Calcite precipitation instability under laminar, open-channel flow

We present a 2D numerical model for the growth of calcite from supersaturated aqueous solutions under laminar, open-channel flow conditions. The model couples solution chemistry, precipitation at solution/calcite interfaces, hydrodynamics, diffusion and degassing. The model output is compared with experimental results obtained using an oversaturated calcite solution produced by mixing CaCl₂ and Na₂CO₃. The precipitation rate is observed to increase when the supersaturated solution flows over an obstruction, leading to a growth instability that causes the formation of terraces. At relatively high flow rates, the most important mechanism for this behaviour seems to be hydrodynamic advection of dissolved species either towards or away from the calcite surface, depending on location relative to the obstruction, which deforms the concentration gradients. At lower flow rates, steepening of diffusion gradients around protrusions becomes important. Enhanced degassing over the obstruction due to shallowing and pressure drop is not important on small scales. Diffusion controlled transport close to the calcite surface can lead to a fingering-type growth instability, which generates porous textures. Our results are consistent with existing diffusive boundary layer theory, but for flow over non-smooth surfaces, simple calcite precipitation models that include empirical correlations between fluid flow rate and calcite precipitation rate are inaccurate.     

Mud and fluid migration in active mud volcanoes in Azerbaijan

Mud volcanic eruptions in Azerbaijan normally last for less than a few hours, and are characterized by vigorous extrusion of mud breccias, hydrocarbon gases, and waters. Recent fieldwork and mapping on four active mud volcanoes show that dormant period activity ranges from quiet to vigorous flow of mud and fluids. Geochemical analyses of expelled waters show a wide range in solute concentrations, suggesting the existence of a complex plumbing system. The mud and fluids have a deep origin, but are sometimes stored in intermediate-depth mud chambers. A mixing model between deep-seated saline waters and shallow meteoric water is proposed.     

A model of oscillatory zoning in solid solutions grown from aqueous solutions: Applications to the (Ba,Sr)SO4 system

Barite-celestite crystals can be synthesized from aqueous solutions during counter-diffusion in a gel column connecting two reservoirs. It is known that such crystals may exhibit oscillatory zoning, whereby the barium composition in the crystal fluctuates more or less regularly from the core of the crystal to its rim. We present here a simple model of oscillatory zoning in such binary solid solutions A₁A₂ grown from aqueous solutions. The model combines diffusive transport of the relevant ions with an autocatalytic growth process. The latter is formulated as a continuous growth in which the probability of finding a kink site on the growing surface depends on the chemical composition of that surface. Thus, an A₁-rich surface favors the growth of A₁ over A₂, as long as A₁ is present in the vicinity of the surface. Precipitation results in a local depletion of A₁ in the aqueous solution, and the system may switch to a A₂ growth mode, until diffusion replenishes the amount of A₁, and so on. We use a dynamical equation for the molar fraction of component A₁ in the crystal, which results from mass conservation across the rough crystal-solution interface. Linear stability analysis and direct numerical solutions show that the system exhibits oscillatory behavior. Using the barite-celestite system as a framework, the scaling is consistent with the experimental observations. We discuss the variety of zoning patterns and textures numerically obtained as the concentrations of reactants in the reservoirs vary. This model might help in understanding the formation of oscillatory zoning in hydrothermal environments.     

Parallel Force/Position Crane Control in Marine Operations

A parallel force/position controller is proposed for the control of loads through the wave zone in marine operations. The controller structure has similarities to the parallel force/position control scheme used in robotics. The parallel force/position controller is tested for crane control in simulations and model experiments and the results are presented in this paper. To evaluate the performance of the proposed controller, we study three different control strategies for control of loads through the wave zone: active heave compensation, wave synchronization, and parallel force/position control. The parallel force/position controller gave improved results, in particular, a significant improvement of the minimum value of the wire tension, which is important to avoid snatch loads that may break the wire. The three strategies are tested and compared in simulations and experiments     

In situ AFM study of the dissolution and recrystallization behaviour of polished and stressed calcite surfaces

We investigated the dissolution behaviour of polished calcite surfaces in situ using a fluid-cell atomic force microscope. Polished calcite surfaces enabled us to study the effects of applied surface stress and crystallographic orientation on calcite dissolution pattern formation. Thin-sections of Iceland spar single-crystals polished either parallel or with a 5° miscut angle to cleavage planes were studied. Compressive surface stresses of up to 50 MPa were applied to some of the thin-section samples by means of elastic concave bending. Experiments were carried out in semi-stagnant deionized water under mainly transport limited dissolution conditions. Samples polished parallel to cleavage planes dissolved by the formation of etch-pits originating from polishing defects. The dissolution behaviour of 5° miscut surfaces was relatively unaffected by polishing defects, since no etch-pits developed in these samples. Dissolution of the miscut samples led to stepped or rippled surface patterns on the nanometer scale that coarsened during the first 30-40 min of the experiments. Possible reasons for the pattern-coarsening were: (i) progressive bunching of retreating dissolution steps and (ii) surface energy driven recrystallization (Ostwald ripening) under transport limited dissolution conditions. A flat polished miscut surface in calcite may recrystallize into a hill-and-valley structure in a (near-)saturated solution so as to lower its total surface free energy in spite of a larger surface area. No clear effect of applied stress on dissolution pattern formation has been observed.     

Halogen contents of eclogite facies fluid inclusions and minerals: Caledonides,western Norway

Primary multiphase brine fluid inclusions in omphacite and garnet from low‐ to medium‐temperature eclogites have been analysed for Cl, Br, I, F, Li and SO₄. Halogen contents and ratios provide information about trapped lower crustal fluids, even though the major element (Na, K, Ca) contents of inclusion fluids have been modified by fluid–mineral interactions and (step‐) daughter‐crystal formation after trapping. Halogens in the inclusion fluids were analysed with crush–leach techniques. Cl/Br and Cl/I mass ratios of eclogite fluids are in the range 31–395 and 5000–33 000, respectively. Most fluids have a Cl/Br ratio lower than modern seawater and a Cl/I ratio one order of magnitude lower than modern seawater. Fluids with the lowest Cl/Br and highest Cl/I ratios come from an eclogite that formed by hydration of granulite facies rocks, and may indicate that Br and I are fractionated into hydrous minerals. Reconstructions indicate that the inclusion fluids originally contained 500–4000 ppm Br, 1–14 ppm I and 33–438 ppm Li. Electron microprobe analyses of eclogite facies amphibole, biotite, phengite and apatite indicate that F and Cl fractionate most strongly between phengite (F/Cl mass ratio of 1469 ± 1048) and fluid (F/Cl mass ratio of 0.008), and the least between amphibole and fluid. The chemical evolution of Cl and Br in pore fluids during hydration reactions is in many ways analogous to Cl and Br in seawater during evaporation: the Cl/Br ratio remains constant until the a_H2O value is sufficiently lowered for Cl to be removed from solution by incorporation into hydrous minerals.     

Morphological instabilities during rapid growth of metamorphic garnets

Hydrothermal grossular-andradite garnets from contact aureoles in the Oslo region show morphological transitions from planar via cellular to hopper-like structures. Dodecahedral surfaces {110} dominate during the planar growth stage, whereas the stable crystal faces, developed during the cellular and hopper stages also includes the ikositetrahedron {211} and possibly the hexoctahedron {321}. Faceted cells develope when initially ‘wavy’ perturbations on the dodecahedral surfaces become tangential to lower-index planar surfaces. Inclusion patterns and morphologies of almandinerich garnets from Magerøy (northernmost Norway) that formed during a period of rapid heating, suggest an early stage of cellular growth followed by planar growth. The morphological transitions suggest that the hydrothermal garnets experienced an increase in the overstepping of the garnet precipitation reaction at some stage during their growth whereas the opposite was the case during growth of the Magerøy garnets. The present observations put constraints on the garnet growth rates and emphasize the importance of growth kinetics during metamorphic processes.     

The preservation potential of microstructures during static grain growth

Grain growth simulations using the microstructure simulation system Elle have been performed in materials with a pre‐existing grain shape foliation. As might be expected, the foliation is destroyed by the end of the experiment, and grain areas have increased by a factor of seven. The area of material swept by the migrating grain boundaries was monitored, and it was found that at every stage, virtually all of the grains which survived the grain growth process contain one and only one core of ‘unswept’ material. Remarkably these remnant unswept cores preserve a useable record of the initial grain size and the orientation of the grain shape foliation. This work suggests that, even for samples where no equivalent protolith can be found, it may be possible to see past a grain growth episode to estimate the original grain shape and grain size of the rock, and perhaps even reconstruct the grain boundary kinematics. In addition the identification of unswept cores has the potential to help unravel the evolution of grain boundary chemistry in rocks during metamorphism. As an example of a natural system showing these microstructures, we describe a peridotite from Almklovdalen, Norway. This peridotite was infiltrated by aqueous fluids at several stages during late Caledonian exhumation and retrogressive metamorphism. Grain boundary migration associated with the last of these infiltration events swept off abundant intragranular fluid inclusions in the original chlorite‐peridotite. At the grain scale, microstructural mapping of the fluid inclusion rich areas shows that, as with the numerical simulations, many of the grains retain exactly one core of unswept material. Examples of other natural systems discussed include dislocation density distributions and trace element zoning.     

Analytical transmission electron microscopy of oscillatory zoned grandite garnets

Oscillatory zoned grandite garnets from skarns of the Oslo rift region (southern Norway) have been studied using analytical transmission electron microscopy (ATEM). Our results show lamellae with a width varying from about 10 nm to more than 500 nm in both periodic and non-periodic sequences, which represent oscillatory zoning at a very fine scale. The compositions of adjacent lamellae alternate bimodally from X_and=0.55-0.75 to X_and=0.95-1.0. High resolution (HRTEM) images show that the compositional interfaces are sharp and coherent. Oscillatory zoning at the nm-scale puts constrains on the origin of oscillatory zoning in grandites and underlines the dynamic nature of the crystal growth process. The influence of growth rate is discussed against the background of local growth dynamics and external forcing at different length scales. This study emphasises the importance of adequate spatial resolution in analysing chemical variations in grandite garnets and shows that commonly applied methods (e.g. optical microscopy, backscattered electron imaging and electron or ion microprobe) are not sufficient to detect 'real' zonation patterns. Finally, proposed hypotheses on the origin of birefringence of grandite garnets with intermediate compositions are reviewed and discussed on the basis of the observed microstructure.