ALBERT

Notes: Abstract A garnet–hornblende Fe–Mg exchange geothermometer has been calibrated against the garnet–clinopyroxene geothermometer of Ellis & Green (1979) using data on coexisting garnet + hornblende + clinopyroxene in amphibolite and granulite facies metamorphic assemblages. Data for the Fe–Mg exchange reaction between garnet and hornblende have been fitted to the equation. In KD=Δ (XCa,g) where KD is the Fe–Mg distribution coefficient, using a robust regression approach, giving a thermometer of the form: with very satisfactory agreement between garnet–hornblende and garnet–clinopyroxene temperatures. The thermometer is applicable below about 850°C to rocks with Mn-poor garnet and common hornblende of widely varying chemistry metamorphosed at low aO2.Application of the garnet–hornblende geothermometer to Dalradian garnet amphibolites gives temperatures in good agreement with those predicted by pelite petrogenetic grids, ranging from 520°C for the lower garnet zone to 565–610°C for the staurolite to kyanite zones. These results suggest that systematic errors introduced by closure temperature problems in the application of the garnet–clinopyroxene geothermometer to the ‘calibration’data set are not serious. Application to ‘eclogitic’garnet amphibolites suggests that garnet and hornblende seldom attain Fe–Mg exchange equilibrium in these rocks.Quartzo-feldspathic and mafic schists of the Pelona Schist on Sierra Pelona, Southern California, were metamorphosed under high pressure greenschist, epidote–amphibolite and (oligoclase) amphibolite facies beneath the Vincent Thrust at pressures deduced to be 10±1 kbar using the phengite geobarometer, and 8–9kbar using the jadeite content of clinopyroxene in equilibrium with oligoclase and quartz. Application of the garnet–hornblende thermometer gives temperatures ranging from about 480°C at the garnet isograd through 570°C at the oligoclase isograd to a maximum of 620–650°C near the thrust. Inverted thermal gradients beneath the Vincent Thrust were in the range 170 to 250°C per km close to the thrust.

Notes: [Auszug] No crustal rocks are known to have survived since the time of the intense meteor bombardment that affected Earth between its formation about 4,550 Myr ago and 4,030 Myr, the age of the oldest known components in the Acasta Gneiss of northwestern Canada. But evidence of an ...

Notes: [Auszug] The subduction of oceanic lithosphere is thought to enrich the mantle in elements concentrated in altered oceanic crust and its sedimentary cover (for example, H2O, CO2 and alkalis),. This enrichment is generally inferred from the geochemistry of island-arc lavas. More ...

Notes: Abstract Heats of mixing of synthetic C2/m fluortremolite-fluoredenite amphiboles measured at 985 K show a systematic deviation from ideal mixing consistent with a subregular solution model. The deviations from ideal mixing are interpreted in terms of Na ordering in the A-site and Na-Al interactions in edenite-poor compositions. Enthalpies of ‘edenite’ substitution reactions in amphiboles and in SiO2-NaAlO2 glasses and framework silicates are comparable. Gibbs free energies of formation of fluortremolite and fluoredenite at 298K are -2,821.07±3.34 kcal mol−1 and -2,889.59±2.40 kcal mol−1 respectively. The former value is in good agreement with values calculated from both F-OH exchange experiments and from a natural fluortremolite-bearing metamorphic rock. Least-squares fitted sub-regular heat-of-mixing parameters are poorly constrained and unrealistically high, but estimated subregular mixing parameters consistent with 95% confidence interval uncertainties in the calorimetric data and with TEM constraints give activity-composition relations in good agreement with the A-site compositions of natural metamorphic and igneous hornblendes. These relations predict unmixing in edenite-rich compositions over a wide range of temperature, but lend no support to the existence of a hornblende-actinolite miscibility gap. Calibration of the reaction tremolite+ albite=edenite+4 quartz as a function ofP,T andX ed amph indicates negativedP/dT slopes and a limited range of X ed amph (0.3 to 0.5) in equilibrium with plagioclase and quartz over a wide range of pressure and temperature, consistent with metamorphic hornblende-plagioclase assemblages. The energetics of this reaction suggest, however, that amphibole-plagioclase disequilibrium may be common.

Notes: Abstract Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 18O/16O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in 18O and Sr compared to PLC, and is much more 18O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of 18O-depleted (metamorphic or magmatic) fluid (initial δ18O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10−8 m2, from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼103 to ∼104 years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of 18O/16O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ18O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen.

Notes: Abstract  Quartz grains in hydrothermally altered granites from the Isle of Skye are highly heterogeneous and not equilibrated in oxygen isotope ratio at the 20 μm scale. Ion microprobe analysis of one grain shows a gradient of 13‰ over 400 μm and a greater range in δ 18O than all quartz previously analyzed on the Isle of Skye. Other crystals from the same outcrop are homogeneous. Digitized cathodoluminescence images reveal patterns of magmatic zoning and brittle fracturing not otherwise detectable. The ion probe analysis correlates low δ 18O values on a micro-scale to one set of healed cracks. Thus, quartz exchanges oxygen isotopes primarily by solution and reprecipitation along fractures, in contrast to more reactive feldspar that appears to exchange from the grain boundary inward. Macroscopic models of isotope exchange are not realistic for these rocks; the flow of hydrothermal fluids was heterogeneous, anisotropic and crack controlled.

Notes: Abstract Blue-green hornblendes are observed in metabasite assemblages throughout the chlorite, biotite and garnet zones of the southwest Scottish Highlands. Actinolites are common in more Mg-rich metabasites in these zones. At low grade, hornblendes are relatively edenite-rich, and may sometimes occur together with a more Mg-rich, Al-poor actinolite. Within the garnet zone, hornblendes are pargasitic, showing extensive tschermakite substitution. Textural and chemical evidence do not indicate the presence of any miscibility gap between hornblende and actinolite within the chlorite to garnet zones in the southwest Highlands. The occurrence of hornblende-actinolite pairs in metabasites of the Scottish Dalradian, and perhaps also in other metamorphic terrains, is considered to reflect the incomplete chemical equilibration of lower grade actinolitic amphibole during prograde metamorphism, rather than a miscibility gap. The paucity of amphibole compositions intermediate between hornblende and actinolite in many metamorphic terrains is thought to reflect the rapid but continuous change of stable amphibole compositions in metabasites over a small range of increased metamorphic grade.

Notes: Abstract Diffusion parameters for hydrogen diffusion in epidote-group minerals and micas have been measured under hydrothermal conditions, or calculated from existing experimental data, for bulk hydrogen isotope exchange experiments between hydrous minerals and water. Activation energies in the range 14 to 31 kcals/g-atom H are comparable to those derived by application of kinetic theory to experimental hydrogen isotope exchange data, and to those for oxygen diffusion in minerals under hydrothermal conditions. Diffusion of hydrogen in epidote is about four orders of magnitude faster than in muscovite, and about two orders of magnitude faster than in zoisite. Hydrogen diffusion in micas is about five orders of magnitude faster than oxygen diffusion, and hydrogen transport occurs dominantly parallel to the layers rather than parallel to the c-axis as for oxygen. Rapid hydrogen transport in minerals may proceed by hydrolysis of Si-O and Al-O bonds, followed by exchange of hydrolyzed oxygens with slower-diffusing (OH) or H2O. Water appears to be essential for stable isotope exchange between minerals in slowly cooling metamorphic rocks. Stable isotope data for regional metamorphic mineral assemblages suggests that water is usually present in small amounts during cooling of prograde regional metamorphic systems, and estimated closure temperatures for cessation of stable isotope exchange are often more comparable to those calculated from diffusion data than to likely temperatures of metamorphism. Alpine deformation of the Hercynian Monte Rose Granite (Frey et al. 1976) permitted access of water and initiated stable isotope exchange amongst coexisting minerals. The diffusional behaviour of species in relict Hercynian muscovites is consistent with available experimental diffusion data.

Notes: Abstract The diffusion rate of 18O tracer atoms in anorthite (An97Ab03) under anhydrous conditions has been measured using SIMS techniques. The tracer source was 18O2 98.4% gas at 1 bar, in the temperature range 1300° C−850° C. The measured diffusion constants are D 0=1 −0.6 +1 ×10−9 m2s−1 Q=236±8 kJ mol−1 Comparison of these values with published data for 18O diffusion in anorthite under hydrothermal conditions shows that “dry” oxygen diffusivities are orders of magnitude lower than equivalent “wet” values at similar temperatures. The effect of these differences on oxygen isotope equilibration during cooling is discussed.

Notes: Abstract Fluid-calcite-calcite dihedral angles have been measured for fluids in the system H2O−CO2−NaCl, between 1 and 2 kbar, and 550–750° C. It is found that the calcite-calcite-H2O dihedral angle decreases steadily with addition of NaCl from a value of about 80° (pure water) to 44° (60 wt% NaCl). The CO2−H2O system displays a well-defined minimum at $$X_{CO_2 } = 0.5$$ , with a dihedral angle of 50°, in contrast to those of pure CO2 and H2O which are 90° and 80° respectively. Experiments containing fluids which are immiscible at run conditions showed a bimodal distribution of dihedral angles in the CO2−H2O−NaCl system, which can be approximately correlated with the compositions of the two fluid phases. Such bimodality was only observed for immiscible fluids in the H2O−NaCl system if the quench rate exceeded about 200°C per min. This is probably due to the extremely rapid establishment of the single phase dihedral angle on quenching. The fluid phase topology in devolatilising marbles will only be a connected network for very saline brines and fluids with $$X_{CO_2 } $$ close to 0.5. Fluids trapped in fluid inclusions in calcite grains in marbles may be predominantly H2O-rich or CO2-rich, and of low salinity. All other fluid compositions in the H2O−CO2−NaCl-calcite system will occupy isolated pores, the largest of which will grow at the expense of the smallest. Escape of fluid produced during devolatilisation reactions under such conditions will occur by fluid overpressuring and hydrofracture. In contrast, previous experimental studies of quartz-fluid dihedral angles between 950° and 1100° C (Watson and Brenan 1987) predict that quartz-dominated lithologies will permit pervasive flow of H2O−NaCl fluids, but not of H2O−CO2 fluids. Documented geological examples of differences in permeability and fluid flow mechanism between metamorphic argillites, psammites and limestones which support the results of the experimental studies are discussed.