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We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H2O (ΔFMQ = − 0.21 to − 1.01), employing a double-capsule setting. Fluids, binary H2O– CO2 mixtures at the P, T, and fO2 conditions investigated, were generated from graphite, oxalic acid anhydrous ( H2C2O4) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO2- bearing fluids. The experimental data show that forsterite + enstatite solubility in H2O– CO2 fluids is higher compared to pure water, both in terms of dissolved silica (mSiO2 = 1.24 mol/kgH2O versus mSiO2 = 0.22 mol/kgH2O at P = 1 GPa, T = 800 °C) and magnesia (mMgO = 1.08 mol/kgH2O versus mMgO = 0.28 mol/ kgH2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H2O– CO2 fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO2 ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO2 ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.

Monazite-bearing Alpine clefts located in the Sonnblick region of the eastern Tauern Window, Austria, are oriented perpendicular to the foliation and lineation. Ion probe (SIMS) Th–Pb and U–Pb dating of four cleft monazites yields crystallization ages of different growth domains and aggregate regions ranging from 18.99 ± 0.51 to 15.00 ± 0.51 Ma. The crystallization ages obtained are overlapping or slightly younger than zircon fission track ages but older than zircon (U–Th)/He cooling ages from the same area. This constrains cleft monazite crystallization in this area to ~300–200 °C. LA-ICP-MS data of dated hydrothermal monazites indicate that in graphite-bearing, reduced host lithologies, cleft monazite is poor in As and has higher La/Yb values and U concentrations, whereas in oxidised host rocks opposite trends are observed. Monazites show negative Eu anomalies and variable La/Yb values ranging from 520 to 6050. The positive correlation between Ca and Sr concentration indicates dissolution of plagioclase or carbonates as the source of these elements. The data show that early exhumation and cleft formation in the Tauern is related to metamorphic dome formation caused by the collision of the Adriatic with the European plate and that monazite crystallization in the clefts occurred later. Our data also demonstrate that hydrothermal monazite ages offer great potential in helping to constrain the chronology of exhumation in collisional orogens.

The phase assemblages and compositions in a K free lherzolite + H2O system were determined between 4 and 6 GPa and 700 800A degrees C and the dehydration reactions occurring at subarc depth in subduction zones were constrained. Experiments were performed on a rocking multi anvil apparatus using a diamond trap setting. The composition of the fluid phase was measured using the recently developed cryogenic LA ICP MS technique. Results show that at 4 GPa the aqueous fluid coexisting with residual lherzolite (similar to 85 wt H2O) doubles its solute load when chlorite transforms to the 10 phase between 700 and 750 degrees C. The 10 phase breaks down at 4 and 5 GPa between 750 and 800 degrees C and at 6 GPa between 700 and 750 degrees C leaving a dry lherzolite coexisting with a fluid phase containing 58 67 wt H2O again doubling the total dissolved solute load. The fluid fraction in the system increases from 0.2 when a hydrous mineral is present to 0.4 when coexisting with a dry lherzolite. Our data do not reveal the presence of a hydrous peridotite solidus below 800 degrees C. The directly measured fluid compositions demonstrate a fundamental change in the (MgO + FeO) to SiO2 mass ratio of fluid solutes occurring at a depth of ca. 120 150 km (in the temperature window of 700 800 degrees C) from (MgO FeO) dominated at 4 GPa [with (MgO + FeO)/SiO2 ratio of 1.41 1.56] to SiO2 dominated at 5 6 GPa (ratios of 0.61 0.82). The mobility of Al2O3 increases by more than one order of magnitude across this P T interval and demonstrates that Al2O3 is compatible in an aqueous fluid coexisting with the anhydrous ol opx cpx +/ A grt assemblage. This shift in the fluid composition correlates with changes in the phase assemblage of the residual silicates. The hitherto unknown fundamental change in (MgO + FeO)/SiO2 ratio and prominent increase in Al2O3 of the aqueous fluid with progressive subduction will likely inspire novel concepts on mantle wedge metasomatism by slab fluids.

Contributions to Mineralogy and Petrology, 157 (4), ISSN:0010-7999, ISSN:1432-0967

Plagioclase-melt partition coefficients (D) for 34 trace elements at natural concentration levels were determined experimentally in a natural MORB composition at atmospheric pressure using thin Pt-wire loops. Experiments were carried out at three temperatures (1,220, 1,200, and 1,180°C), and at three different oxygen fugacities (fO2 = IW, QFM, air) in order to assess the effect of fO2 on the partitioning of elements with multiple valence (Fe, Eu, Cr). Run products were analyzed by laser-ablation ICP-MS. Most trace element Ds increase slightly as temperature decreases, except for D Zr, D Fe, D Eu and D Cr that vary systematically with fO2. Applying the Lattice Strain Model to our data suggests the presence of Fe2+ entirely in the octahedral site at highly to moderate reducing conditions, while Fe3+ was assigned wholly to the tetrahedral site of the plagioclase structure. Furthermore, we provide a new quantitative framework for understanding the partitioning behaviour of Eu, which occurs as both 2+ and 3+ cations, depending on fO2and confirm the greater compatibility of Eu2+, which has an ionic radius similar to Sr, relative to Eu3+ in plagioclase and the higher Eu2+/ Eu3+ under reducing conditions. For petrogenetic basaltic processes, a combined fractionation of Eu2+–Sr and Fe–Mg by plagioclase has considerable potential as an oxybarometer for natural magmatic rocks.

Contributions to Mineralogy and Petrology, 152 (4), ISSN:0010-7999, ISSN:1432-0967

We report methane-dominant hydrocarbon (fluid) inclusions (CH4±C2H6–C2H2, C3H8) coexisting with primary brine inclusions and secondary halide melt (solid NaCl) inclusions in Au–Pt-rich quartz-sulfide-epidote alteration veins associated with the footwall-style Cu–PGE (platinum-group element)–Au deposits at the Fraser Mine (North Range of the Sudbury Igneous Complex). Evidence for coentrapment of immiscible hydrocarbon–brine, and hydrocarbon–halide melt mixtures is demonstrated. A primary CH4–brine assemblage was trapped during quartz growth at relatively low T (min. T trapping∼145–315°C) and P (max. P trapping∼500 bar), prior to the crystallization of sulfide minerals in the veins. Secondary inclusions contain solid halite and a mixture of CH4, C2H6–C2H2 and C3H8 and were trapped at a minimum T of ∼710°C. The halite inclusions may represent halide melt that exsolved from crystallizing sulfide ores that texturally postdate (by replacement) early alteration quartz hosting the primary, lower T brine–CH4 assemblage. Laser ablation ICP-MS analyses show that the brine, hydrocarbon and halide melt inclusions contain significant concentrations of Cu (0.1–1 wt% range), Au, Bi, Ag and Pt (all 0.1–10 ppm range). Cu:Pt and Cu:Au ratios in the inclusions are significantly (up to 4 log units) lower than in the host alteration veins and adjacent massive sulfide ore veins, suggesting either (1) early Cu loss from the volatiles by chalcopyrite precipitation or (2) enhanced Au and Pt solubilities relative to Cu at the temperatures of entrapment. Concentration ratios between coexisting brine and CH4 inclusions $$[C^{{\rm elem}}_{{\rm brine}}/C^{{\rm elem}}_{{\rm CH_{4}}}]$$ are lower for Cu, Au, Bi and Ag than for other elements (Na, Ca, Fe, Mn, Zn, Pb) indicating that during interaction with the brine, the hydrocarbon phase was enriched in ore metals. The high concentrations of ore metals in hydrocarbon, brine and halide melt phases confirm that both aqueous and non-aqueous volatiles were carriers of precious metals in the Sudbury environment over a wide range of temperatures. Volatile evolution and magmatic sulfide differentiation were clearly part of a single, continuous process in the Sudbury footwall. The exsolution of H2O-poor volatiles from fractionated sulfide liquid may have been a principal mechanism controlling the final distribution of PGE and Au in the footwall ore systems. The study reports the first measurements of precious metal concentrations in fluid inclusions from a magmatic Ni–Cu–PGE environment (the Sudbury district).

Contributions to Mineralogy and Petrology, 147 (4), ISSN:0010-7999, ISSN:1432-0967

Contributions to Mineralogy and Petrology, 147 (4), ISSN:0010-7999, ISSN:1432-0967