Formation of the Fe,Mg-Silicates,Fe<Superscript>0</Superscript>, and Graphite (Diamond) Assemblage as a Result of Cohenite Oxidation under Lithospheric Mantle Conditions

Experimental studies in the Fe₃C–SiO₂–MgO system (P = 6.3 GPa, T = 1100–1500°C, t = 20–40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe–C–O melt (1300–1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe–C–O) with oxides and silicates. The carbide–oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO₂ values near the iron–wustite buffer.     

Effect of sulfur concentration on diamond crystallization in the Fe–C–S system at 5.3–5.5 GPa and 1300–1370°C

The paper presents results of experiments aimed at diamond synthesis in the Fe–C–S system at 5.3–5.5 GPa and temperatures of 1300–1370°C and detailed data on the microtextures of the experimental samples and the composition of the accompanying phases (Fe₃C and Fe₇C₃ carbides, graphite, and FeS). It is demonstrated that diamond can be synthesized after temperatures at which carbides are formed are overcome and can crystallize within the temperature range of 1300°C (temperature of the peritectic reaction melt + diamond = Fe₇C₃) to 1370°C (of thermodynamically stable graphite) under the appearance experimental pressure. The possible involvement of natural metal- and sulfur-bearing compounds in the origin of natural diamond is discussed.     

Conditions of Formation of Iron–Carbon Melt Inclusions in Garnet and Orthopyroxene under <Emphasis Type="Italic">P-T</Emphasis> Conditions of Lithospheric Mantle

Of great importance in the problem of redox evolution of mantle rocks is the reconstruction of scenarios of alteration of Fe⁰- or Fe₃C-bearing rocks by oxidizing mantle metasomatic agents and the evaluation of stability of these phases under the influence of fluids and melts of different compositions. Original results of high-temperature high-pressure experiments (P = 6.3 GPa, T = 1300–1500°С) in the carbide–oxide–carbonate systems (Fe₃C–SiO₂–(Mg,Ca)CO₃ and Fe₃C–SiO₂–Al₂O₃–(Mg,Ca)CO₃) are reported. Conditions of formation of mantle silicates with metallic or metal–carbon melt inclusions are determined and their stability in the presence of CO₂-fluid representing the potential mantle oxidizing metasomatic agent are estimated. It is established that garnet or orthopyroxene and CO₂-fluid are formed in the carbide–oxide–carbonate system through decarbonation, with subsequent redox interaction between CO₂ and iron carbide. This results in the formation of assemblage of Fe-rich silicates and graphite. Garnet and orthopyroxene contain inclusions of a Fe–C melt, as well as graphite, fayalite, and ferrosilite. It is experimentally demonstrated that the presence of CO₂-fluid in interstices does not affect on the preservation of metallic inclusions, as well as graphite inclusions in silicates. Selective capture of Fe–C melt inclusions by mantle silicates is one of the potential scenarios for the conservation of metallic iron in mantle domains altered by mantle oxidizing metasomatic agents.     

Phase relations in the carbon-saturated C–Mg–Fe–Si–O system and C and Si solubility in liquid Fe at high pressure and temperature: implications for planetary interiors

The phase and melting relations of the C-saturated C–Mg–Fe–Si–O system were investigated at high pressure and temperature to understand the role of carbon in the structure of the Earth, terrestrial planets, and carbon-enriched extraterrestrial planets. The phase relations were studied using two types of experiments at 4 GPa: analyses of recovered samples and in situ X-ray diffractions. Our experiments revealed that the composition of metallic iron melts changes from a C-rich composition with up to about 5 wt.% C under oxidizing conditions (ΔIW = ?1.7 to ?1.2, where ΔIW is the deviation of the oxygen fugacity (fO₂) from an iron-wüstite (IW) buffer) to a C-depleted composition with 21 wt.% Si under reducing conditions (ΔIW < ?3.3) at 4 GPa and 1,873 K. SiC grains also coexisted with the Fe–Si melt under the most reducing conditions. The solubility of C in liquid Fe increased with increasing fO₂, whereas the solubility of Si decreased with increasing fO₂. The carbon-bearing phases were graphite, Fe₃C, SiC, and Fe alloy melt (Fe–C or Fe–Si–C melts) under the redox conditions applied at 4 GPa, but carbonate was not observed under our experimental conditions. The phase relations observed in this study can be applicable to the Earth and other planets. In hypothetical reducing carbon planets (ΔIW < ?6.2), graphite/diamond and/or SiC exist in the mantle, whereas the core would be an Fe–Si alloy containing very small amount of C even in the carbon-enriched planets. The mutually exclusive nature of C and Si may be important also for considering the light elements of the Earth’s core.     

The formation of graphite upon the interaction of subducted carbonates and sulfur with metal-bearing rocks of the lithospheric mantle

Experimental studies of the Fe⁰–(Mg, Ca)CO₃–S system were carried out during 18–20 h at 6.3 GPa, 900–1400°C. It is shown that the major processes resulting in the formation of free carbon include reduction of carbonates upon redox interaction with Fe⁰ (or Fe₃C), extraction of carbon from iron carbide upon interaction with a sulfur melt/fluid, and reduction of the carbonate melt by Fe–S and Fe?S–C melts. Reconstruction of the processes of graphite formation indicates that carbonates and iron carbide may be potential sources of carbon under the conditions of subduction, and participation of the sulfur melt/fluid may result in the formation of mantle sulfides.     

Voluminous arc dacites as amphibole reaction-boundary liquids

Dacites dominate the large-volume, explosive eruptions in magmatic arcs, and compositionally similar granodiorites and tonalites constitute the bulk of convergent margin batholiths. Shallow, pre-eruptive storage conditions are well known for many dacitic arc magmas through melt inclusions, Fe–Ti oxides, and experiments, but their potential origins deeper in the crust are not well determined. Accordingly, we report experimental results identifying the P–T–H₂O conditions under which hydrous dacitic liquid may segregate from hornblende (hbl)-gabbroic sources either during crystallization–differentiation or partial melting. Two compositions were investigated: (1) MSH–Yn?1 dacite (SiO₂: 65 wt%) from Mount St. Helens’ voluminous Yn tephra and (2) MSH–Yn?1?+?10% cpx to force saturation with cpx and map a portion of the cpx?+?melt?=?hbl peritectic reaction boundary. H₂O-undersaturated (3, 6, and 9 wt% H₂O) piston cylinder experiments were conducted at pressures, temperatures, and fO₂ appropriate for the middle to lower arc crust (400, 700, and 900 MPa, 825–1100?°C, and the Re–ReO₂ buffer?≈?Ni–NiO?+?2). Results for MSH–Yn?1 indicate near-liquidus equilibrium with a cpx-free hbl-gabbro residue (hbl, plg, magnetite, ± opx, and ilmeno-hematite) with 6–7 wt% dissolved H₂O, 925?°C, and 700–900 MPa. Opx disappears down-temperature consistent with the reaction opx?+?melt?=?hbl. Cpx-added phase relations are similar in that once ~10% cpx crystallizes, multiple saturation is attained with cpx, hbl, and plg, +/? opx, at 6–7 wt% dissolved H₂O, 940?°C, and 700–900 MPa. Plg–hbl–cpx saturated liquids diverge from plg–hbl–opx saturated liquids, consistent with the MSH–Yn?1 dacite marking a liquid composition along a peritectic distributary reaction boundary where hbl appears down-temperature as opx?+?cpx are consumed. The abundance of saturating phases along this distributary peritectic (liquid?+?hbl?+?opx?+?cpx?+?plg?+?oxides) reduces the variance, so liquids are restricted to dacite–granodiorite–tonalite compositions. Higher-K dacites than the Yn would also saturate with biotite, further limiting their compositional diversity. Theoretical evaluation of the energetics of peritectic melting of pargasitic amphiboles indicates that melting and crystallization of amphibole occur abruptly, proximal to amphibole’s high-temperature stability limit, which causes the system to dwell thermally under the conditions that produce dacitic compositions. This process may account for the compositional homogeneity of dacites, granodiorites, and tonalites in arc settings, but their relative mobility compared to rhyolitic/granitic liquids likely accounts for their greater abundance.     

Stability of phlogopite in ultrapotassic kimberlite-like systems at 5.5–7.5 GPa

Hydrous K-rich kimberlite-like systems are studied experimentally at 5.5–7.5 GPa and 1200–1450?°C in terms of phase relations and conditions for formation and stability of phlogopite. The starting samples are phlogopite–carbonatite–phlogopite sandwiches and harzburgite–carbonatite mixtures consisting of Ol?+?Grt?+?Cpx?+?L (±Opx), according to the previous experimental results obtained at the same P–T parameters but in water-free systems. Carbonatite is represented by a K- and Ca-rich composition that may form at the top of a slab. In the presence of carbonatitic melt, phlogopite can partly melt in a peritectic reaction at 5.5 GPa and 1200–1350?°C, as well as at 6.3–7.0 GPa and 1200?°C: 2Phl?+?CaCO₃ (L)?Cpx?+?Ol?+?Grt?+?K₂CO₃ (L)?+?2H₂O (L). Synthesis of phlogopite at 5.5 GPa and 1200–1350?°C, with an initial mixture of H₂O-bearing harzburgite and carbonatite, demonstrates experimentally that equilibrium in this reaction can be shifted from right to left. Therefore, phlogopite can equilibrate with ultrapotassic carbonate–silicate melts in a?≥?150?°C region between 1200 and 1350?°C at 5.5 GPa. On the other hand, it can exist but cannot nucleate spontaneously and crystallize in the presence of such melts in quite a large pressure range in experiments at 6.3–7.0 GPa and 1200?°C. Thus, phlogopite can result from metasomatism of peridotite at the base of continental lithospheric mantle (CLM) by ultrapotassic carbonatite agents at depths shallower than 180–195 km, which creates a mechanism of water retaining in CLM. Kimberlite formation can begin at 5.5 GPa and 1350?°C in a phlogopite-bearing peridotite source generating a hydrous carbonate–silicate melt with 10–15 wt% SiO₂, Ca# from 45 to 60, and high K enrichment. Upon further heating to 1450?°C due to the effect of a mantle plume at the CLM base, phlogopite disappears and a kimberlite-like melt forms with SiO₂ to 20 wt% and Ca#?=?35–40.     

Graphite and diamond formation via the interaction of iron carbide and Fe,Ni-sulfide under mantle <Emphasis Type="Italic">P–T</Emphasis> parameters

Experimental research in the Fe₃C–(Fe,Ni)S system was carried out. The objective of the investigation was to model the reactions of carbide–sulfide interaction related to graphite (diamond) formation in reduced lithosphere mantle domains. T ≤ 1200°C is the formation temperature of the Ni-cohenite + graphite assemblage coexisting with two immiscible melts such as sulfide (Fe₆₀–Ni₃–S₃₇)_L and metal–sulfide (Fe₇₁–Ni₇–S₂₁–C₁)_L containing dissolved carbon. Т ≥ 1300°C is the generation temperature of a unified melt such as (Fe₈₀–Ni₆–S₁₀–C₄)_L characterized by graphite crystallization and diamond growth. The extraction of carbide carbon during the interaction with the sulfide melt can be considered as one of the potential mechanisms of graphite and diamond formation in the reduced mantle.     

Rutile/TiO<Subscript>2</Subscript>II phase equilibria

The transition between rutile and α-PbO₂ structured TiO₂ (TiO₂II) has been investigated at 700–1,200 °C and 4.2–9.6 GPa. Hydrothermal phase equilibrium experiments were performed in the multi-anvil apparatus to bracket the phase boundary at 700, 1,000, and 1,200 °C. The equilibrium phase boundary is described by the equation: P (GPa)=1.29+0.0065 T ( °C). In addition, growth of TiO₂II was observed in experiments at 500 and 600 °C, although growth of rutile was too slow to bracket unambiguously the equilibrium boundary at these temperatures. Water was not detected in either rutile or TiO₂II, and dry synthesis experiments at 1,200 °C were consistent with the phase boundary determined in the fluid-bearing experiments, suggesting that the equilibrium is unaffected by the presence of water. Our bracket of the phase boundary at 700 °C is consistent with the reversed, dry experiments of Akaogi et al. (1992) and the reversals of Olsen et al. (1999). The new data suggest that the phase boundary is linear, in agreement with Akaogi et al. (1992), but in striking contrast to the phase diagram inferred by Olsen et al. (1999). The natural occurrence of TiO₂II requires formation pressures considerably higher than the graphite–diamond phase boundary.     

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle,and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

We performed an experimental study, designed to reproduce the formation of an unusual merwinite?+?olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca?=?1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite?+?olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300–1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca#?=?molar 100?×?Ca/(Ca?+?Mg)?>?0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca?=?1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg₂SiO₄ (olivine)?+?6CaCO₃ (liquid)?=?Ca₃MgSi₂O₈ (merwinite)?+?3CaMg(CO₃)₂ (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.     

Petrogenesis of Fe–Ti oxides in amphibole-rich veins from the Lherz orogenic peridotite (Northeastern Pyrénées, France)

Accessory, homogeneous ilmenite and rutile are important oxide phases in amphibole-rich high-pressure cumulate veins which crosscut the Lherz orogenic lherzolite massif. Those veins crystallized from alkaline melts at P = 1.2–1.5 GPa within the uppermost lithospheric mantle. Transitional basalts contaminated by peridotitic wall-rocks and then uncontaminated alkali basalts (basanites) reused the same vein conduits. Petrographic observations give evidence that Fe–Ti oxide saturation depends on the silica contents of each parental melt. The water-poor silica-rich transitional melts that generated websterites and plagioclase-rich clinopyroxenites reached early Ti-oxide saturation (1,200°C; 1.5 GPa). Rutile is as abundant as ilmenite. It is enriched with Nb–Zr–Hf by a factor of 10–100 relative to either amphibole or ilmenite. The amphibole pyroxenites and hornblendites crystallized from basanites reached late Fe–Ti oxide saturation after precipitation of amphibole, with ilmenite crystallizing along with phlogopite in the latter. The Lherz ilmenites are devoid of exsolution and contain very little trivalent iron. This compositional feature indicates more reducing crystallization conditions than usually inferred for alkali lavas and their megacrysts (FMQ ± 1). The veins incompletely equilibrated for redox conditions with their wall-rock peridotites which record more oxidizing conditions (FMQ ± 1). The veins also exchanged magnesium and chromium, as suggested by Cr-bearing, Mg-rich ilmenite (up to 44 mol% MgTiO₃₎ in veins less than 3–4 cm thick. Mg-rich ilmenite megacrysts occurring in alkali basalts could be actually xenocrysts from veins similar in thickness to those occurring at the Lherz massif, although crystallized from more oxidized magmas.     

Experimental growth of åkermanite reaction rims between wollastonite and monticellite: evidence for volume diffusion control

Growth rates of monomineralic, polycrystalline åkermanite (Ca₂MgSi₂O₇) rims produced by solid-state reactions between monticellite (CaMgSiO₄) and wollastonite (CaSiO₃) single crystals were determined at 0.5 GPa dry argon pressure, 1,000–1,200°C and 5 min to 60 h, using an internally heated pressure vessel. Inert Pt-markers, initially placed at the monticellite–wollastonite interface, indicate symmetrical growth into both directions. This and mass balance considerations demonstrate that rim growth is controlled by transport of MgO. At 1,200°C and run durations between 5 min and 60 h, rim growth follows a parabolic rate law with rim widths ranging from 0.4 to 16.3 μm indicating diffusion-controlled rim growth. The effective bulk diffusion coefficient \( D_{\text{eff,MgO}}^{\text{Ak}} \) is calculated to 10^?15.8±0.1 m² s^?1. Between 1,000°C and 1,200°C, the effective bulk diffusion coefficient follows an Arrhenius law with E _a = 204 ± 18 kJ/mol and D ₀ = 10^?8.6±1.6 m² s^?1. Åkermanite grains display a palisade texture with elongation perpendicular to the reaction interface. At 1,200°C, average grain widths measured normal to elongation, increase with the square root of time and range from 0.4 to 5.4 μm leading to a successive decrease in the grain boundary area fraction, which, however, does not affect \( D_{\text{eff,MgO}}^{\text{Ak}} \) to a detectible extent. This implies that grain boundary diffusion only accounts for a minor fraction of the overall chemical mass transfer, and rim growth is essentially controlled by volume diffusion. This is corroborated by the agreement between our estimates of the effective MgO bulk diffusion coefficient and experimentally determined volume diffusion data for Mg and O in åkermanite from the literature. There is sharp contrast to the MgO–SiO₂ binary system, where grain boundary diffusion controls rim growth.     

Phase relations and melting of carbonated peridotite between 10 and 20 GPa: a proxy for alkali- and CO<Subscript>2</Subscript>-rich silicate melts in the deep mantle

We determined the melting phase relations, melt compositions, and melting reactions of carbonated peridotite on two carbonate-bearing peridotite compositions (ACP: alkali-rich peridotite + 5.0 wt % CO₂ and PERC: fertile peridotite + 2.5 wt % CO₂) at 10–20 GPa and 1,500–2,100 °C and constrain isopleths of the CO₂ contents in the silicate melts in the deep mantle. At 10–20 GPa, near-solidus (ACP: 1,400–1,630 °C) carbonatitic melts with < 10 wt % SiO₂ and > 40 wt % CO₂ gradually change to carbonated silicate melts with > 25 wt % SiO₂ and < 25 wt % CO₂ between 1,480 and 1,670 °C in the presence of residual majorite garnet, olivine/wadsleyite, and clinoenstatite/clinopyroxene. With increasing degrees of melting, the melt composition changes to an alkali- and CO₂-rich silicate melt (Mg# = 83.7–91.6; ~ 26–36 wt % MgO; ~ 24–43 wt % SiO₂; ~ 4–13 wt % CaO; ~ 0.6–3.1 wt % Na₂O; and ~ 0.5–3.2 wt % K₂O; ~ 6.4–38.4 wt % CO₂). The temperature of the first appearance of CO₂-rich silicate melt at 10–20 GPa is ~ 440–470 °C lower than the solidus of volatile-free peridotite. Garnet + wadsleyite + clinoenstatite + carbonatitic melt controls initial carbonated silicate melting at a pressure < 15 GPa, whereas garnet + wadsleyite/ringwoodite + carbonatitic melt dominates at pressure > 15 GPa. Similar to hydrous peridotite, majorite garnet is a liquidus phase in carbonated peridotites (ACP and PERC) at 10–20 GPa. The liquidus is likely to be at ~ 2,050 °C or higher at pressures of the present study, which gives a melting interval of more than 670 °C in carbonated peridotite systems. Alkali-rich carbonated silicate melts may thus be produced through partial melting of carbonated peridotite to 20 GPa at near mantle adiabat or even at plume temperature. These alkali- and CO₂-rich silicate melts can percolate upward and may react with volatile-rich materials accumulate at the top of transition zone near 410-km depth. If these refertilized domains migrate upward and convect out of the zone of metal saturation, CO₂ and H₂O flux melting can take place and kimberlite parental magmas can be generated. These mechanisms might be important for mantle dynamics and are potentially effective metasomatic processes in the deep mantle.     

Formation of corundum megacrysts during H<Subscript>2</Subscript>O-saturated incongruent melting of feldspar: P–T pseudosection-based modelling from the Skattøra migmatite complex,North Norwegian Caledonides

Corundum megacryst-bearing rocks associated with the high-pressure migmatites of the Skattøra migmatite complex (SMC) belonging to the Nakkedal Nappe Complex, North Norwegian Caledonides, display a classical example of incongruent melting of plagioclase under water-saturated conditions. Petrography and micro-textures suggest that several centimetre long corundum megacrysts formed from the silicate melt along with amphibole (pargasite) and plagioclase (X_An ~ 0.47). The corundum-bearing leucosomes are rich in biotite compared to the other mafic units of SMC. Locally, margarite occurs in coronas around corundum megacrysts. Geochemically, the corundum-bearing rocks are enriched in Al, K, Rb and Ba and depleted in Fe, Mg and Ca compared to the leucogabbroic host rock. A P–T pseudosection of the leucogabbro indicates that feldspar breakdown and corundum formation occurred at temperatures >850 °C and pressure >1.2 GPa. The calculated equilibrium P–T of the corundum-bearing rock corresponds to 750–825 °C and 0.9–1.1 GPa. The P–T pseudosection of margarite indicates that margarite formed after cooling and decompression to P–T conditions corresponding to 600 °C at 0.5 GPa. Based on geochemical and mineral chemical analysis coupled with thermodynamic modelling, we suggest that formation of corundum occurred as a result of high-pressure incongruent melting of plagioclase in the presence of a K-, Rb- and Ba-rich external fluid. It is also suggested that the external fluid transported out portions of Ca, Fe and Mg, resulting in an increase of the peraluminousity of the melt and promoting further growth of corundum.     

Transport properties of olivine grain boundaries from electrical conductivity experiments

Grain boundary processes contribute significantly to electronic and ionic transports in materials within Earth’s interior. We report a novel experimental study of grain boundary conductivity in highly strained olivine aggregates that demonstrates the importance of misorientation angle between adjacent grains on aggregate transport properties. We performed electrical conductivity measurements of melt-free polycrystalline olivine (Fo₉₀) samples that had been previously deformed at 1200 °C and 0.3 GPa to shear strains up to γ?=?7.3. The electrical conductivity and anisotropy were measured at 2.8 GPa over the temperature range 700–1400 °C. We observed that (1) the electrical conductivity of samples with a small grain size (3–6 µm) and strong crystallographic preferred orientation produced by dynamic recrystallization during large-strain shear deformation is a factor of 10 or more larger than that measured on coarse-grained samples, (2) the sample deformed to the highest strain is the most conductive even though it does not have the smallest grain size, and (3) conductivity is up to a factor of ~?4 larger in the direction of shear than normal to the shear plane. Based on these results combined with electrical conductivity data for coarse-grained, polycrystalline olivine and for single crystals, we propose that the electrical conductivity of our fine-grained samples is dominated by grain boundary paths. In addition, the electrical anisotropy results from preferential alignment of higher-conductivity grain boundaries associated with the development of a strong crystallographic preferred orientation of the grains.     

Metasomatism of continental crust during subduction: the UHP whiteschists from the Southern Dora-Maira Massif (Italian Western Alps)

The ultrahigh‐pressure pyrope whiteschists from the Brossasco‐Isasca Unit of the Southern Dora‐Maira Massif represent metasomatic rocks originated at the expense of post‐Variscan granitoids by the influx of fluids along shear zones. In this study, geochemical, petrological and fluid‐inclusion data, correlated with different generations of pyrope‐rich garnet (from medium, to very‐coarse‐grained in size) allow constraints to be placed on the relative timing of metasomatism and sources of the metasomatic fluid. Geochemical investigations reveal that whiteschists are strongly enriched in Mg and depleted in Na, K, Ca and LILE (Cs, Pb, Rb, Sr, Ba) with respect to the metagranite. Three generations of pyrope, with different composition and mineral inclusions, have been distinguished: (i) the prograde Prp I, which constitutes the large core of megablasts and the small core of porphyroblasts; (ii) the peak Prp II, which constitutes the inner rim of megablasts and porphyroblasts and the core of small neoblasts; and (iii) the early retrograde Prp III, which locally constitutes an outer rim. Two generations of fluid inclusions have been recognized: (i) primary fluid inclusions in prograde kyanite that represent a NaCl‐MgCl₂‐rich brine (6–28 wt% NaCl_eq with Si and Al as other dissolved cations) trapped during growth of Prp I (type‐I fluid); (ii) primary multiphase‐solid inclusions in Prp II that are remnants of an alumino‐silicate aqueous solution, containing Mg, Fe, alkalies, Ca and subordinate P, Cl, S, CO₃^2‐, LILE (Pb, Cs, Sr, Rb, K, LREE, Ba), U and Th (type‐II fluid), at the peak pressure stage. We propose a model that illustrates the prograde metasomatic and metamorphic evolution of the whiteschists and that could also explain the genesis of other Mg‐rich, alkali‐poor schists of the Alps. During Alpine metamorphism, the post‐Variscan metagranite of the Brossasco‐Isasca Unit experienced a prograde metamorphism at HP conditions (stage A: ～1.6 GPa and ≤ 600 °C), as indicated by the growth of an almandine‐rich garnet in some xenoliths. At stage B (1.7–2.1 GPa and 560–590 °C), the influx of external fluids, originated from antigorite breakdown in subducting oceanic serpentinites, promoted the increase in Mg and the decrease of alkalies and Ca in the orthogneiss toward a whiteschist composition. During stage C (2.1 < P < 2.8 GPa and 590 < T < 650 °C), the metasomatic fluid influx coupled with internal dehydration reactions involving Mg‐chlorite promoted the growth of Prp I in the presence of the type‐I MgCl₂‐brine. At the metamorphic peak (stage D: 4.0–4.3 GPa and 730 °C), Prp II growth occurred in the presence of a type–II alumino‐silicate aqueous solution, mostly generated by internal dehydration reactions involving phlogopite and talc. The contribution of metasomatic external brines at the metamorphic climax appears negligible. This fluid, showing enrichment in LILE and depletion in HFSE, could represent a metasomatic agent for the supra‐subduction mantle wedge.     

Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers

Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X _Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10^?11 to 10^?17 bar. Diffusion couples were prepared by ablating an olivine (X _Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D ^Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di₉₃–Di₆₅) or oxygen fugacity could be detected within the resolution of the study. The lack of fO₂-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D ^Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D ^Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D ^Ca–Mg) while it is slower than D ^Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks).     

Sound velocity and elastic properties of Fe–Ni and Fe–Ni–C liquids at high pressure

The sound velocity (V _P) of liquid Fe–10 wt% Ni and Fe–10 wt% Ni–4 wt% C up to 6.6 GPa was studied using the ultrasonic pulse-echo method combined with synchrotron X-ray techniques. The obtained V _P of liquid Fe–Ni is insensitive to temperature, whereas that of liquid Fe–Ni–C tends to decrease with increasing temperature. The V _P values of both liquid Fe–Ni and Fe–Ni–C increase with pressure. Alloying with 10 wt% of Ni slightly reduces the V _P of liquid Fe, whereas alloying with C is likely to increase the V _P. However, a difference in V _P between liquid Fe–Ni and Fe–Ni–C becomes to be smaller at higher temperature. By fitting the measured V _P data with the Murnaghan equation of state, the adiabatic bulk modulus (K _S0) and its pressure derivative (K _S ^′ ) were obtained to be K _S0 = 103 GPa and K _S ^′  = 5.7 for liquid Fe–Ni and K _S0 = 110 GPa and K _S ^′  = 7.6 for liquid Fe–Ni–C. The calculated density of liquid Fe–Ni–C using the obtained elastic parameters was consistent with the density values measured directly using the X-ray computed tomography technique. In the relation between the density (ρ) and sound velocity (V _P) at 5 GPa (the lunar core condition), it was found that the effect of alloying Fe with Ni was that ρ increased mildly and V _P decreased, whereas the effect of C dissolution was to decrease ρ but increase V _P. In contrast, alloying with S significantly reduces both ρ and V _P. Therefore, the effects of light elements (C and S) and Ni on the ρ and V _P of liquid Fe are quite different under the lunar core conditions, providing a clue to constrain the light element in the lunar core by comparing with lunar seismic data.     

The effect of deformation on the TitaniQ geothermobarometer: an experimental study

We performed high strain (up to 47 %) axial compression experiments on natural quartz single crystals with added rutile powder (TiO₂) and ~0.2 wt% H₂O to investigate the effects of deformation on the titanium-in-quartz (TitaniQ) geothermobarometer. One of the objectives was to study the relationships between different deformation mechanisms and incorporation of Ti into recrystallized quartz grains. Experiments were performed in a Griggs-type solid-medium deformation apparatus at confining pressures of 1.0–1.5 GPa and temperatures of 800–1,000 °C, at constant strain rates of 1 × 10^?6 or 1 × 10^?7 s^?1. Mobility of Ti in the fluid phase and saturation of rutile at grain boundaries during the deformation experiments are indicated by precipitation of secondary rutile in cracks and along the grain boundaries of newly recrystallized quartz grains. Microstructural analysis by light and scanning electron microscopy (the latter including electron backscatter diffraction mapping of grain misorientations) shows that the strongly deformed quartz single crystals contain a wide variety of deformation microstructures and shows evidence for subgrain rotation (SGR) and grain boundary migration recrystallization (GBMR). In addition, substantial grain growth occurred in annealing experiments after deformation. The GBMR and grain growth are evidence of moving grain boundaries, a microstructure favored by high temperatures. Electron microprobe analysis shows no significant increase in Ti content in recrystallized quartz grains formed by SGR or by GBMR, nor in grains grown by annealing. This result indicates that neither SGR nor moving grain boundaries during GBMR and grain growth are adequate processes to facilitate re-equilibration of the Ti content in experimentally deformed quartz crystals at the investigated conditions. More generally, our results suggest that exchange of Ti in quartz at low H₂O contents (which may be realistic for natural deformation conditions) is still not fully understood. Thus, the application of the TitaniQ geothermobarometer to deformed metamorphic rocks at low fluid contents may not be as straightforward as previously thought and requires further research.     

Synthesis of New Polytypic Modifications of Fe7C3 at 5.5 GPa

Doklady Earth Sciences - The results of experimental synthesis of carbide Fe7C3 at 5.5 GPa are presented. It is found that carbide Fe3C and several polytypes of carbide Fe7C3 are formed along with...