Grain boundary and volume diffusion experiments in yttrium aluminium garnet bicrystals at 1,723 K: a miniaturized study

Yb-Y inter-diffusion along a single grain boundary of a synthetic yttrium aluminium garnet (YAG) bicrystal has been studied using analytical transmission electron microscopy (ATEM). To investigate the diffusion, a thin-film containing Yb as the diffusant was deposited perpendicular to the bicrystal grain boundary by pulsed laser deposition (PLD). Structural properties and their change with time in both the diffusant source and the grain boundary are reported. The diffusion profiles are incorporated in a numerical diffusion model, which is applied to determine the grain boundary diffusion coefficient, D _gb , at 1.723 K it is equal to 3 × 10⁻¹⁵ m²/s. We find that grain boundary diffusion is 4.85 orders of magnitude faster than volume diffusion, which was determined from the same diffusion experiment. This result is discussed in the context of special versus general grain boundaries. Finally, we successfully tested the capability of synchrotron-based nano-X-ray fluorescence analysis to map micro-chemical patterns in two dimensions with sub-micrometre resolution.     

Growth of multilayered polycrystalline reaction rims in the MgO–SiO<Subscript>2</Subscript> system,part II: modelling

Part I of this contribution (Gardés et al. in Contrib Mineral Petrol, 2010) reported time- and temperature-dependent experimental growth of polycrystalline forsterite-enstatite double layers between single crystals of periclase and quartz, and enstatite single layers between forsterite and quartz. Both double and single layers displayed growth rates decreasing with time and pronounced grain coarsening. Here, a model is presented for the growth of the layers that couples grain boundary diffusion and grain coarsening to interpret the drop of the growth rates. It results that the growth of the layers is such that (Δx)² ∝ t ^1−1/n , where Δx is the layer thickness and n the grain coarsening exponent, as experimentally observed. It is shown that component transport occurs mainly by grain boundary diffusion and that the contribution of volume diffusion is negligible. Assuming a value of 1 nm for the effective grain boundary width, the following Arrhenius laws for MgO grain boundary diffusion are derived: log D _gb,0^Fo (m²/s) = −2.71 ± 1.03 and E _gb^Fo = 329 ± 30 kJ/mol in forsterite and log D _gb,0^En (m²/s) = 0.13 ± 1.31 and E _gb^En = 417 ± 38 kJ/mol in enstatite. The different activation energies are responsible for the changes in the enstatite/forsterite thickness ratio with varying temperature. We show that significant biases are introduced if grain boundary diffusion-controlled rim growth is modelled assuming constant bulk diffusivities so that differences in activation energies of more than 100 kJ/mol may arise. It is thus important to consider grain coarsening when modelling layered reaction zones because they are usually polycrystalline and controlled by grain boundary transport.     

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.     

Provenance of Pleistocene Rhine River Middle Terrace sands between the Swiss–German border and Cologne based on U–Pb detrital zircon ages

Detrital zircon U–Pb age distributions derived from samples representing ancient or relatively young large-scale continental drainage networks are commonly taken to reflect the geochronological evolution of the tapped continental area. Here, we present detrital zircon U–Pb ages and associated heavy mineral data from Pleistocene Rhine River Middle Terrace sands and equivalents between the Swiss–German border and Cologne in order to test the commonly assumed Alpine provenance of the material. Samples from eight localities were analyzed for their heavy mineral assemblages. Detrital zircon U–Pb ages were determined by laser ablation inductively coupled mass spectrometry on selected samples from five locations along the Rhine River. The zircon age populations of all samples show a similar distribution, their main peaks being between 300 and 500 Ma. Minor age populations are recognized at 570 and 1,070 Ma. The 300–400 Ma maximum reflects the Variscan basement drained by or recycled into the Rhine River and its tributaries. The 400–500 Ma peak with predominantly Early Silurian ages points to Baltica or to the mid-German crystalline rise as original sources. One distinct peak at c. 570 Ma probably represents input from Cadomian terranes. The Precambrian U–Pb ages are compatible with derivation from sources in Baltica and in northern Gondwana. The heavy mineral populations of Middle Terrace sands and equivalents are characterized to a variable extend by garnet, epidote, and green hornblende. This association is often referred to as the Alpine spectrum and is considered to be indicative of an Alpine provenance. However, hornblende, epidote, and garnet are dominant heavy minerals of collisional orogens in general and may also be derived from Variscan and Caledonian units or from intermittent storage units. A remarkable feature of the detrital zircon age distribution in the Rhine River sediments from the Swiss–German border to Cologne is the absence of ages younger than 200 Ma and in particular of any ages reflecting the Alpine orogeny between c. 100 and 35 Ma. Sediments from rivers draining the equally collisional Himalaya orogen contain detrital zircons as young as 20 Ma. Our results question the assumption that Pleistocene Rhine River sediments were directly derived from the Alps. The lag time between the formation and deposition age of the youngest zircon in the studied Pleistocene Rhine River deposits is 200 Ma. Together with the absence of Alpine zircon ages, this stresses that detrital zircon age data from ancient sedimentary units found in poorly understood tectonic or paleogeographic settings need to be interpreted with great care, one could miss an entire orogenic cycle.     

Analytical Solution for Testing Debris Avalanche Numerical Models

—We present here the analytical solution of a one-dimensional dam-break problem over inclined planes. This solution is used to test a numerical model developed for debris avalanches. We consider a dam with infinite length in one direction where material is released from rest at the initial instant. We solve analytically and numerically the depth-averaged long-wave equations derived in a topography-linked coordinate system. The numerical and analytical solutions provide for a Coulomb-type friction law at the base of the flow. The analytical solution is obtained by using the method of characteristics and describes the flow over a constant slope, provided that the angle is higher than the friction angle. The numerical model utilizes a finite-difference method based on a Godunov-type scheme. Comparison between analytical and numerical results illustrates the remarkable stability and precision of the numerical method as well as its ability to deal with strong discontinuities.     

Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part I: Crystallization of zircon and REE-phosphates over three million years—a geochemical and U–Pb geochronological study

Zircon, monazite and xenotime crystallized over a temperature interval of several hundred degrees at the magmatic to hydrothermal transition of the Sn and W mineralized Mole Granite. Magmatic zircon and monazite, thought to have crystallized from hydrous silicate melt, were dated by conventional U–Pb techniques at an age of 247.6 ± 0.4 and 247.7 ± 0.5 Ma, respectively. Xenotime occurring in hydrothermal quartz is found to be significantly younger at 246.2 ± 0.5 Ma and is interpreted to represent hydrothermal growth. From associated fluid inclusions it is concluded that it precipitated from a hydrothermal brine ≤ 600 °C, which is below the accepted closure temperature for U–Pb in this mineral. These data are compatible with a two-stage crystallization process: precipitation of zircon and monazite as magmatic liquidus phases in deep crustal magma followed by complete crystallization and intimately associated Sn–W mineralization after intrusion of the shallow, sill-like body of the Mole Granite. Later hydrothermal formation of monazite in a biotite–fluorite–topaz reaction rim around a mineralized vein was dated at 244.4 ± 1.4 Ma, which distinctly postdates the Mole Granite and is possibly related to a younger hidden intrusion and its hydrothermal fluid system.

Obtaining precise age data for magmatic and hydrothermal minerals of the Mole Granite is hampered by uncertainties introduced by different corrections required for multiple highly radiogenic minerals crystallising from evolved hydrous granites, including ²³⁰Th disequilibrium due to Th/U fractionation during monazite and possibly xenotime crystallization, variable Th/U ratios of the fluids from which xenotime was precipitating, elevated contents of common lead, and post-crystallization lead loss in zircon, enhanced by the fluid-saturated environment. The data imply that monazite can also survive as a liquidus phase in protracted magmatic systems over periods of 10⁶ years. The outlined model is in agreement with prominent chemical core-rim variation of the zircon.     

Extended regional climate model projections for Europe until the mid-twentyfirst century: combining ENSEMBLES and CMIP3

This study aims at sharpening the existing knowledge of expected seasonal mean climate change and its uncertainty over Europe for the two key climate variables air temperature and precipitation amount until the mid-twentyfirst century. For this purpose, we assess and compensate the global climate model (GCM) sampling bias of the ENSEMBLES regional climate model (RCM) projections by combining them with the full set of the CMIP3 GCM ensemble. We first apply a cross-validation in order to assess the skill of different statistical data reconstruction methods in reproducing ensemble mean and standard deviation. We then select the most appropriate reconstruction method in order to fill the missing values of the ENSEMBLES simulation matrix and further extend the matrix by all available CMIP3 GCM simulations forced by the A1B emission scenario. Cross-validation identifies a randomized scaling approach as superior in reconstructing the ensemble spread. Errors in ensemble mean and standard deviation are mostly less than 0.1 K and 1.0 % for air temperature and precipitation amount, respectively. Reconstruction of the missing values reveals that expected seasonal mean climate change of the ENSEMBLES RCM projections is not significantly biased and that the associated uncertainty is not underestimated due to sampling of only a few driving GCMs. In contrast, the spread of the extended simulation matrix is partly significantly lower, sharpening our knowledge about future climate change over Europe by reducing uncertainty in some regions. Furthermore, this study gives substantial weight to recent climate change impact studies based on the ENSEMBLES projections, since it confirms the robustness of the climate forcing of these studies concerning GCM sampling.