Arno Rohrbach

Redox freezing and melting in the Earth’s deep mantle resulting from carbon–iron redox coupling

Very low seismic velocity anomalies in the Earth’s mantle may reflect small amounts of melt present in the peridotite matrix, and the onset of melting in the Earth’s upper mantle is likely to be triggered by the presence of small amounts of carbonate. Such carbonates stem from subducted oceanic lithosphere in part buried to depths below the 660-kilometre discontinuity and remixed into the mantle. Here we demonstrate that carbonate-induced melting may occur in deeply subducted lithosphere at near-adiabatic temperatures in the Earth’s transition zone and lower mantle. We show experimentally that these carbonatite melts are unstable when infiltrating ambient mantle and are reduced to immobile diamond when recycled at depths greater than ∼250 kilometres, where mantle redox conditions are determined by the presence of an (Fe,Ni) metal phase. This ‘redox freezing’ process leads to diamond-enriched mantle domains in which the Fe0, resulting from Fe2+ disproportionation in perovskites and garnet, is consumed but the Fe3+ preserved. When such carbon-enriched mantle heterogeneities become part of the upwelling mantle, diamond will inevitably react with the Fe3+ leading to true carbonatite redox melting at ∼660 and ∼250 kilometres depth to form deep-seated melts in the Earth’s mantle.

Metal saturation in the upper mantle.

The oxygen fugacity fO2of the Earth’s mantle is one of the fundamental variables in mantle petrology. Through ferric–ferrous iron and carbon–hydrogen–oxygen equilibria, fO2 influences the pressure–temperature positions of mantle solidi and compositions of small-degree mantle melts. Among other parameters, fO2 affects the water storage capacity and rheology of the mantle. The uppermost mantle, as represented by samples and partial melts, is sufficiently oxidized to sustain volatiles, such as H2O and CO2, as well as carbonatitic melts, but it is not known whether the shallow mantle is representative of the entire upper mantle. Using high-pressure experiments, we show here that large parts of the asthenosphere are likely to be metal-saturated. We found that pyroxene and garnet synthesized at >7 GPa in equilibrium with metallic Fe can incorporate sufficient ferric iron that the mantle at >250 km depth is so reduced that an (Fe,Ni)-metal phase may be stable. Our results indicate that the oxidized nature of the upper mantle can no longer be regarded as being representative for the Earth’s upper mantle as a whole and instead that oxidation is a shallow phenomenon restricted to an upper veneer only about 250 km in thickness.

New thermodynamic data for CoTiO3, NiTiO3 and CoCO3 based on low-temperature calorimetric measurements

The low-temperature heat capacities of nickel titanate (NiTiO3), cobalt titanate (CoTiO3), and cobalt carbonate (CoCO3) were measured between 2 and 300 K, and thermochemical functions were derived from the results. Our new data show previously unknown low-temperature lambda-shaped heat capacity anomalies peaking at 37 K for CoTiO3 and 26 K for NiTiO3. From our data we calculate standard molar entropies (298.15 K) for NiTiO3 of 90.9 ± 0.7 J mol-1 K-1 and for CoTiO3 of 94.4 ± 0.8 J mol-1 K-1. For CoCO3, we find only a small broad heat capacity anomaly, peaking at about 31 K. From our data, we suggest a new standard entropy (298.15 K) for CoCO3 of 88.9 ± 0.7 J mol-1 K-1.

The role of F-clinohumite in volatile recycling processes in subduction zones

It is not well understood how much water and other volatiles are really contained in different mantle rocks or minerals, and how these volatiles are transported down into the deeper mantle in subduction zones. Here we present new experimental data showing that a common mineral found in subduction zone rocks, the hydrated Mg-silicate clinohumite, is much more stable in the mantle than previously anticipated. We show that even small amounts of F – substituting for OH – are sufficient to stabilize clinohumite to temperatures well above the normal mantle geotherm. Based on this finding we propose that in subduction zones, clinohumite effectively transports water and other volatiles from shallow depths to the transition zone of the mantle. This can drastically increase the amount of fluorine and water recycled into the deep mantle.

Synthesis of trace element bearing single crystals of Chlor-Apatite (Ca5(PO4)3Cl) using the flux growth method

We present a new strategy on how to synthesize trace-element bearing (REE, Sr) chlorapatites Ca5(PO4)3Cl using the flux growth method. Synthetic apatites were up to several mm long, light blue in colour. The apatites were characterized using XRD, electron microprobe and laser ablation ICP-MS (LA-ICPMS) techniques and contained several hundred μg/g La, Ce, Pr, Sm, Gd and Lu and about 1700 μg/g Sr. The analyses indicate that apatites were homogenous (within the uncertainties) for major and trace elements.

Experimental constraints on the stability of baddeleyite and zircon in carbonate- and silicate-carbonate melts

Abstract Carbonatites are rare igneous carbonate-rich rocks. Most carbonatites contain a large number of accessory oxide, sulfide, and silicate minerals. Baddeleyite (ZrO2) and zircon (ZrSiO4) are common accessory minerals in carbonatites and because these minerals host high concentrations of U and Th, they are often used to determine the ages of formation of the carbonatite. In an experimental study, we constrain the stability fields of baddeleyite and zircon in Ca-rich carbonate melts with different silica concentrations. Our results show that SiO2-free and low silica carbonate melts crystallize baddeleyite, whereas zircon only crystallizes in melts with higher concentration of SiO2. We also find that the zirconsilicate baghdadite (Ca3ZrSi2O9) crystallizes in intermediate compositions. Our experiments indicate that zircon may not be a primary mineral in a low-silica carbonatite melt and care must be taken when interpreting zircon ages from low-silica carbonatite rocks.