Ocean) have a somewhat peculiar trace element pattern, but this is thought to reflect secondary processes operating at shallow depth, not an anomalous source region in the mantle. Our data rather indicate that heterogeneities in the mantle are confined to the highly incompatible lithophile elements.Chemical fractionations during petrogenesis of tholeiitic basalts are discussed in the light of literature data for primitive peridotitic upper mantle nodules. (Ir, Os), Au, Pd, Ni and Re are strongly fractionated from each other in igneous processes; the unfractionated chondritic mantle pattern thus imposes firm constraints on mantle evolution models. The potentially chalcophile elements Ag, Cd, In and Zn do not behave differently from lithophile elements of the same valency and comparable ionic radius. Residual sulfides are not abundant enough to efficiently control the partitioning of these elements during basalt petrogenesis. However, the poor coherence of Tl to Rb and U in ocean floor basalts could point to retention of Tl by residual sulfides during depletion of the MORB source regions. Sb is strongly depleted in the source regions of ocean ridge basalts; most likely, it was present as a highly incompatible Sb⁵⁺ cation. The limited Rb/Cs fractionation in oceanic tholeiites, as opposed to continental tholeiites and acidic rocks, appears to reflect the low abundance of volatile constituents and hydrous silicates in normal ocean ridge basalts.     

Mineralogical and geochemical constraints on the shallow origin, ancient veining, and multi-stage modification of the Lherz peridotite

New major- and trace-element data of bulk-rocks and constituent minerals, and whole-rock Re-Os isotopic compositions of samples from the Lherz Massif, French Pyrenees, reveal complex petrological relationships between the dominant lithologies of lherzolite ± olivine-websterite and harzburgite. The Lherz peridotite body contains elongate, foliation parallel, lithological strips of harzburgite, lherzolite, and olivine-websterite cross-cut by later veins of hornblende-bearing pyroxenites. Peridotite lithologies are markedly bimodal, with a clear compositional gap between harzburgites and lherzolites ± olivine-websterite. Bulk-rock and mineral major-element oxide (Mg-Fe-Si-Cr) compositions show that harzburgites are highly-depleted and result from ∼20-25 wt.% melt extraction at pressures <2 GPa. Incompatible and moderately-compatible trace-element abundances of hornblendite-free harzburgites are analogous to some mantle-wedge peridotites. In contrast, lherzolites ± olivine-websterite overlap estimates of primitive mantle composition, yet these materials are composite samples that represent physical mixtures of residual lherzolites and clinopyroxene dominated cumulates equilibrated with a LREE-enriched tholeiitic melt. Trace-element compositions of harzburgite, and some lherzolite bulk-rocks and pyroxenes have been modified by; (1) wide-spread interaction with a low-volume LREE-enriched melt +/− fluid that has disturbed highly-incompatible elements (e.g., LREEs, Zr) without enrichment of alkali- and Ti-contents; and (2) intrusion of relatively recent, small-volume, hornblendite-forming, basanitic melts linked to modal and cryptic metasomatism resulting in whole-rock and pyroxene Ti, Na and MREE enrichment.Rhenium-Os isotope systematics of Lherz samples are also compositionally bimodal; lherzolites ± olivine-websterite have chondritc to suprachondritic ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os values that overlap the range reported for Earth’s primitive upper mantle, whereas harzburgites have sub-chondritic ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os values. Various Os-model age calculations indicate that harzburgites, lherzolites, and olivine-websterites have been isolated from convective homogenisation since the Meso-Proterozoic and this broadly coincides with the time of melt extraction controlled by harzburgite Os-isotope compositions. The association between harzburgites resulting from melting in mantle-wedge environments and Os-rich trace-phases (laurite-erlichmanite sulphides and Pt-Os-Ir-alloys) suggests that a significant portion of persistent refractory anomalies in the present-day convecting mantle of Earth may be linked to ancient large-scale melting events related to wide-spread subduction-zone processing.     

Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (δ¹⁸O_olivine = 5.17 ± 0.08‰; ⁸⁷Sr/⁸⁶Sr = 0.7029 to 0.7031; ε_Nd = +5.7 to +7.1; ¹⁸⁷Os/¹⁸⁸Os = 0.1481 to 0.1750; ²⁰⁶Pb/²⁰⁴Pb = 19.1 to 19.7; Pd/Ir = 6 ± 3) versus those from La Palma (δ¹⁸O_olivine = 4.87 ± 0.18‰; ⁸⁷Sr/⁸⁶Sr = 0.7031 to 0.7032; ε_Nd = +5.0 to +6.4; ¹⁸⁷Os/¹⁸⁸Os = 0.1421 to 0.1460; ²⁰⁶Pb/²⁰⁴Pb = 19.5 to 20.2; Pd/Ir = 11 ± 4) are revealed from the dataset.Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (?110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 ± 0.05 Os, 0.17 ± 0.16 Ir, 0.34 ± 0.32 Ru, 2.6 ± 2.5 Pt, 1.4 ± 1.2 Pd, 0.39 ± 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites.The HIMU affinities of the lavas, in conjunction with the low δ¹⁸O_olivine and high ²⁰⁶Pb/²⁰⁴Pb for La Palma, and elevated ¹⁸⁷Os/¹⁸⁸Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic ²⁰⁶Pb/²⁰⁴Pb, ¹⁸⁷Os/¹⁸⁸Os, elevated Re/Os and Pt/Os, and low-δ¹⁸O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50 km).     

Rhenium and chalcophile elements in basaltic glasses from Ko’olau and Moloka’i volcanoes: Magmatic outgassing and composition of the Hawaiian plume

The behavior of chalcophile metals in volcanic environments is important for a variety of economic and environmental applications, and for understanding large-scale processes such as crustal recycling into the mantle. In order to better define the behavior of chalcophile metals in ocean island volcanoes, we measured the concentrations of Re, Cd, Bi, Cu, Pb, Zn, Pt, S, and a suite of major elements and lithophile trace elements in moderately evolved (6-7% MgO) tholeiitic glasses from Ko’olau and Moloka’i volcanoes. Correlated variations in the Re, Cd, and S contents of these glasses are consistent with loss of these elements as volatile species during magmatic outgassing. Bismuth also shows a good correlation with S in the Ko’olau glasses, but undegassed glasses from Moloka’i have unexpectedly low Bi contents. Rhenium appears to have been more volatile than either Cd or Bi in these magmas.Undegassed glasses with 880-1400 ppm S have 1.2-1.5 ppb Re and 130-145 ppb Cd. In contrast, outgassed melts with low S (<200 ppm) are depleted in these elements by factors of 2-5. Key ratios such as Re/Yb and Cu/Re are fractionated significantly from mantle values. Copper, Pb, and Pt contents of these glasses show no correlation with S, ruling out segregation of an immiscible magmatic sulfide phase as the cause of these variations. Undegassed Hawaiian tholeiites have Re/Yb ratios significantly higher than those of MORB, and extend to values greater than that of the primitive mantle. Loss of Re during outgassing of ocean island volcanoes, may help resolve the apparent paradox of low Re/Os ratios in ocean island basalts with radiogenic Os isotopic compositions. Plume source regions with Re/Yb ratios greater than that of the primitive mantle may provide at least a partial solution to the “missing Re” problem in which one or more reservoirs with high Re/Yb are required to balance the low Re/Yb of MORB.Lithophile trace element compositions of most Ko’olau and Moloka’i tholeiites are consistent with variable degrees of melting of fertile mantle peridotite. However, light rare earth element (LREE)-enriched glasses have trace element compositions more consistent with a garnet-rich source having a distinctive trace element composition. This provides additional evidence for a unique source component possibly related to recycled oceanic crust contributing to Ko’olau tholeiites.     

Constraints on the Trace Element Composition of the Archean Mantle Root beneath Somerset Island, Arctic Canada

Peridotites that sample Archean mantle roots are frequentlyincompatible trace element enriched despite their refractorymajor element compositions. To constrain the trace element budgetof the lithosphere beneath the Canadian craton, trace elementand rare earth element (REE) abundances were determined fora suite of garnet peridotites and garnet pyroxenites from theNikos kimberlite pipe on Somerset Island, Canadian Arctic, theirconstituent garnet and clinopyroxene, and the host kimberlite.These refractory mantle xenoliths are depleted in fusible majorelements, but enriched in incompatible trace elements, suchas large ion lithophile elements (LILE), Th, U and light rareearth elements (LREE). Mass balance calculations based on modalabundances of clinopyroxene and garnet and their respectiveREE contents yield discrepancies between calculated and analyzedREE contents for the Nikos bulk rocks that amount to LREE deficienciesof 70–99%, suggesting the presence of small amounts ofinterstitial kimberlite liquid (0·4–2 wt %) toaccount for the excess LREE abundances. These results indicatethat the peridotites had in fact depleted or flat LREE patternsbefore contamination by their host kimberlite. LREE and Sr enrichmentin clinopyroxene and low Zr and Sr abundances in garnet in low-temperatureperidotites (800–1100°C) compared with high-temperatureperidotites (1200–1400°C) suggest that the shallowlithosphere is geochemically distinct from the deep lithospherebeneath the northern margin of the Canadian craton. The Somersetmantle root appears to be characterized by a depth zonationthat may date from the time of its stabilization in the Archean. KEY WORDS: Canada; mantle; metasomatism; peridotite; trace elements     

Unravelling the effects of melt depletion and secondary infiltration on mantle Re-Os isotopes beneath the French Massif Central

Spinel lherzolite xenoliths from Mont Briançon, French Massif Central, retain evidence for multiple episodes of melt depletion and melt/fluid infiltration (metasomatism). Evidence for primary melt depletion is still preserved in the co-variation of bulk-rock major elements (MgO 38.7-46.1 wt.%; CaO 0.9-3.6 wt.%), and many samples yield unradiogenic bulk-rock Os isotope ratios (¹⁸⁷Os/¹⁸⁸Os = 0.11541-0.12626). However, many individual xenoliths contain interstitial glasses and melt inclusions that are not in equilibrium with the major primary minerals. Incompatible trace element mass balance calculations demonstrate that metasomatic components comprise a significant proportion of the bulk-rock budget for these elements in some rocks, ranging to as much as 25% of Nd and 40% of Sr Critically, for Re-Os geochronology, melt/fluid infiltration is accompanied by the mobilisation of sulfide. Consequently, bulk-rock isotope measurements, whether using lithophile (e.g. Rb-Sr, Sm-Nd) or siderophile (Re-Os) based isotope systems, may only yield a perturbed and/or homogenised average of these multiple events.Osmium mass balance calculations demonstrate that bulk-rock Os in peridotite is dominated by contributions from two populations of sulfide grain: (i) interstitial, metasomatic sulfide with low [Os] and radiogenic ¹⁸⁷Os/¹⁸⁸Os, and (ii) primary sulfides with high [Os] and unradiogenic ¹⁸⁷Os/¹⁸⁸Os, which have been preserved within host silicate grains and shielded from interaction with transient melts and fluid. The latter can account for >97% of bulk-rock Os and preserve geochronological information of the melt from which they originally precipitated as an immiscible liquid. The Re-depletion model ages of individual primary sulfide grains preserve evidence for melt depletion beneath the Massif Central from at least 1.8 Gyr ago despite the more recent metasomatic event(s).     

Minor and trace elements in some meteoritic minerals

The mineral phases including olivine, orthopyroxene, clinopyroxene, troilite, nickel-iron, plagioclase, chromite and the phosphates were separated from several meteorites. These were a hypersthene chondrite (Modoc), a bronzite chondrite (Guareña), an enstatite chondrite (Khairpur), and two eucrites (Haraiya and Moore County); diopside was separated from the Nakhla achondrite. The purified minerals were analyzed for trace and minor elements by spark source mass spectrometry and instrumental neutron activation analysis. On the meteorites examined our results show that Co, Ni, Cu, Ge, As, Ru, Rh, Pd, Sn, Sb, W, Re, Os, Ir, Pt and Au are entirely or almost entirely siderophile; Na, Rb, Sr, Y, Ba and the rare earth elements lithophile; Se chalcophile. The transition elements So, Ti, V, Cr and Mn are lithophile in most stony meteorites, but show chalcophile affinities in the enstatite chondrites (and enstatite achondrites), as do Zn, Zr and Nb. In the ordinary chondrites Ga shows both lithophile and siderophile affinities, but becomes entirely siderophile in the enstatite chondrites. Molybdenum and tellurium show strong siderophile and weaker chalcophile affinity. The lithophile elements are distributed among the minerals according to the crystallochemical factors, the most effective controlling factor being ionic size.     

Chemical composition and origin of the earth's primitive mantle

An attempt has been made to estimate the chemical composition of the earth's primitive mantle by a critical evaluation of data derived from ultramafic mantle samples and partial melting model calculations for mafic and ultramafic magmas of various ages.Compatible (Al, Ca, Si, Mg, Fe) and moderately incompatible (Ti, Zr, heavy and middle rare earth) elements in basaltic magma sources have not changed significantly since the early Archaean (~3.5 Byr). Estimated abundances for refractory lithophile elements (such as Al, Ca, Ti, Zr, Y, Se, REE etc.) in the primitive mantle are about 2.0 times ordinary chondrites (~ 1.1 times Cl chondrites relative to Mg). Highly incompatible volatile elements (K, Rb, Cs, Tl, Pb etc.) are depleted in the mantle throughout geological time. Abundances of Fe, Ni and Co are obtained on the basis of values for ultramafic nodules and model calculations using komatiites of various ages. The results show little (? 20%?) dispersion and there is no obvious secular variation since 3.5 Byr. Noble metals show similar effects. These data permit constraints to be placed on the timing of core formation.The estimated elemental abundances for the primitive mantle are normalized to Cl chondrites relative to Mg and plotted against the solar condensation temperature at 10^?4 atm. Above 700 K there are two parallel trends which are defined by lithophile elements (Al, Ca, REE, Ti, Mg, Si, Cr, Mn, Na, K, Rb, F, Zn etc.) and siderophile elements (W, Ni, Co, P, As, Ag, Sb and Ge) respectively. The depletion factor for the siderophile trend relative to the lithophile trend is about 0.085. Within each trend there is a continuous depletion towards lower temperature. A third trend is defined by noble metals (Ir, Os, Re, Pd, Pt and Au) with a depletion factor of about 0.003 relative to Cl chondrites. These trends are interpreted in terms of core-mantle differentiation and volatility-controlled processes operating before and during earth accretion.     

Tungsten in Hawaiian picrites: A compositional model for the sources of Hawaiian lavas

Concentrations of tungsten (W) and uranium (U), which represent two of the most highly incompatible elements during mantle melting, have been measured in a suite of Hawaiian picrites and primitive tholeiites from nine main-stage shield volcanoes. Tungsten abundances in the parental melts are estimated from correlations between sample W abundances and MgO contents, and/or by olivine correction calculations. From these parental melt determinations, along with independent estimates for the degree of partial melting at each volcanic center, we extrapolate the W content of the mantle sources for each shield volcano. The mantle sources of Hualalai, Mauna Loa, Kohala, Kilauea, Mauna Kea, Koolau and Loihi contain 9 ± 2 (2σ), 11 ± 5, 10 ± 4, 12 ± 4, 10 ± 5, 8 ± 7 and 11 ± 5 ng/g, respectively. When combined, the mean Hawaiian source has an average of 10 ± 3 ng/g W, which is three-times as enriched as the Depleted MORB Mantle (DMM; 3.0 ± 2.3 ng/g).The relatively high abundances of W in the mantle sources that contribute to Hawaiian lavas may be explained as a consequence of the recycling of W-rich oceanic crust and sediment into a depleted mantle source, such as the depleted MORB mantle (DMM). However, this scenario requires varying proportions of recycled materials with different mean ages to account for the diversity of radiogenic isotope compositions observed between Kea- and Loa-trend volcanoes. Alternatively, the modeled W enrichments may also reflect a primary source component that is less depleted in incompatible trace elements than the DMM. Such a source would not necessarily require the addition of recycled materials, although the presence of some recycled crust is permitted within our model parameters and likely accounts for some of the isotopic variations between volcanic centers.The physical admixture of ?0.5 wt.% outer core material with the Hawaiian source region would not be resolvable via W source abundances or W/U ratios; however, W isotopes may provide a more sensitive to this mixing process. Recent W isotopic studies show no indication of core-mantle interaction, indicating that either such a process does not occur, or that mechanisms other than physical mixing may operate at the core-mantle boundary.     

Geochemical anomalies in the mantle of the Pamirs and Tien Shan with applications to the deep-seated sources of ore material

The mantle metasomatites (fluidized magmatic rocks) of the Pamir-Tien Shan region show extremely high contents of lithophile and chalcophile trace elements, which often exceeds the regional average abundances of the Earth’s crust. Geochemical relations were established between mantle and crustal rocks, and it was shown that the compositions of magmatic rocks of different age and formation depth and polychronous mineralization are relatively stable. These data and some other facts indicate the possible influence of mantle fluids (melts) on the crustal rocks and processes. An alternative model implies the geochemical influence of crustal rocks on the geochemical characteristics of the regional mantle. The ore material of alkali basic rocks and some hydrothermal and rare metal deposits shows a geochemical affinity to the supposed mantle (mantle-crustal) sources. The ore-bearing fluids (melts) were presumably related to the evolution of ultradeep “hot” material of mantle plumes and “daughter” diapirs carrying alkaline, trace, and ore elements.     

Evidence for high-pressure core-mantle differentiation from the metal-silicate partitioning of lithophile and weakly-siderophile elements

Liquid Fe metal-liquid silicate partition coefficients for the lithophile and weakly-siderophile elements Ta, Nb, V, Cr, Si, Mn, Ga, In and Zn have been measured in multianvil experiments performed from 2 to 24 GPa, 2023-2873 K and at oxygen fugacities of −1.3 to −4.2 log units relative to the iron-wüstite buffer. Compositional effects of light elements dissolved in the metal liquid (S, C) have been examined and experiments were performed in both graphite and MgO capsules, specifically to address the effect of C solubility in Fe-metal on siderophile element partitioning. The results were used to examine whether there is categorical evidence that a significant portion of metal-silicate equilibration occurred under very high pressures during core-mantle fractionation on Earth. Although the depletion of V from the mantle due to core formation is significantly greater than that of Nb, our results indicate that both elements have similar siderophile tendencies under reducing conditions at low pressures. With increasing pressure, however, Nb becomes less siderophile than V, implying that average metal-silicate equilibration pressures of at least 10-40 GPa are required to explain the Nb/V ratio of the mantle. Similarly the moderately-siderophile, volatile element ratios Ga/Mn and In/Zn are chondritic in the mantle but both volatility and core-mantle equilibration at low pressure would render these ratios strongly sub-chondritic. Our results indicate that pressures of metal-silicate partitioning exceeding 30-60 GPa would be required to render these element ratios chondritic in the mantle. These observations strongly indicate that metal-silicate equilibration must have occurred at high pressures, and therefore support core-formation models that involve deep magma oceans. Moreover, our results allow us to exclude models that envisage primarily low-pressure (<1 GPa) equilibration in relatively small planetary bodies. We also argue that the core cannot contain significant U as this would require metal-silicate equilibration at oxygen fugacities low enough for significant amounts of Ta to have also been extracted from the mantle. Likewise, as In is more siderophile than Pb but similarly volatile and also quite chalcophile it would have been difficult for Pb to enter the core without reversing the relative depletions of these elements in the mantle unless metal-silicate equilibration occurred at high pressures >20 GPa.     

Sources of unique rhenium enrichment in fumaroles and sulphides at Kudryavy volcano

Rhenium (Re) is one of the least abundant elements in Earth, averaging 0.28 ppb in the primitive mantle. The unique occurrence of rheniite ReS₂ (74.5 wt% of Re) in Kudryavy volcano precipitates raises questions about recycling of Re-rich reservoirs within the Kurile-Kamchatka volcanic Island arc setting. The sources of this unique Re enrichment have been inferred from studies of Re-Os isotope systematic and trace elements in volcanic gases, sulphide precipitates and host volcanic rocks. The fumarolic gas condensates are enriched in hydrophile trace elements relative to fluid-immobile elements and exhibit high Ba/Nb (133-204), Rb/Y (16-406) and Th/Zr (0.01-0.25) ratios. They are characterised by high Re (7-210 ppb) and Os abundances (0.4-0.9 ppb), with ¹⁸⁷Os/¹⁸⁸Os ratios in a range 0.122-0.152. This Os isotopic compositional range is similar to that of the peridotite xenoliths from the metasomatised mantle wedge above the subducted Pacific plate, the radiogenic isotopic signature of which is probably due to radiogenic addition from a slab-derived fluid.Re- and Os-rich sulphide and oxide minerals precipitate from volcanic gases within fumarolic fields. Molybdenite (MoS₂), powellite (CaMoO₄) and cannizzarite (Pb₄Bi₆S₁₃) contain 1.5-1.7 wt%, 10 ppm, and 65-252 ppb of Re, respectively. Both molybdenite and rheniite contain normal Os concentrations, with total Os abundances in a range from 0.6 to 3.1 ppm for molybdenite, and 2.3-24.3 ppb for the rheniite samples. Repeated analyses of osmium isotope ratios for two rheniite samples form a best-fit line with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.32 ± 0.15 and an age of 79 ± 11 yr, which is the youngest age ever measured in natural samples. The high Re contents in molybdenite and rheniite led to high radiogenic ¹⁸⁷Os values, even in the limited period of time, with ¹⁸⁷Os/¹⁸⁸Os ratios up to 3.3 for molybdenite and up to 4.4 for rheniite.The Os isotopic compositions of andesite-basaltic rocks from the Kudryavy volcano (¹⁸⁷Os/¹⁸⁸Os up to 0.326) are more radiogenic than those of residual peridotites and fumarolic gas condensates that are mainly constituted from magmatic vapor. Such radiogenic values can be attributed either to the addition of a radiogenic Os-rich subduction component to the depleted mantle, or to the assimilation of older dacitic caldera walls (¹⁸⁷Os/¹⁸⁸Os = 0.6) during arc magma ascent and emplacement. The latter hypothesis is supported by the correlation between ¹⁸⁷Os/¹⁸⁸Os ratio and indicators of fractionation such as MgO or Ni, and by low contents of potentially hydrophile trace elements such as Ba, Rb and Th relative to fluid-immobile elements such as Nb, Zr and Y. The high Re flux in the Kudryavy volcano (estimated at ∼46 kg/yr) can be explained by remobilisation of Re by Cl-rich water from an underplated mantle wedge and subducted organic-rich sediments of the Pacific plate.     

Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths

We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ²⁵Mg = −0.14 ± 0.06; δ²⁶Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ⁷Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ⁷Li = 3.5 ± 0.5‰, δ²⁵Mg = −0.10 ± 0.03‰ and δ²⁶Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ⁷Li and δ²⁶Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ⁷Li and δ²⁶Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ⁷Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ⁷Li seen in some oceanic basalts.     

Granulite sulphides as tracers of lower crustal origin and evolution: An example from the Slave craton, Canada

We carried out a detailed study of sulphide minerals, a ubiquitous mineral group in lower crustal mafic to peraluminous granulite xenoliths from the Diavik kimberlites, to assess their use in constraining the origin and tectonothermal evolution of the deep crust, and to obtain additional data on the composition of lower crust beneath ancient continents. Sulphides are overwhelmingly pyrrhotite with minor Ni (0.7-3.9 at.%), Co (0.1-0.7 at.%), and Cu contents (0.4-3.9 at.%). Sulphide modes in mafic granulites range from 0.14 to 0.55 vol%, translating into bulk rock S contents from ∼600 to 2000 ppm, similar to S contents in other mafic igneous rocks and indicating preservation of primary igneous S contents. In mafic granulites, Re and Os abundances in sulphides range from 42.5 to 726 ppb and 3.2 to 180 ppb, respectively, whereas those in peraluminous granulites are distinctly lower (36.1-282 ppb and 1.8-7.2 ppb, respectively), suggestive of Re and Os loss to fractionating sulphides in the more evolved precursors of these rocks.The significant within-sample variability of ¹⁸⁷Os/¹⁸⁸Os and correlation with ¹⁸⁷Re/¹⁸⁸Os indicates the preservation of primary Re-Os isotope systematics and time-integrated decay of the measured ¹⁸⁷Re. Within the large uncertainties inherent in the nature of the samples and technique, sulphides in some granulites may record major tectonothermal events in the central Slave craton spanning several billion years of evolution. Multiple generations of sulphide can occur in a single sample. These data attest to the heterogeneous composition and complex history of the Slave craton lower crust.     

The Lithium, Boron and Beryllium content of serpentinized peridotites from ODP Leg 209 (Sites 1272A and 1274A): Implications for lithium and boron budgets of oceanic lithosphere

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 μg g⁻¹) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 μg g⁻¹), depleted in Li (most values below 1 μg g⁻¹) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 μg g⁻¹), H₂O and Cl contents and to lower Li contents (0.07-3.37 μg g⁻¹) of peridotites, implying that—contrary to alteration of oceanic crust—B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m × 1 m × thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.     

Highly siderophile element composition of the Earth’s primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths

Osmium, Ru, Ir, Pt, Pd and Re abundances and ¹⁸⁷Os/¹⁸⁸Os data on peridotites were determined using improved analytical techniques in order to precisely constrain the highly siderophile element (HSE) composition of fertile lherzolites and to provide an updated estimate of HSE composition of the primitive upper mantle (PUM). The new data are used to better constrain the origin of the HSE excess in Earth’s mantle. Samples include lherzolite and harzburgite xenoliths from Archean and post-Archean continental lithosphere, peridotites from ultramafic massifs, ophiolites and other samples of oceanic mantle such as abyssal peridotites. Osmium, Ru and Ir abundances in the peridotite data set do not correlate with moderately incompatible melt extraction indicators such as Al₂O₃. Os/Ir is chondritic in most samples, while Ru/Ir, with few exceptions, is ca. 30% higher than in chondrites. Both ratios are constant over a wide range of Al₂O₃ contents, but show stronger scatter in depleted harzburgites. Platinum, Pd and Re abundances, their ratios with Ir, Os and Ru, and the ¹⁸⁷Os/¹⁸⁸Os ratio (a proxy for Re/Os) show positive correlations with Al₂O₃, indicating incompatible behavior of Pt, Pd and Re during mantle melting. The empirical sequence of peridotite-melt partition coefficients of Re, Pd and Pt as derived from peridotites () is consistent with previous data on natural samples. Some harzburgites and depleted lherzolites have been affected by secondary igneous processes such as silicate melt percolation, as indicated by U-shaped patterns of incompatible HSE, high ¹⁸⁷Os/¹⁸⁸Os, and scatter off the correlations defined by incompatible HSE and Al₂O₃. The bulk rock HSE content, chondritic Os/Ir, and chondritic to subchondritic Pt/Ir, Re/Os, Pt/Re and Re/Pd of many lherzolites of the present study are consistent with depletion by melting, and possibly solid state mixing processes in the convecting mantle, involving recycled oceanic lithosphere. Based on fertile lherzolite compositions, we infer that PUM is characterized by a mean Ir abundance of 3.5 ± 0.4 ng/g (or 0.0080 ± 0.0009*CI chondrites), chondritic ratios involving Os, Ir, Pt and Re (Os/Ir_PUM of 1.12 ± 0.09, Pt/Ir_PUM = 2.21 ± 0.21, Re/Os_PUM = 0.090 ± 0.002) and suprachondritic ratios involving Ru and Pd (Ru/Ir_PUM = 2.03 ± 0.12, Pd/Ir_PUM = 2.06 ± 0.31, uncertainties 1σ). The combination of chondritic and modestly suprachondritic HSE ratios of PUM cannot be explained by any single planetary fractionation process. Comparison with HSE patterns of chondrites shows that no known chondrite group perfectly matches the PUM composition. Similar HSE patterns, however, were found in Apollo 17 impact melt rocks from the Serenitatis impact basin [Norman M.D., Bennett V.C., Ryder G., 2002. Targeting the impactors: siderophile element signatures of lunar impact melts from Serenitatis. Earth Planet. Sci. Lett, 217-228.], which represent mixtures of chondritic material, and a component that may be either of meteoritic or indigenous origin. The similarities between the HSE composition of PUM and the bulk composition of lunar breccias establish a connection between the late accretion history of the lunar surface and the HSE composition of the Earth’s mantle. Although late accretion following core formation is still the most viable explanation for the HSE abundances in the Earth’s mantle, the “late veneer” hypothesis may require some modification in light of the unique PUM composition.     

Sulfur and selenium systematics of the subcontinental lithospheric mantle: Inferences from the Massif Central xenolith suite (France)

Selenium has been analyzed in addition to S in 58 spinel peridotite xenoliths collected in Cenozoic alkali basalts from the Massif Central (France). The S concentration range now available for this suite, calculated from 123 samples, is the largest ever reported for alkali basalt-hosted xenoliths (<3-592 ppm). Likewise, the Se concentrations range between 0.2 and 67 ppb. No partial melting signature can be identified from the S and Se systematic. Half of the analyzed xenoliths have lost S during supergene weathering. By contrast, neither surficial alteration, nor loss of chalcophile elements during eruption can explain the regional-scale variations of S and Se concentrations. A first group of lherzolite xenoliths sampled in Southern Massif Central, from volcanic centers older and spatially unrelated to the Massif Central plume that triggered the Cenozoic volcanism, contains between 20 and 250 ppm S (with occasional S concentrations up to 592 ppm) and 12-67 ppb Se. It is clear that the highest S values, originally interpreted as representing S abundances in the primitive mantle, were in fact enriched by metasomatism. Highly variable S and Se contents (<5-360 ppm; 9-52 ppb) have also been observed in peridotite xenoliths collected in the Northern Massif Central, from volcanic centers mostly older than the plume. Like Group I xenoliths, these Group II xenoliths were strongly metasomatized by volatile-rich carbonated/silicated melts which precipitated Cu-rich sulfides. A third group of xenoliths from Plio-Quaternary basalts spatially related to the Massif Central Plume are uniformly poor in S (10-60 ppm) and Se (9-29 ppb). In this Group III, poikiloblastic textured xenoliths have lost most of their S and Se budget by peridotite-melt interactions at high melt/rock ratios. Taken as a whole, the Massif Central xenolith suite provides further evidence for strong heterogeneities in the S and Se budget of the sub-continental lithospheric mantle. However, the few LREE-depleted fertile lherzolites that escaped strong metasomatic alterations suggest a S- and Se-depleted primitive mantle reservoir compared to currently accepted primitive mantle estimates.