Zr-in-rutile thermometry in HP/UHP eclogites from Western China

Four Zr-in-rutile thermometry calibrations are applied to eclogites from Western China. Here, we show that if rutile grows in equilibrium with Qtz and Zrn, and is isolated inside garnet, it preserves its Zr composition and does not undergo compositional change due to cation exchange with the host garnet. It thus preserves the composition for the P–T conditions of its formation and the growth zoning of the host garnet. For the HP/UHP metamorphic temperature, the Tomkins et al. (J Metamorph Geol 25:703–713, 2007) calibration yields temperatures that agree well with previous studies, whereas the other three calibrations (Zack et al. in Contrib Mineral Petrol 148:471–488, 2004; Watson et al. in Contrib Mineral Petrol 151:413–433, 2006; Ferry and Watson in Contrib Mineral Petrol in 154:429–437, 2007), which do not include a pressure correction, give systematically lower temperatures. Zr contents of rutile inclusions within garnet show systematic decrease from garnet core to rim. The rutile inclusions in garnet rims contain the lowest Zr content, similar to that in the matrix. Analyses confirm that the pressure plays a significant role in modifying the primary temperature dependence of the Zr content of rutile. Rutiles trapped in garnets are unable to re-equilibrate easily during retrogression, but those in the matrix can do so, providing retrograde P–T path information.     

Modeling of the solubility of a one-component H2O or CO2 fluid in silicate liquids

The modeling of the solubility of water and carbon dioxide in silicate liquids (flash problem) is performed by assuming mechanical, thermal, and chemical equilibrium between the liquid magma and the gas phase. The liquid phase is treated as a mixture of ten silicate components + H₂O or CO₂, and the gas phase as a pure H₂O or CO₂. A general model for the solubility of a volatile component in a liquid is adopted. This requires the definition of a mixing equation for the excess Gibbs free energy of the liquid phase and an appropriate reference state for the dissolved volatile. To constrain the model parameters and identify the most appropriate form of the solubility equations for each dissolved volatile, a large number of experimental solubility determinations (640 for H₂O and 263 for CO₂) have been used. These determinations cover a large region of the P-T-composition space of interest. The resultant water and carbon dioxide solubility models differ in that the water model is regular and isometric, and the carbon dioxide model is regular and non-isometric. This difference is consistent with the different speciation modalities of the two volatiles in the silicate liquids, producing a composition-independent partial molar volume of dissolved water and a composition-dependent partial molar volume of dissolved carbon dioxide. The H₂O solubility model may be applied to natural magmas of virtually any composition in the P-T range 0.1 MPa–1 GPa and > 1000 K, whereas the CO₂ solubility model may be applied to several GPa pressures. The general consistency of the water solubility data and their relatively large number as compared to the calibrated model parameters (11) contrast with the large inconsistencies of the carbon dioxide solubility determinations and their low number with respect to the CO₂ model parameters (22). As a result, most of the solubility data in the database are reproduced within 10% of approximation in the case of water, and 30% in the case of carbon dioxide. When compared with the experimental data, the H₂O and CO₂ solubility models correctly predict many features of the saturation surface in the P-T-composition space, including the change from retrograde to prograde H₂O solubility in albitic liquids with increasing pressure, the so-called alkali effect, the increasing CO₂ solubility with increasing degree of silica undersaturation, the Henrian behavior of CO₂ in most silicate liquids up to about 30–50 MPa, and the proportionality between the fugacity in the gas phase, or the saturation activity in the liquid phase, and the square of the mole fraction of the dissolved volatile found in some unrelated silicate liquid compositions. Received: 21 August 1995 / Accepted: 8 July 1996     

Cordierite as a sensor of fluid conditions in high-grade metamorphism and crustal anatexis

Cordierite H₂O and CO₂ volatile saturation surfaces derived from recent experimental studies are presented for P–T conditions relevant to high‐grade metamorphism and used to evaluate fluid conditions attending partial melting and granulite formation. The volatile saturation surfaces and saturation isopleths for both H₂O and CO₂ in cordierite are strongly pressure dependent. In contrast, the uptake of H₂O by cordierite in equilibrium with melts formed through biotite dehydration melting, controlled by the distribution of H₂O between granitic melt and cordierite, D_w[D_w = wt% H₂O (melt)/wt% H₂O(Crd)], is mainly temperature dependent. D_w = 2.5–6.0 for the H₂O contents (0.4–1.6 wt percentage) typical of cordierite formed through biotite dehydration melting at 3–7 kbar and 725–900 °C. This range in D_w causes a 15–30% relative decrease in the total wt% of melt produced from pelites. Cordierite in S‐type granites are H₂O‐rich (1.3–1.9 wt%) and close to or saturated in total volatiles, signifying equilibration with crystallizing melts that achieved saturation in H₂O. In contrast, the lower H₂O contents (0.6–1.2 wt percentage) preserved in cordierite from many granulite and contact migmatite terranes are consistent with fluid‐absent conditions during anatexis. In several cases, including the Cooma migmatites and Broken Hill granulites, the cordierite volatile compositions yield a_H2O values (0.15–0.4) and melt H₂O contents (2.2–4.4 wt%) compatible with model dehydration melting reactions. In contrast, H₂O leakage is indicated for cordierite from Prydz Bay, Antarctica that preserve H₂O contents (0.5–0.3 wt%) which are significantly less than those required (1.0–0.8 wt%) for equilibrium with melt at conditions of 6 kbar and 860 °C. The CO₂ contents of cordierite in migmatites range from negligible (< 0.1 wt%) to high (0.5–1.0 wt%), and bear no simple relationship to preserved cordierite H₂O contents and a_H2O. In most cases the cordierite volatile contents yield total calculated fluid activities (a_H2O + a_CO2) that are significantly less than those required for fluid saturation at the P–T conditions of their formation. Whether this reflects fluid absence, dilution of H₂O and CO₂ by other components, or leakage of H₂O from cordierite is an issue that must be evaluated on a case‐by‐case basis.     

Application of the Ti-in-quartz thermobarometer to rutile-free systems. Reply to: a comment on: ‘TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz’ by Thomas et al.

The premise of the Wilson et al. comment is that the Ti-in-quartz solubility calibration (Thomas et al. in Contrib Mineral Petrol 160:743–759, 2010) is fundamentally flawed. They reach this conclusion because P–T estimates using the Ti-in-quartz calibration differ from their previous interpretations for crystallization conditions of the Bishop and Oruanui rhyolites. If correct, this assertion has far-reaching implications, so a careful assessment of the Wilson et al. reasoning is warranted. Application of the Ti-in-quartz calibration as a thermobarometer in rutile-free rocks requires an estimation of TiO₂ activity in the liquid ( (liquid–rutile); referenced to rutile saturation) and an independent constraint on either P or T to obtain the crystallization temperature or pressure, respectively. The foundation of Wilson et al.’s argument is that temperature estimates obtained from Fe–Ti oxide thermometry accurately reflect crystallization conditions of quartz in the two rhyolites discussed. We maintain that our experimental approach is sound, the thermodynamic basis of the Ti-in-quartz calibration is fundamentally correct, and our experimental results are robust and reproducible. We suggest that the reason Wilson et al. obtain implausible pressure estimates is because estimates for T and they used as input values for the Ti-in-quartz calibration are demonstrably too high. Numerous studies show that Fe–Ti oxide temperature estimates of some rhyolites are substantially higher than those predicted by well-constrained phase equilibria. In this reply, we show that when reasonable input values for T and (liquid–rutile) are used, pressure estimates obtained from the Ti-in-quartz calibration are well aligned with phase equilibria and essentially identical to melt inclusion volatile saturation pressures.     

The thermodynamic properties of H2O in magnesium and iron cordierite

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996     

Variations in fluid activity across the Etive thermal aureole, Scotland: evidence from cordierite volatile contents

The H₂O and CO₂ content of cordierite was analysed in 34 samples from successive contact metamorphic zones of the Etive thermal aureole, Scotland, using Fourier‐transform infrared spectroscopy (FTIR). The measured volatile contents were used to calculate peak metamorphic H₂O and CO₂ activities. Total volatile contents are compared with recently modelled cordierite volatile saturation surfaces in order to assess the extent of fluid‐present v. fluid‐absent conditions across the thermal aureole. In the middle aureole, prior to the onset of partial melting, calculated aH₂O values are high, close to unity, and measured volatile contents intersect modelled H₂O–CO₂ saturation curves at the temperature of interest, suggesting that fluid‐present conditions prevailed. Total volatile contents and aH₂O steadily decrease beyond the onset of partial melting, consistent with the notion of aH₂O being buffered to lower values as melting progresses once free hydrous fluid is exhausted. All sillimanite zone samples record total volatile contents that are significantly lower than modelled H₂O–CO₂ saturation surfaces, implying that fluid‐absent conditions prevailed. The lowest recorded aH₂O values lie entirely within part of the section where fluid‐absent melting reactions are thought to have dominated. Samples within 30 m of the igneous contact appear to be re‐saturated, possibly via a magmatically derived fluid. In fluid‐absent parts of the aureole, cordierite H₂O contents yield melt–H₂O contents that are compatible with independently determined melt–H₂O contents. The internally consistent cordierite volatile data and melt–H₂O data support the conclusion that the independent P–T estimates applied to the Etive rocks were valid and that measured cordierite volatile contents are representative of peak metamorphic values. The Etive thermal aureole provides the most compelling evidence, suggesting that the cordierite fluid monitor can be used to accurately assess the fluid conditions during metamorphism and partial melting in a thermal aureole.     

Refining the P–T records of UHT crustal metamorphism

Ultra‐high‐temperature (UHT) metamorphism occurs when the continental crust is subjected to temperatures of greater than 900 °C at depths of 20–40 km. UHT metamorphism provides evidence that major tectonic processes may operate under thermal conditions more extreme than those generally produced in numerical models of orogenesis. Evidence for UHT metamorphism is recorded in mineral assemblages formed in magnesian pelites, supported by high‐temperature indicators including mesoperthitic feldspar, aluminous orthopyroxene and high Zr contents in rutile. Recent theoretical, experimental and thermodynamic data set constraints on metamorphic phase equilibria in FMAS, KFMASH and more complex chemical systems have greatly improved quantification of the P–T conditions and paths of UHT metamorphic belts. However, despite these advances key issues that remain to be addressed include improving experimental constraints on the thermodynamic properties of sapphirine, quantifying the effects of oxidation state on sapphirine, orthopyroxene and spinel stabilities and quantifying the effects of H₂O–CO₂ in cordierite on phase equilibria and reaction texture analysis. These areas of uncertainty mean that UHT mineral assemblages must still be examined using theoretical and semi‐quantitative approaches, such as P(–T)–μ sections, and conventional thermobarometry in concert with calculated phase equilibrium methods. In the cases of UHT terranes that preserve microtextural and mineral assemblage evidence for steep or ‘near‐isothermal’ decompression P–T paths, the presence of H₂O and CO₂ in cordierite is critical to estimates of the P–T path slopes, the pressures at which reaction textures have formed and the impact of fluid infiltration. Many UHT terranes have evolved from peak P–T conditions of 8–11 kbar and 900–1030 °C to lower pressure conditions of 8 to 6 kbar whilst still at temperature in the range of 950 to 800 °C. These decompressional P–T paths, with characteristic dP/dT gradients of ～25 ± 10 bar °C^?1, are similar in broad shape to those generated in deep‐crustal channel flow models for the later stages of orogenic collapse, but lie at significantly higher temperatures for any specified pressure. This thermal gap presents a key challenge in the tectonic modelling of UHT metamorphism, with implications for the evolution of the crust, sub‐crustal lithosphere and asthenospheric mantle during the development of hot orogens.     

The stability of sapphirine-quartz and hypersthene-sillimanite-quartz assemblages: an experimental investigation in the system FeO−MgO−Al2O3−SiO2 under H2O and CO2 conditions

Phase relations and mineral chemistry involving the phases garnet (Gt), spinel (Sp), hypersthene (Hy), sapphirine (Sa), cordierite (Cd), sillimanite (Sil) and quartz (Qz) have been experimentally determined in the system FMAS (FeO−MgO−Al₂O₂−SiO₂) under low fO₂ and for various H₂O/CO₂ conditions. Several compositions were studied with 100 (Mg/Mg+Fe) ratio ranging from 64 to 87 with excess quartz and sillimanite. Our data do not show any differences in Gt−Cd stability and composition as a function of H₂O, CO₂ and H₂O−CO₂ (±CH₄) content, in good agreement with a previous experimental study at lower temperature (Aranovich and Podlesskii 1983). At 1,000° C and 11 kbar, under CO₂-saturated conditions, cordierite grew from a crystalline mix unseeded with cordierite. Thus, under water-absent conditions, cordierite will have a high-P stability field in the presence of CO₂. If water has a pressure stabilizing effect on cordierite, then our results would indicate that the effects of H₂O and CO₂ are of the same magnitude at high temperature. Our data support the theoretical P-T grid proposed by Hensen (1986) for high-T metapelites and are largely consistent with the high-temperature experimental data of Hensen and Green (1973). The univariant boundary Gt+Cd=Hy+Sil+Qz, which marks the disappearance of Hy−Sil−Qz assemblages, has a negative dP/dT slope above 1,000° C and a positive one below this temperature. Extrapolation of our data to iron-free systems shows that the high-P breakdown limit of Mg-cordierite has a negative slope in the range 1,025–1,300° C and probably positive below 1,000° C. This indicates a maximum of stability for Mg-cordierite at around 1,000° C and 13 kbar. Because of the curvature of the univariant reactions En+Sil=Py+Qz, Mg−Cd=En+Sil+Qz and Gt+Cd=Hy+Sil+Qz, the iron-free invariant point involving the phases Py, En, Cd, Sil and Qz probably does not exist. Sapphirine—Qz-bearing assemblages are stable only at temperatures above 1,050° C. At 1,075° C, the joint Gt−Sa is stable up to 11 kbar. At higher pressure, garnet, sapphirine and quartz react according to the reaction Gt+Sa+Qz=Hy+Sil. Reequilibrated sapphirines are more aluminous than the theoretical endmember Mg₂Al₄SiO₁₀ due to AlAl=MgSi substitutions [100(Al₂O₃/Al₂O₃+FeO+MgO) in experimental sapphirines ranges from 50.5 to 52.2]. Sapphirine in the assemblage Sa−Cd−Sil−Qz shows a decrease in Al content with decreasing temperature and pressure, such that the alumina isopleths for sapphirine have a slight negative dP/dT slope. A similar decrease in Al content of sapphirine with temperature is also observed in Sa−Sil−Qz assemblages.     

Zr diffusion in titanite

Chemical diffusion of Zr under anhydrous, pO₂-buffered conditions has been measured in natural titanite. The source of diffusant was either zircon powder or a ZrO₂–Al₂O₃–titanite mixture. Experiments were run in sealed silica glass capsules with solid buffers (to buffer at NNO or QFM). Rutherford Backscattering Spectrometry (RBS) was used to measure diffusion profiles. The following Arrhenius parameters were obtained for Zr diffusion parallel to c over the temperature range 753–1,100°C under NNO-buffered conditions: D _Zr = 5.33 × 10⁻⁷ exp(−325 ± 30 kJ mol⁻¹/RT) m² s⁻¹ Diffusivities are similar for experiments buffered at QFM. These data suggest that titanite should be moderately retentive of Zr chemical signatures, with diffusivities slower than those for O and Pb in titanite, but faster than those for Sr and the REE. When applied in evaluation of the relative robustness of the recently developed Zr-in-titanite geothermometer (Hayden and Watson, Abstract, 16th V.M. Goldschmidt Conference 2006), these findings suggest that Zr concentrations in titanite will be less likely to be affected by later thermal disturbance than the geothermometer based on Zr concentrations in rutile (Zack et al. in Contrib Mineral Petrol 148:471–488, 2004; Watson et al. in Contrib Mineral. Petrol, 2006), but much less resistant to diffusional alteration subsequent to crystallization than the Ti-in-Zircon geothermometer (Watson and Harrison in Science 308:841–844, 2005).     

Double carbonate breakdown reactions at high pressures: an experimental study in the system CaO–MgO–FeO–MnO–CO2

The pressure–temperature conditions of the reactions of the double carbonates CaM(CO₃)₂, where M = Mg (dolomite), Fe (ankerite) and Mn (kutnohorite), to MCO₃ plus CaCO₃ (aragonite) have been investigated at 5–8 GPa, 600–1,100°C, using multi-anvil apparatus. The reaction dolomite = magnesite + aragonite is in good agreement with the results of Sato and Katsura (Earth Planet Sci 184:529–534, 2001), but in poor agreement with the results of Luth (Contrib Mineral Petrol 141:222–232, 2001). The dolomite is partially disordered at 620°C, and fully disordered at 1,100°C. All ankerite and kutnohorite samples, including the synthetic starting materials, are disordered. The P–T slopes of the three reactions increase in the order M = Mg, Fe, Mn. The shallower slope for the reaction involving magnesite is due partly to its having a higher compressibility than expected from unit-cell volume considerations. At low pressures there is a preference for partitioning into the double carbonate of Mg > Fe > Mn. At high pressures the partitioning preference is reversed. Using the measured reaction positions, the P–T conditions at which dolomite solid solutions will break down on increasing P and T in subduction zones can be estimated.     

Evolution of metamorphic volatiles during exhumation of microdiamond-bearing granulites in the Western Gneiss Region, Norway

Fluid inclusions in garnet, kyanite and quartz from microdiamond-bearing granulites in the Western Gneiss Region, Norway, document a conspicuous fluid evolution as the rocks were exhumed following Caledonian high- and ultrahigh-pressure (HP–UHP) metamorphism. The most important of the various fluid mixtures and daughter minerals in these rocks are: (N₂ + CO₂ + magnesian calcite), (N₂ + CO₂ + CH₄ + graphite + magnesian calcite), (N₂ + CH₄), (N₂ + CH₄ + H₂O), (CO₂) and (H₂O + NaCl + CaCl₂ + nahcolite). Rutile also occurs in the N₂ + CO₂ inclusions as a product of titanium diffusion from the garnet host into the fluid inclusions. Volatiles composed of N₂ + CO₂ + magnesian calcite characterise the ambient metamorphic environment between HP–UHP (peak) and early retrograde metamorphism. During progressive decompression, the mole fraction of N₂ increased in the fluid mixtures; as amphibolite-facies conditions were reached, CH₄ and later, H₂O, appeared in the fluids, concomitant with the disappearance of CO₂ and magnesian calcite. Graphite is ubiquitous in the host lithologies and fluid inclusions. Thermodynamic modelling of the metamorphic volatiles in a graphite-buffered C-O-H system demonstrates that the observed metamorphic volatile evolution was attainable only if the f _O2 increased from c. −3.5 (±0.3) to −0.8 (±0.3) log units relative to the FMQ oxygen buffer. External introduction of oxidising aqueous solutions along a system of interconnected ductile shear zones adequately explains the dramatic increase in the f _O2. The oxidising fluids introduced during exhumation were likely derived from dehydration of oceanic crust and continental sediments previously subducted during an extended period of continental collision in conjunction with the Caledonian orogeny. Received: 15 December 1997 / Accepted: 25 May 1998     

Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.

Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) ¹⁸O/¹⁶O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ¹⁸O_ol (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ¹⁸O_ol values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ¹⁸O_ol values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ¹⁸O_ol is weakly correlated (R ² = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ¹⁸O values for HIMU-peridotite (δ¹⁸O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ¹⁸O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ¹⁸O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ¹⁸O (<5 ‰), rather than higher-δ¹⁸O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ¹⁸O_ol and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.     

<Emphasis Type="Italic">P</Emphasis>–<Emphasis Type="Italic">T</Emphasis> and fluid evolution of barren and lithium pegmatites from Vlastějovice,Bohemian Massif,Czech Republic

Fluid inclusions, mineral thermometry and stable isotope data from two types of mineralogically and texturally contrasting pegmatites, barren ones and lithium ones, from the Moldanubian Zone of the Bohemian Massif were studied in order to constrain P–T conditions of their emplacement, subsolidus hydrothermal evolution and to estimate composition of the early exsolved fluid and that of the parental melt. Despite the fact that the lithium pegmatites are abundant throughout the crystalline units of the Bohemian Massif, data similar to this paper have not been published yet. The studied pegmatites are hosted by iron-rich calcic skarn bodies. This specific setting allowed scavenging of calcium, fluorine and some other elements from the host rocks into the pegmatitic melts and post-magmatic fluids. Such contamination process was important namely in the case of barren pegmatites, as can be deduced from the variation in anorthite contents in plagioclase and from the presence of fluorite, hornblende (with F content) or garnet in the contact zones of pegmatite dykes. Fluid inclusions were studied mostly in quartz, but also in fluorite, titanite and apatite. Early aqueous–carbonic and late aqueous fluids were identified in both pegmatite types. The P–T conditions of crystallization as well as the detailed composition of exsolved magmatic fluid, however, particularly differ. The magmatic fluids associated with barren pegmatites correspond to H₂O–CO₂ low salinity fluids, composition of which evolved from 20 to 23 to <5 mol% CO₂, and from 2 to 4–6 mol% NaCl eq. Sudden decrease in the CO₂ content of the post-magmatic fluids (<5 mol% CO₂) seems to coincide with the enrichment of the fluid in calcium (from the contamination process) and resulted in precipitation of calcites (frequently found as trapped solid phases in fluid inclusions). The fluids associated with lithium pegmatites are more complex (H₂O–CO₂/N₂–H₃BO₃–NaCl). The CO₂ content of early exsolved fluid is 26–20 mol% CO₂ and remains the same in the next fluid generation. The main difference between the magmatic and the first post-magmatic fluids is the presence of 7–9 wt% of H₃BO₃ (identified as daughter mineral sassolite) in the former. The second post-magmatic fluids are again CO₂-poor (∼4 mol%) and more saline (∼4 mol% NaCl eq.). The composition of exsolved fluid was further used to constrain volatile composition and content of the parental melts. Finally, P–T conditions of pegmatite crystallization are constrained: 600–640°C and 420–580 MPa for the barren pegmatites and 500–570°C and 310–430 MPa for the lithium pegmatite. While the emplacement of the former occurred in thermal equilibrium with the Moldanubian host rock environment, the emplacement of the later suggests substantial thermal disequilibrium.     

P–T–t evolution of spinel–cordierite–garnet gneisses from the Sauwald Zone (Southern Bohemian Massif, Upper Austria): is there evidence for two independent late-Variscan low-P/high-T events in the Moldanubian Unit?

The Sauwald Zone, located at the southern rim of the Bohemian Massif in Upper Austria, belongs to the Moldanubian Unit. It exposes uniform biotite + plagioclase ± cordierite paragneisses that formed during the post-collisional high-T/low-P stage of the Variscan orogeny. Rare metapelitic inlayers contain the mineral assemblage garnet + cordierite + green spinel + sillimanite + K-feldspar + plagioclase + biotite + quartz. Mineral chemical and textural data indicate four stages of mineral growth: (1) peak assemblage as inclusions in garnet (stage 1): garnet core + cordierite + green spinel + sillimanite + plagioclase (An_35–65); (2) post-peak assemblages in the matrix (stages 2, 3): cordierite + spinel (brown-green and brown) ± sillimanite ± garnet rim + plagioclase (An_10–45); and (3) late-stage growth of fibrolite, muscovite and albite (An_0–15) during stage 4. Calculation of the P–T conditions of the peak assemblage (stage 1) yields 750–840°C, 0.29–0.53 GPa and for the stage 2 matrix assemblage garnet + cordierite + green spinel + sillimanite + plagioclase 620–730°C, 0.27–0.36 GPa. The observed phase relations indicate a clockwise P–T path, which terminates below 0.38 GPa. The P–T evolution of the Sauwald Zone and the Monotonous Unit are very similar, however, monazite ages of the former are younger (321 ± 9 Ma vs. 334 ± 1 Ma). This indicates that high-T/low-P metamorphism in the Sauwald Zone was either of longer duration or there were two independent phases of late-Variscan low-P/high-T metamorphism in the Moldanubian Unit.     

Experimental studies of the <Emphasis Type="Italic">P</Emphasis>–<Emphasis Type="Italic">T</Emphasis>–H<Subscript>2</Subscript>O near-liquidus phase relations of basaltic andesite from North Sister Volcano,High Oregon Cascades: constraints on lower-crustal mineral assemblages

We have mapped the mineralogy onto the H₂O-undersaturated liquidus surface of basaltic andesite from North Sister Volcano to constrain the crystalline assemblage with which, and P–T–H₂O conditions at which, the melt last equilibrated before erupting. Combining our high pressure experimental results with examples of tectonically exposed lower arc crust, geophysical constraints, trace element geochemistry, and melt inclusion volatile contents, we conclude that an anhydrous, augite-rich gabbro at ∼12 kbar and ∼1,175°C is the most probable lithology with which North Sister basaltic andesite with ∼3.5 wt% H₂O last equilibrated before erupting. We speculate that reaction between this gabbro and primitive mantle-derived precursor melts buffered the compositions of magmas erupted from this volcano resulting in their remarkably limited compositional range.     

Modelling phase–assemblage diagrams for magnesian metapelites in the system K2O–FeO–MgO–Al2O3–SiO2–H2O: geodynamic consequences for the Monte Rosa nappe, Western Alps

Magnesian metamorphic rocks with metapelitic mineral assemblage and composition are of great interest in metamorphic petrology for their ability to constrain P–T conditions in terranes where metamorphism is not easily visible. Phase–assemblage diagrams for natural and model magnesian metapelites in the system KFMASH are presented to document how phase relationships respond to water activity, bulk composition, pressure and temperature. The phase assemblages displayed on these phase diagrams are consistent with natural mineral assemblages occurring in magnesian metapelites. It is shown that the equilibrium assemblages at high pressure conditions are very sensitive to a(H₂O). Specifically, the appearance of the characteristic HP assemblage chloritoid–talc–phengite–quartz (with excess H₂O) in the magnesian metapelites of the Monte Rosa nappe (Western Alps) is due to the reduction of a(H₂O). Furthermore, the mineral assemblages are determined by the whole-rock FeO/(FeO+MgO) ratio and effective Al content X _A as well as P and T. The predicted mineral associations for the low- and high-X _A model bulk compositions of magnesian metapelites at high pressure are not dependent on the X _A variations as they show a similar sequence of mineral assemblages. Above 20 kbar, the prograde sequence of assemblages associated with phengite (with excess SiO₂ and H₂O) for low- and high-X _A bulk compositions of magnesian metapelites is: carpholite–chlorite → chlorite–chloritoid → chloritoid–talc → chloritoid–talc–kyanite → talc–garnet–kyanite → garnet–kyanite ± biotite. At low to medium P–T conditions, a low-X _A stabilises the phengite-bearing assemblages associated with chlorite, chlorite + K-feldspar and chlorite + biotite while a high-X _A results in the chlorite–phengite bearing assemblages associated with pyrophyllite, andalusite, kyanite and carpholite. A high-X _A magnesian metapelite with nearly iron-free content stabilises the talc–kyanite–phengite assemblage at moderate to high P–T conditions. Taking into account the effective bulk composition and a(H₂O) involved in the metamorphic history, the phase–assemblage diagrams presented here may be applied to all magnesian metapelites that have compositions within the system KFMASH and therefore may contribute to gaining insights into the metamorphic evolution of terranes. As an example, the magnesian metapelites of the Monte Rosa nappe have been investigated, and an exhumation path with P–T conditions for the western roof of the Monte Rosa nappe has been derived for the first time. The exhumation shows first a near-isothermal decompression from the Alpine eclogite peak conditions around 24 kbar and 505°C down to approximately 8 kbar and 475°C followed by a second decompression with concomitant cooling.M. Frey: deceased     

Reply to “Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.”

The comment by Day et al. (Contrib Mineral Petrol, 2012) (1) discusses the validity of the previously obtained oxygen isotope data for El Hierro and La Palma (Canary Island) olivines, (2) questions the approach by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) of using weakly correlated variations of δ¹⁸O_olivine values with X _px (proportion of pyroxenite-derived melt in the parental magma), and (3) provides reasons why oxygen isotope data by secondary ion mass spectrometry (SIMS) “offer sensitive means for detecting melt-crust interactions.” We respond these comments and report a new set of oxygen isotope measurements performed by SIMS and single-grain laser fluorination methods. These measurements confirm our previous data and conclusions and demonstrate the ability of the SIMS technique to analyze O isotopes in terrestrial samples with 2-sigma uncertainty better than ±0.25 ‰.     

H2O activity in concentrated NaCl solutions at high pressures and temperatures measured by the brucite-periclase equilibrium

 H₂O activities in concentrated NaCl solutions were measured in the ranges 600°–900° C and 2–15 kbar and at NaCl concentrations up to halite saturation by depression of the brucite (Mg(OH)₂) – periclase (MgO) dehydration equilibrium. Experiments were made in internally heated Ar pressure apparatus at 2 and 4.2 kbar and in 1.91-cm-diameter piston-cylinder apparatus with NaCl pressure medium at 4.2, 7, 10 and 15 kbar. Fluid compositions in equilibrium with brucite and periclase were reversed to closures of less than 2 mol% by measuring weight changes after drying of punctured Pt capsules. Brucite-periclase equilibrium in the binary system was redetermined using coarsely crystalline synthetic brucite and periclase to inhibit back-reaction in quenching. These data lead to a linear expression for the standard Gibbs free energy of the brucite dehydration reaction in the experimental temperature range: ΔG° (±120J)=73418–134.95T(K). Using this function as a baseline, the experimental dehydration points in the system MgO−H₂O−NaCl lead to a simple systematic relationship of high-temperature H₂O activity in NaCl solution. At low pressure and low fluid densities near 2 kbar the H₂O activity is closely approximated by its mole fraction. At pressures of 10 kbar and greater, with fluid densities approaching those of condensed H₂O, the H₂O activity becomes nearly equal to the square of its mole fraction. Isobaric halite saturation points terminating the univariant brucite-periclase curves were determined at each experimental pressure. The five temperature-composition points in the system NaCl−H₂O are in close agreement with the halite saturation curves (liquidus curves) given by existing data from differential thermal analysis to 6 kbar. Solubility of MgO in the vapor phase near halite saturation is much less than one mole percent and could not have influenced our determinations. Activity concentration relations in the experimental P-T range may be retrieved for the binary system H₂O-NaCl from our brucite-periclase data and from halite liquidus data with minor extrapolation. At two kbar, solutions closely approach an ideal gas mixture, whereas at 10 kbar and above the solutions closely approximate an ideal fused salt mixture, where the activities of H₂O and NaCl correspond to an ideal activity formulation. This profound pressure-induced change of state may be characterized by the activity (a) – concentration (X) expression: a _{H 2}O=X _{H 2}O/(1+αX _NaCl), and a _NaCl=(1+α)^(1+α)[X _NaCl/(1+αX _NaCl)]^(1+α). The parameter α is determined by regression of the brucite-periclase H₂O activity data: α=exp[A–B/ϱ_{H 2}O ]-CP/T, where A=4.226, B=2.9605, C=164.984, and P is in kbar, T is in Kelvins, and ϱ_{H 2}O is the density of H₂O at given P and T in g/cm³. These formulas reproduce both the H₂O activity data and the NaCl activity data with a standard deviation of ±0.010. The thermodynamic behavior of concentrated NaCl solutions at high temperature and pressure is thus much simpler than portrayed by extended Debye-Hückel theory. The low H₂O activity at high pressures in concentrated supercritical NaCl solutions (or hydrosaline melts) indicates that such solutions should be feasible as chemically active fluids capable of coexisting with solid rocks and silicate liquids (and a CO₂-rich vapor) in many processes of deep crustal and upper mantle metamorphism and metasomatism. Received: 1 September 1995 / Accepted: 24 March 1996     

A comment on: ‘TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz’, by Jay B. Thomas,E. Bruce Watson,Frank S. Spear,Philip T. Shemella,Saroj K. Nayak and Antonio Lanzirotti

Trace concentrations of Ti in quartz are used to indicate the pressure and temperature conditions of crystallization in the ‘TitaniQ’ geothermobarometer of Thomas et al. (Contrib Miner Petrol 160:743–759, 2010). It utilises the partitioning of Ti into quartz as an indicator of the pressures and/or temperatures of crystal growth. For a given value of TiO₂ activity in the system, if temperatures are inferred to ±20 °C, pressure is constrained to ±1 kbar and vice versa. There are significant contrasts, however, between the conclusions from TitaniQ and those for natural quartz (as well as other mineral phases) in volcanic rocks. Application of the TitaniQ model to quartz from the 27 ka Oruanui and 760 ka Bishop high-silica rhyolites, where the values of T, P and TiO₂ activity are constrained by other means (Fe–Ti oxide equilibria, melt inclusion entrapment pressures in gas-saturated melts, melt and amphibole compositions), yields inconsistent results. If realistic values are given to any two of these three parameters, then the value of the third is wholly unrealistic. The model yields growth temperatures at or below the granite solidus, pressures in the lower crust or upper mantle, or TiO₂ activities inconsistent with the mineralogical and chemical compositions of the magmas. CL imagery and measurements of Ti (and other elements) in quartz are of great value in showing the growth histories and changes in conditions experienced by crystals, but direct linkages to P, T conditions during crystal growth cannot be achieved.     

Fluid influence on mineral reactions in ultrahigh-pressure granulites: a case study in the Śnieżnik Mts. (West Sudetes, Poland)

Small tectonic slices of undeformed eclogites and ultrahigh-pressure granulites occur in three tectonic units of the Śnieżnik Mts. (SW Poland). Ultrahigh-pressure granulite/eclogite transitions with peak metamorphic conditions between 21 and 28 kbar at 800 to 1000 °C occur only in the Złote unit. Conventional U-Pb multigrain analyses of zircons from a mafic granulite provided ²⁰⁷Pb/²⁰⁶Pb ages between 360 to 369 Ma which are interpreted to approximate timing of original crystallisation from a melt. Diffusion kinetics and the restricted availability of a fluid phase mainly controlled the conversion from granulite to eclogite, although some bulk-chemical differences were also recognised. The ultrahigh-pressure granulites from the Złote unit exclusively contain H₂O-rich inclusions with variable salinities which distinguishes them from high-temperature (HT)-granulites world-wide. This is also in contrast to the fluid regime (H₂O-N₂-CO₂) recognised in the lower-temperature eclogites (600–800 °C) from the closely associated Międzygórze and Śnieżnik units. The variation in fluid composition between the lower-temperature eclogites and ultrahigh-pressure granulites on the one hand and ultrahigh-pressure granulites and HT-granulites on the other hand probably indicates contrasting P-T-t paths as a result of different tectonic environments. Received: 15 June 1998 / Accepted: 2 March 1999