An experimental study of carbonated eclogite at 3.5-5.5 GPa – Implications for silicate and carbonate metasomatism in the cratonic mantle

We have experimentally investigated a K-bearing altered mid-ocean ridge basalt (MORB) composition to which 10% CaCO3 was added (GA1+10%cc), at temperatures of 1050-1400oC and pressures of 3•5-5•5 GPa. Experiments were conducted in piston-cylinder apparatus in Pt-Gr (Pt with inner graphite) and Au-Pd capsules. Sub-solidus assemblages for both sets of experiments contain clinopyroxene, garnet, carbonate, rutile, coesite and K-feldspar. Apatite was observed only in the Pt-Gr experiments. Melting behaviour in experiments using different capsule materials contrasted markedly. Experiments in Pt-Gr capsules showed the silicate solidus to be at temperatures less than 1100oC at 3•5GPa and less than 1050oC at 4•5-5•0 GPa.These are similar (3•5GPa) or lower (4•5-5•0 GPa) temperatures compared with the carbonate solidus (1075-1125oC at 3•5-5•0 GPa). Melts in the Pt-Gr runs evolve with increasing degree of melting from K-rich silicate melts at the lowest degree of melting to carbonate-silicate immiscible liquids and silicate-carbonate melts at intermediate degrees of melting, and finally to silicate melts at the highest degrees of melting. Experiments in Au-Pd capsules were performed only at 5•0GPa. The carbonate solidus is between 1200 and 1225oC (at least 100oC higher than in the experiments in Pt-Gr capsules at the same pressure-temperature conditions).The first melts to be produced are carbonatitic and exhibit increasing SiO2 content with increasing temperature.This contrast in melting behaviour is explained by the relatively rapid diffusion of H through the Pt-Gr capsules, resulting in formation of H2O, and thus dramatically depressing both the silicate and the carbonate solidi in the Pt-Gr experiments compared with those in the Au-Pd experiments. This presumably reflects the lower permeability of Au-Pd to H, resulting in a much lower H2O/CO2 ratio in the Au-Pd encapsulated experiments. The presence of water in the melt was demonstrated by Fourier transform infrared (FTIR) spectroscopic analysis of one Pt-Gr experiment, indicating ~0•5wt % H2O in the bulk composition. Further confirmation that H2O plays such a role in the Pt-Gr experiments was provided by an additional experiment performed in a Au-Pd capsule with ~10 wt % H2Ospecifically added. In this experiment immiscible carbonate and silicate melts were observed. Carbonate- silicate liquid immiscibility is considered to occur as a result of the H2O present in the system. These results can be applied to natural systems in several ways. First, the presence of a small amount of either silicate melt or H2O-fluid in the system will act as a ‘flux’, depressing the carbonate solidus to much lower temperatures than inanhydrous systems. Second, the full trend in melt evolution from silicate-rich to carbonate-rich melts, which is also observed in inclusions in diamonds, can be explained by melting of K- and CO2-bearing, water-undersaturated MORB compositions. In cratonic environments low-degree silicate and immiscible silicate and carbonate melts will metasomatize the overlying mantle in different ways, producing, in the first instance, Si enrichment and crystallization of additional orthopyroxene, phlogopite, pyrope-rich garnet and consuming olivine, and, in the second case, carbonate metasomatism, with additional magnesite-dolomite, clinopyroxene and apatite. Both metasomatic styles have been described in natural peridotite xenoliths from the cratonic lithosphere

Base metal sulphide geochemistry of southern African mantle eclogites (Roberts Victor): Implications for cratonic mafic magmatism and metallogenesis

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this recordPlatinum-group elements (PGE) display a chalcophile behaviour and are largely hosted by base metal sulphide (BMS) minerals in the mantle. During partial melting of the mantle, BMS release their metal budget into the magma generated. The fertility of magma sources is a key component of the mineralisation potential of large igneous provinces (LIP) and the origin of orthomagmatic sulphide deposits hosted in cratonic mafic magmatic systems. Fertility of mantle-derived magma is therefore predicated on our understanding of the abundance of metals, such as the PGE, in the asthenospheric and lithospheric mantle. Estimations of the abundance of chalcophile elements in the upper mantle are based on observations from mantle xenoliths and BMS inclusions in diamonds. Whilst previous assessments exist for the BMS composition and chalcophile element budget of peridotitic mantle, relatively few analyses have been published for eclogitic mantle. Here, we present sulphide petrography and an extensive in situ dataset of BMS trace element compositions from Roberts Victor eclogite xenoliths (Kaapvaal Craton, South Africa). The BMS are dominated by pyrite-chalcopyrite-pentlandite (± pyrrhotite) assemblages with S/Se ratios ranging 1200 to 36,840 (with 87% of analyses having S/Se this editing is incorrect. This should read "(with 87% of analyses having S/Se 100 ppm) and are characteristically enriched in Os, Ir, Ru and Rh. Nano- and micron-scale Pd-Pt antimonide, telluride and arsenide platinum-group minerals (PGM) are observed spatially associated with BMS. We suggest that the predominance of pyrite in the xenoliths reflects the process of eclogitisation and that the trace element composition of the eclogite BMS was inherited from oceanic crustal protoliths of the eclogites, introduced into the SCLM via ancient subduction during formation of the Colesberg Magnetic Lineament c. 2.9 Ga and the cratonisation of the Kaapvaal Craton. Crucially, we demonstrate that the PGE budget of eclogitic SCLM may be substantially higher than previously reported, akin to peridotitic compositions, with significant implications for the PGE fertility of cratonic mafic magmatism and metallogenesis. We quantitatively assess these implications by modelling the chalcophile geochemistry of an eclogitic melt component in parental magmas of the mafic Rustenburg Layered Suite of the Bushveld Complex.Natural Environment Research Council (NERC)Russian Science Foundatio

Cumulate causes for the low contents of sulfide-loving elements in the continental crust

Despite the economic importance of chalcophile (sulfide-loving) and siderophile (metal-loving) elements (CSEs), it is unclear how they become enriched or depleted in the continental crust, compared with the oceanic crust. This is due in part to our limited understanding of the partitioning behaviour of the CSEs. Here I compile compositional data for mid-ocean ridge basalts and subduction-related volcanic rocks. I show that the mantle-derived melts that contribute to oceanic and continental crust formation rarely avoid sulfide saturation during cooling in the crust and, on average, subduction-zone magmas fractionate sulfide at the base of the continental crust prior to ascent. Differentiation of mantle-derived melts enriches lower crustal sulfide- and silicate-bearing cumulates in some CSEs compared with the upper crust. This storage predisposes the cumulate-hosted compatible CSEs (such as Cu and Au) to be recycled back into the mantle during subduction and delamination, resulting in their low contents in the bulk continental crust and potentially contributing to the scarcity of ore deposits in the upper continental crust. By contrast, differentiation causes the upper oceanic and continental crust to become enriched in incompatible CSEs (such as W) compared with the lower oceanic and continental crust. Consequently, incompatible CSEs are predisposed to become enriched in subduction-zone magmas that contribute to continental crust formation and are less susceptible to removal from the continental crust via delamination compared with the compatible CSEs

Slab melting as a barrier to deep carbon subduction

Interactions between crustal and mantle reservoirs dominate the surface inventory of volatile elements over geological time, moderating atmospheric composition and maintaining a lifesupporting planet1. While volcanoes expel volatile components into surface reservoirs, subduction of oceanic crust is responsible for replenishment of mantle reservoirs2,3. Many natural, ‘superdeep’ diamonds originating in the deep upper mantle and transition zone host mineral inclusions, indicating an affinity to subducted oceanic crust4–7. Here we show that the majority of slab geotherms will intersect a deep depression along the melting curve of carbonated oceanic crust at depths of approximately 300 to 700 kilometres, creating a barrier to direct carbonate recycling into the deep mantle. Low-degree partial melts are alkaline carbonatites that are highly reactive with reduced ambient mantle, producing diamond. Many inclusions in superdeep diamonds are best explained by carbonate melt–peridotite reaction. A deep carbon barrier may dominate the recycling of carbon in the mantle and contribute to chemical and isotopic heterogeneity of the mantle reservoir

Diamondites: evidence for a distinct tectono-thermal diamond-forming event beneath the Kaapvaal craton

The petrogenesis and relationship of diamondite to well-studied monocrystalline and fibrous diamonds are poorly understood yet would potentially reveal new aspects of how diamond-forming fluids are transported through the lithosphere and equilibrate with surrounding silicates. Of 22 silicate- and oxide-bearing diamondites investigated, most yielded garnet intergrowths (n = 15) with major element geochemistry (i.e. Ca–Cr) classifying these samples as low-Ca websteritic or eclogitic. The garnet REE patterns fit an equilibrium model suggesting the diamond-forming fluid shares an affinity with high-density fluids (HDF) observed in fibrous diamonds, specifically on the join between the saline–carbonate end-members. The δ13C values for the diamonds range from − 5.27 to − 22.48‰ (V-PDB) with δ18O values for websteritic garnets ranging from + 7.6 to + 5.9‰ (V-SMOW). The combined C–O stable isotope data support a model for a hydrothermally altered and organic carbon-bearing subducted crustal source(s) for the diamond- and garnet-forming media. The nitrogen aggregation states of the diamonds require that diamondite-formation event(s) pre-dates fibrous diamond-formation and post-dates most of the gem monocrystalline diamond-formation events at Orapa. The modelled fluid compositions responsible for the precipitation of diamondites match the fluid-poor and fluid-rich (fibrous) monocrystalline diamonds, where all grow from HDFs within the saline-silicic-carbonatitic ternary system. However, while the nature of the parental fluid(s) share a common lithophile element geochemical affinity, the origin(s) of the saline, silicic, and/or carbonatitic components of these HDFs do not always share a common origin. Therefore, it is wholly conceivable that the diamondites are evidence of a distinct and temporally unconstrained tectono-thermal diamond-forming event beneath the Kaapvaal craton

Chalcophile elements and sulfides in the upper mantle

Sulfides are among the most important petrogenetic agents in magmatic systems. They are ubiquitous in most upper-mantle rock types, common as inclusions in diamonds and they host significant amounts of geochemically and economically important chalcophile (‘sulfur-loving’) elements, such as Cu, Ni, Pb, In, Au and the platinum-group elements. Despite their low abundance (<< 1% of the bulk rock), residual sulfides have a disproportionate control over the chalcophile element budget in upper mantle lithologies, as well as that of melts derived from the Earth's mantle

Chalcophile elements and sulfides in the upper mantle

Sulfides are among the most important petrogenetic agents in magmatic systems. They are ubiquitous in most upper-mantle rock types, common as inclusions in diamonds and they host significant amounts of geochemically and economically important chalcophile (‘sulfur-loving’) elements, such as Cu, Ni, Pb, In, Au and the platinum-group elements. Despite their low abundance (<< 1% of the bulk rock), residual sulfides have a disproportionate control over the chalcophile element budget in upper mantle lithologies, as well as that of melts derived from the Earth's mantle