Experimental hydrogen isotope studies III: Diffusion of hydrogen in hydrous minerals,and stable isotope exchange in metamorphic rocks

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.     

Recharge and pollution of the english chalk: Some possible mechanisms

Pore water in the Chalk is likely to remain essentially static under the influence of environmental forces with the exception of evapotranspiration. A process of piston displacement of water through networks of microfissures provides a possible mechanism for downward percolation through the unsaturated Chalk.

Maintenance of continuous diffusion equilibrium between fissure and pore water throughout downward migration allows the explanation of the observed rates of movement for thermonuclear tritium in the unsaturated zone. Activation of increasingly large fissures with increasing infiltration rates explains observed rapid water-table response under conditions of sustained high inflow, and is consistent with the behaviour of water quality parameters in the saturated aquifer. Whereas in the unsaturated zone it is suggested that 80 to 90% of total flow passes through microfissures, in the saturated aquifer fluid transport is essentially through macrofissures. Diffusion equilibrium between pore water and fissure water in the saturated zone is not therefore expected.

Individual macrofissures occasionally are enlarged by solution, making it possible for a large proportion of saturated flow to take place through relatively few preferential flow channels. Although the macrofissures, and particularly enlarged macrofissures, are largely responsible for aquifer transmissivity, microfissure storage may often be highly significant in terms of specific yield.     

Bayesian modelling the retreat of the Irish Sea Ice Stream

We present an 8000‐year history spanning 650 km of ice margin retreat for the largest marine‐terminating ice stream draining the former British–Irish Ice Sheet. Bayesian modelling of the geochronological data shows the ISIS expanded 34.0–25.3 ka, accelerating into the Celtic Sea to reach maximum limits 25.3–24.5 ka before a collapse with rapid marginal retreat to the northern Irish Sea Basin (ISB). This retreat was rapid and driven by climatic warming, sea‐level rise, mega‐tidal amplitudes and reactivation of meridional circulation in the North Atlantic. The retreat, though rapid, is uneven, with the stepped retreat pattern possibly a function of the passage of the ice stream between normal and adverse ice bed gradients and changing ice stream geometry. Initially, wide calving margins and adverse slopes encouraged rapid retreat (～550 m a^?1) that slowed (～100 m a^?1) at the topographic constriction and bathymetric high between southern Ireland and Wales before rates increased (～200 m a^?1) across adverse bed slopes and wider and deeper basin configuration in the northern ISB. These data point to the importance of the ice bed slope and lateral extent in predicting the longer‐term (>1000 a) patterns and rates of ice‐marginal retreat during phases of rapid collapse, which has implications for the modelling of projected rapid retreat of present‐day ice streams. Copyright © 2013 John Wiley & Sons, Ltd.     

Probabilistic domain decomposition for the solution of the two-dimensional magnetotelluric problem

Probabilistic domain decomposition is proposed as a novel method for solving the two-dimensional Maxwell’s equations as used in the magnetotelluric method. The domain is split into non-overlapping sub-domains and the solution on the sub-domain boundaries is obtained by evaluating the stochastic form of the exact solution of Maxwell’s equations by a Monte-Carlo approach. These sub-domains can be naturally chosen by splitting the sub-surface domain into regions of constant (or at least continuous) conductivity. The solution over each sub-domain is obtained by solving Maxwell’s equations in the strong form. The sub-domain solver used for this purpose is a meshless method resting on radial basis function-based finite differences. The method is demonstrated by solving a number of classical magnetotelluric problems, including the quarter-space problem, the block-in-half-space problem and the triangle-in-half-space problem.     

Periglacial trimlines,former nunataks and the altitude of the last ice sheet in Wester Ross,northwest Scotland

High-level weathering limits separating ice-scoured topography from frost-weathered detritus were identified on 28 mountains in Wester Ross at altitudes of 700–960 m, and a further 22 peaks support evidence of ice scouring to summit level. Weathering limits are defined most clearly on sandstone and gneiss, which have resisted frost shattering during the Late Devensian Lateglacial, but can also be distinguished on schists and quartzite. Schmidt hammer measurements and analyses of clay mineral assemblages indicate significantly more advanced rock and soil weathering above the weathering limits. The persistence of gibbsite above weathering limits indicates that they represent the upper limit of Late Devensian glacial erosion. The regular decline of weathering-limit altitudes along former flowlines eliminates the possibility that the weathering limits represent former thermal boundaries between protective cold-based and erosive warm-based ice. The weathering limits are therefore interpreted as periglacial trimlines that define the maximum surface altitude of the last ice sheet. Calculated basal shear stresses of 50–95 kPa are consistent with this interpretation. Reconstruction of ice-sheet configuration indicates that the former ice-shed lay above 900 m along the present watershed, and that the ice surface descended northwestwards, with broad depressions along major troughs and localised domes around independent centres of ice dispersal. Extrapolation of the ice surface gradient and altitude suggests that the ice sheet did not overrun the Outer Hebrides, but was confluent with the independent Outer Hebrides ice-cap in the North Minch basin. Erratics located up to 140 m above the reconstructed ice surface are inferred to have been emplaced by a pre-Late Devensian ice sheet (or ice sheets) of unknown age. © 1997 John Wiley & Sons, Ltd.     

Platinum and palladium mobility in supergene environment: The residual origin of the Pirogues River mineralization, New Caledonia

Eluvial concentration of platinum-group minerals (PGM) has developed in the south of New Caledonia, from the weathering of a mafic and ultramafic cumulate. The platinum/palladium (Pt/Pd) ratio evolution from the bottom to the top of the weathering profile indicates a chemical mobilization of Pd in supergene environment. The examination by scanning electron microscopy of the residual PGM collected in the weathering profile and their chemical characterization by electronic microprobe show a preservation of the structure and chemical signature (in the core of the grains) of the fresh PGM. This clearly demonstrates that the PGM studied here are residual and are affected by dissolution process.     

An experimental study of phase equilibria in the systems H2O–CO2–CaCl2 and H2O–CO2–NaCl at high pressures and temperatures (500–800?°C, 0.5–0.9?GPa): geological and geophysical applications

Phase equilibria in the ternary systems H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ have been determined from the study of synthetic fluid inclusions in quartz at 500 and 800 °C, 0.5 and 0.9 GPa. The crystallographic control on rates of quartz overgrowth on synthetic quartz crystals was exploited to prevent trapping of fluid inclusions prior to attainment of run conditions. Two types of fluid inclusion were found with different density or CO₂ homogenisation temperature (T_h(CO₂)): a CO₂-rich phase with low T_h(CO₂), and a brine with relatively high T_h(CO₂). The density of CO₂ was calibrated using inclusions in the binary system H₂O–CO₂. Mass balance calculations constrain tie lines and the miscibility gap between brines and CO₂-rich fluids in the H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ systems at 500 and 800 °C, and 0.5 and 0.9 GPa. The miscibility gap in the CaCl₂ system is larger than in the NaCl system, and solubilities of CO₂ are smaller. CaCl₂ demonstrates a larger salting-out effect than NaCl at the same P–T conditions. In ternary systems, homogeneous fluids are H₂O-rich and of extremely low salinity, but at medium to high concentrations of salts and non-polar gases fluids are unlikely to be homogeneous. The two-phase state of crustal fluids should be common. For low fluid-rock ratios the cation compositions of crustal fluids are buffered by major crustal minerals: feldspars and micas in pelites and granitic rocks, calcite (dolomite) in carbonates, and pyroxenes and amphiboles in metabasites. Fluids in pelitic and granitic rocks are Na-K rich, while for carbonate and metabasic rocks fluids are Ca-Mg-Fe rich. On lithological boundaries between silicate and carbonate rocks, or between pelites and metabasites, diffusive cation exchange of the salt components of the fluid will cause the surfaces of immiscibility to intersect, leading to unmixing in the fluid phase. Dispersion of acoustic energy at critical conditions of the fluid may amplify seismic reflections that result from different fluid densities on lithological boundaries.Editorial responsibility: I. Parsons