Atomic force microscopy has been used to observe the surface dynamics during dissolution of polished fluorite surfaces with different orientations. These surfaces, with an initially high density of atomic scale defects, showed fast changes during the first seconds in contact with a solution. Different types of structures developed on each surface, depending on its initial orientation and solution composition. These structures dissolved slower than the main surface persisting for at least 67.5 days of continuous dissolution. A new interpretation of traditional kinetic and thermodynamic models of dissolution applied to surfaces with a high density of steps is proposed to explain the observations. The new model includes the following: (a) fast initial dissolution at defect sites, (b) formation of a fluid boundary layer at the mineral solution interface enriched in the dissolving ions, and (c) precipitation of more stable fluorite structures nucleated at surface defects. This model highlights the importance of considering surface defects and crystal orientation for advancing our understanding of processes happening at the mineral solution interface and for developing more accurate kinetic dissolution and crystal growth models essential in Earth and material sciences.

Dissolution rates are usually calculated as a function of surface area, which is assumed to remain constant ignoring the changes occurring on the surface during dissolution. Here we present a study of how topography of natural fluorite surfaces with different orientation changes during up to 3200 h of dissolution. Results are analyzed in terms of changes in surface area, surface reactivity and dissolution rates. All surfaces studied present fast changes in topography during the initial 200 h of dissolution. The controlling factors that cause the development of topography are the stability of the step edges forming the initial surface and its inclination to the closest stable planes, which are specific for each surface orientation. During an initial dissolution regime dissolution rates decrease significantly, even though the total surface area increases. During a second dissolution regime, some surfaces continue to present significant changes in topography, while for others the topography tends to remain approximately constant. The observed variation of dissolution rates are attributed to a decrease of the density of step edges on the surface and the continuous increase in exposure of more stable surfaces. Calculations of dissolution rates, which assume that dissolution rates are directly proportional to surface area, are not valid for the type of surfaces studied. Instead, to develop accurate kinetic dissolution models and more realistic stochastic dissolution simulations the surface reactivity, determined by the relative stability of the planes and type of edges that constitute a surface needs to be considered. Significant differences between dissolution rates calculated based on surface area alone, and based on surface reactivity are expected for materials with the fluorite structure.

Feldspar crystals typically show a range of exsolution and polysynthetic twinning textures that can present problems for their full characterization, but at the same time give important information about their genesis. We present an integrated procedure for the micro-texture analysis, twin law identification plus crystal structure refinement of all components in a feldspar intergrowth. This procedure was applied to perthitic intergrowths in feldspars from two different pegmatites in the Larvik plutonic complex in the southern part of the Oslo region, Norway. It revealed that the two starting high-temperature (HT) feldspars had similar global chemical compositions but underwent significantly different cooling histories, with cooling times probably differing by over an order of magnitude. Powder X-ray diffraction with Rietveld refinement was used for a preliminary identification of the mineral components and concluding quantitative phase analysis. Electron microprobe analysis was used to bracket the chemical compositions of the constituents. Electron backscatter diffraction was used to reveal the texture of the samples, twin laws and spatial distribution and crystallographic orientation of the crystal domains. Single-grain X-ray diffraction recorded by an area detector was applied for a simultaneous integration of reflection intensities for all crystallographic domains with different orientations and severe diffraction overlaps. The crystal structures were refined using the program JANA2006 that allows a simultaneous calculation for structurally different components. Combined results of various methods helped improve accuracy and resolve ambiguities that arise from the application of a single technique. The approach is widely applicable to the study of mineral intergrowths and bridges an existing gap in the routinely accessible data on the structural characteristics of rock constituents.

The hydrothermal transformation of single aragonite crystals into polycrystalline calcite has been studied under hydrothermal conditions. The transformation involves a fluid-mediated replacement reaction, associated with fracturing of the initial aragonite crystal and growth of calcite throughout various parts of the reacted aragonite. The observed overall preservation of the crystal morphology is typical of an interface-coupled dissolution-reprecipitation mechanism Analysis of the crystallographic orientation of the product calcite using electron backscatter diffraction (EBSD) showed little to no link between the two phases under the studied conditions, with calcite crystallites exhibiting dominantly different crystallographic orientations compared to those of the aragonite and of neighbouring calcite domains. The complexity of the observed textures is mainly a result of the combination of fracturing of the crystal and initiation of nucleation and growth at different points of the exposed aragonite surface. Experiments performed with solutions enriched in O-18 as a tracer for oxygen exchange and monitored by Raman spectroscopy, showed that carbonate ions in the starting solution are mixed with carbonate from the dissolving aragonite, resulting in an O-18 concentration in the product calcite which depended on the local fluid transport through the fractures. As replacement processes among the CaCO3 phases are relevant to a wide range of applications, understanding the mechanisms is essential for the interpretation of observations of natural and/or experimental samples. This study describes the interplay between the replacement process, the fracturing of the crystal and growth of the new phase, calcite, and provides new insights into the mechanism of the aragonite to calcite transition. The combination of the two methods, EBSD and Raman spectroscopy, demonstrates the importance of local fluid composition and transport pathways in determining the isotope and element exchange in mineral replacement reactions.

We present microstructural and chemical analyses of chemically zoned and recrystallized plagioclase grains in variably strained samples of a naturally deformed anorthosite-leucogabbro, southern West Greenland. The recorded microstructures formed in the presence of fluids at mid-crustal conditions (620-640 A degrees C, 7.4-8.6 kbar). Recrystallized plagioclase grains (average grain size 342 mu m) with a random crystallographic orientation are volumetrically dominant in high-strain areas. They are characterized by asymmetric chemical zoning (An(80) cores and An(64) rims) that are directly associated with areas exhibiting high amphibole content and phase mixing. Analyses of zoning indicate anisotropic behaviour of bytownite plagioclase with a preferred replacement in the direction and along the (001) plane. In areas of high finite strain, recrystallization of plagioclase dominantly occurred by bulging recrystallization and is intimately linked to the chemical zoning. The lack of CPO as well as the developed asymmetric zoning can be explained by the activity of grain boundary sliding accommodated by dissolution and precipitation creep (DPC). In low-strain domains, grain size is on average larger and the rim distribution is not related to the inferred stress axes indicating chemically induced grain replacement instead of stress-related DPC. We suggest that during deformation, in high-strain areas, pre-existing phase mixture and stress induced DPC-caused grain rotations that allowed a deformation-enhanced heterogeneous fluid influx. This resulted in local plagioclase replacement through interface-coupled dissolution and precipitation and chemically induced grain boundary migration, accompanied by bulging recrystallization, along with neocrystallization of other phases. This study illustrates a strong interaction and feedback between physical and chemical processes where the amount of stress and fluids dictates the dominant active process. The interaction is a cause of deformation and external fluid infiltration with a result of strain localization and chemical re-equilibration at amphibolite facies conditions.

We present an electron backscatter diffraction, cathodoluminescence, and radiogenic U-Pb dating study of large zircon grains (0.8-1.5 mm) that show evidence of intracrystalline deformation, fracturing, grain size reduction and a large spread in U-Pb ages. The samples are from an amphibolite facies deformation zone within granulite facies anorthositic rocks (Bergen Arc, Norway). Large zircon grains show three main lattice distortion types: (I) distortions with rotations around < 001 > and an orientation change of similar to 0.3 degrees/mu m subparallel to (100); (II) highly distorted, half circular shaped zones located at grain edges with at least 0.8-1 degrees/mu m distortions; and (III) low-angle boundary networks forming deformation zones up to 100 mu m wide. Types II and III distortions exhibit significant disturbances of the otherwise homogeneous CL signature. Crystal plastic deformation with the slip system [010](100) resulted in type I distortions. Stress concentrations at grain contacts between rheologically hard grains caused localized crystal plastic deformation with minor amount of microfracturing forming type H distortions. Type Ill distortions formed by crystal plastic deformation often associated with inclusions using several slip systems. Distortions of types I and II show minor and moderate resetting of the original ca. 900 Ma zircon grains, respectively, due to enhanced pipe diffusion along dislocation walls. In type II distortions, accelerated lattice diffusion through the highly distorted crystal lattice, combined with exceptionally high boundary to volume ratio, caused significant chemical disturbance and age resetting to 410 Ma. Fine-grained aggregates contain grains with low internal deformation and an oscillatory zoned CL signature (Z-grains) or high internal deformation and a disturbed CL signature (D-grains). Z- and D-grains are interpreted to have formed by heterogeneous nucleation and growth, and fracturing along strain-hardened low-angle boundaries present within types I and II, respectively. Z-grains show a clustered chemical signature with a 437 +/- 11 Ma age interpreted to directly date the Caledonian amphibolite facies reworking.

We present detailed microstructural and chemical analyses from an initially dry anorthositic rock deformed during wet amphibolite facies conditions. Three different domains representing the microstructural variation of the deformed samples are investigated in detail in terms of fracture morphology and mode, grain characteristics and chemistry of present phases. Results show transient deformational behaviour where a close interaction between brittle, plastic and fluid-assisted deformation mechanisms can be observed. Our analysis allows us to describe the succession, interrelationships and effects of active mechanisms with progressively increasing strain in three so-called stages. In Stage 1, initial fracturing along cleavage planes promoted fluid influx that caused fragmentation and chemical reactions, producing fine-grained mineral assemblages in the fractures. Deformation twins and dislocations developed in clast pieces due to stress relaxation. Passive rotation of conjugate fracture sets and interconnection of intracrystalline fractures formed micro-shear-zones, constituting Stage 2. Microstructures and grain relationships indicate the activity and fluctuation between fracturing, dissolution-precipitation creep, grain boundary sliding and locally dislocation creep, reflecting the transient behaviour of brittle and plastic deformation mechanisms. Further rotation and widening of fractures into overall foliation parallel shear-bands (Stage 3) promoted strain partitioning into these areas through increased fluid influx, influence of fluid-assisted grain boundary sliding, phase mixing and presence of weak phases such as white mica. We suggest that local differences in fluid availability, volume fraction of weak phases produced by fluid present metamorphic reactions coupled with volume increase and local variations in stress concentration induced transient brittle-plastic behaviour. The studied shear-zone represents an example of the transformation of a rigid dry rock to a soft wet rock during deformation through syntectonic fracturing.

This paper reports how during dissolution differences in surface chemistry affect the evolution of topography of CaF2 pellets with a microstructure similar to UO2 spent nuclear fuel. 3D confocal profilometry and atomic force microscopy were used to quantify retreat rates and analyze topography changes on surfaces with different orientations as dissolution proceeds up to 468 h. A NaClO4 (0.05 M) solution with pH 3.6 which was far from equilibrium relative to CaF2 was used. Measured dissolution rates depend directly on the orientation of the exposed planes. The {111} is the most stable plane with a dissolution rate of (1.2 +/- 0.8) x 10(-9) mol m(-2) s(-1), and {112} the least stable plane with a dissolution rate 33 times faster that {111}. Surfaces that expose both Ca and F atoms in the same plane dissolve faster. Dissolution rates were found to be correlated to surface orientation which is characterized by a specific surface chemistry and therefore related to surface energy. It is proposed that every surface is characterized by the relative proportions of the three reference planes {111}, {100} and {110}, and by the high energy sites at their interceptions. Based on the different dissolution rates observed we propose a dissolution model to explain changes of topography during dissolution. Surfaces with slower dissolution rate, and inferred lower surface energy, tend to form while dissolution proceeds leading to an increase of roughness and surface area. This adjustment of the surface suggests that dissolution rates during early stages of dissolution are different from the later stages. The time-dependency of this dynamic system needs to be taken into consideration when predicting long-term dissolution rates.

We examine the partial survival of high-temperature mantle microstructures throughout multi-stage hydration-and dehydration-mediated pseudomorphism at differing pressure-temperature-fluid conditions. Throughout the harzburgitic mantle section of the Leka Ophiolite Complex (Norway), finite domains of parallel olivine encompassed by mesh-textured olivine resembling 'perfectly cleaved' olivine grains were identified. Crystallographic orientation mapping, combined with micro-computed tomography, reveals that the parallel olivine grains are highly misoriented (up to 90 degrees) with no crystal-preferred orientation, despite remaining parallel in three dimensions. Parallel olivine grains exhibit free dislocations with low dislocation density, whereas within mesh-textured olivine dislocations are aligned into walls. MnO is enriched (up to 1.8 wt %) and NiO depleted (0.21 +/- 0.24 wt %) within parallel olivine grains compared with mesh-textured olivine (0.29 +/- 0.14 wt % MnO; 0.38 +/- 0.19 wt % NiO). Clinopyroxene lamellae that are crystal-plastically deformed occur sandwiched in lizardite layers between every parallel olivine grain or fully enclosed within olivine. Al2O3 and Cr2O3 concentrations of clinopyroxene lamellae (2.09 +/- 0.88 wt % Al2O3; 0.79 +/- 0.27 wt % Cr2O3) overlap with those of primary clinopyroxene grains (2.43 +/- 0.69 wt % Al2O3; 0.83 +/- 0.36 wt % Cr2O3) and are distinctly different from those of secondary diopside found within the parallel olivine domains. Intragranular serpentine inclusions (X-Mg = 0.95 +/- 0.01), displaying elevated Al2O3 (3.92 +/- 4.10 wt %) and Cr2O3 (0.78 +/- 0.82 wt %) concentrations, are exclusively found within parallel olivine grains. Lizardite (X-Mg = 0.92 +/- 0.02) within the domains originates from hydration of parallel olivine and compositionally overlaps with mesh-texture lizardite. Antigorite (X-Mg = 0.95 +/- 0.01) replaces both types of olivine grains. Whole-rock compositions indicate a harzburgitic composition; however, microstructural and chemical observations and the current absence of primary orthopyroxene suggest that the precursor silicate of every parallel olivine domain was a single orthopyroxene grain that was initially serpentinized and later dehydrated to result in the present microstructure. Although desilicification is necessary during the transformation of orthopyroxene to olivine via a bastite stage, calculations based on whole-rock compositions imply that the released SiO2(aq) was mobile only over micrometer to centimeter scales, reacting with the surrounding olivine directly to form serpentine. Crosscutting relationships and serpentine compositions imply that dehydration occurred prior to the now evident lizardite-and antigorite-serpentinization. Comparison with the regional geological setting indicates that dehydration may have occurred transiently within the oceanic lithosphere prior to obduction.

Here we present the first four dimensional (time and three dimensional space resolved) experiment on a strongly deformed geological material. Results show that even complicated microstructures with large continuous and discontinuous changes in crystallographic orientation can be resolved quantitatively. The details that can be resolved are unprecedented and therefore the presented technique promises to become influential in a wide range of geoscientific investigations. Grain and subgrain scale processes are fundamental to mineral deformation and associated Earth Dynamics, and time resolved observation of these processes is vital for establishing an in-depth understanding of the latter. However, until recently, in situ experiments were restricted to observations of two dimensional surfaces. We compared experimental results from two dynamic, in situ annealing experiments on a single halite crystal; a 2D experiment conducted inside the scanning electron microscope and a 3D X-ray diffraction experiment. This allowed us to evaluate the possible effects of the free surface on grain and subgrain processes. The extent to which surface effects cause experimental artifacts in 2D studies has long been questioned. Our study shows that, although the nature of recovery processes are the same, the area swept by subgrain boundaries is up to 5 times larger in the volume than observed on the surface. We suggest this discrepancy is due to enhanced drag force on subgrain boundaries by thermal surface grooving. Our results show that while it is problematic to derive absolute mobilities from 2D experiments, derived relative mobilities between boundaries with different misorientation angles can be used.