Dissolution Front Research Articles

Peridotite Weathering and Ni Redistribution in New Caledonian Laterite Profiles: Influence of Climate, Hydrology, and Structure

The peridotite massifs of New Caledonia are characterised by complex hydrodynamics influenced by intense inherited fracturing, uplift, and erosion. Following the formation of the erosion surfaces and alteration processes, these processes drive chemical redistribution during weathering; particularly lateritisation and saprolitisation. Magnesium, silica, and trace elements such as nickel and cobalt—released as the dissolution front advances—are redistributed through the system. New observations and interpretations reveal how lateritic paleo-land surfaces evolved, and their temporal relationship with alteration processes since the Oligocene. Considering the geometry of discontinuity networks ranging from micro-fractures to faults, the transfers occur in dual-permeability environments. Olivine dissolution rates are heterogeneously due to differential solution renewal caused by erosion and valley deepening. Differential mass transfer occurs between mobile regions of highly transmissive faults, while immobile areas correspond to the rock matrix and the secondary fracture network. The progression of alteration fronts controls the formation of boulders and the distribution of nickel across multiple scales. In the saprolite, nickel reprecipitates mostly in talc-like phases, as well as minor nontronite and goethite with partial diffusion in inherited serpentine. The current nickel distribution results from a complex interplay of climatic, hydrological and structural factors integrated into a model across different scales and times.

Migration of dissolution front in a fracture network − Implications for weathering of fractured bedrock systems and boulder formation

Fracture networks contribute to the differential weathering of fractured bedrock at multiple scales. The influence of competing fracture networks is discussed in light of hydrogeochemical conditions to predict the dissolution pattern resulting from spheroidal weathering. The investigation of the dimensionless Péclet (Pe) and Damköhler (Da) numbers on a simple case of a dual-scale fracture network and its application to three fracture network weathering reveals the influence of fluid flow and reaction rate conditions on the dissolution patterns.The conceptual model was numerically validated and compared with observations on lateritic nickel deposits in New Caledonia. A fracture network will contribute to boulder development if the associated fluid flow regime reaches a Pe threshold of around 10. On the other hand, predominant diffusion will inhibit the fracture set in favour of a higher permeability fracture network. The Da drives, for its part, the width of the dissolution halo. Owing to the dependency of the fluid flow regime on the fracture network characteristics, scaling laws were established to estimate the size of the boulders at different scales by predicting the fracture contribution as a function of their Pe.

Controlling release from encapsulated drug-loaded devices: insights from modeling the dissolution front propagation.

Dissolution of drug from its solid form to a dissolved form is an important consideration in the design and optimization of drug delivery devices, particularly owing to the abundance of emerging compounds that are extremely poorly soluble. When the solid dosage form is encapsulated, for example by the porous walls of an implant, the impact of the encapsulant drug transport properties is a further confounding issue. In such a case, dissolution and diffusion work in tandem to control the release of drug. However, the interplay between these two competing processes in the context of drug delivery is not as well understood as it is for other mass transfer problems, particularly for practical controlled-release considerations such as an encapsulant layer around the drug delivery device. To address this gap, this work presents a mathematical model that describes controlled release from a drug-loaded device surrounded by a passive porous layer. A solution for the drug concentration distribution is derived using the method of eigenfunction expansion. The model is able to track the dissolution front propagation, and predict the drug release curve during the dissolution process. The utility of the model is demonstrated through comparison against experimental data representing drug release from a cylindrical drug-loaded orthopedic fixation pin, where the model is shown to capture the data very well. Analysis presented here reveals how the various geometrical and physicochemical parameters influence drug dissolution and, ultimately, the drug release profile. It is found that the non-dimensional initial concentration plays a key role in determining whether the problem is diffusion-limited or dissolution-limited, whereas the nature of the problem is largely independent of other parameters including diffusion coefficient and encapsulant thickness. We expect the model will prove to be a useful tool for those designing encapsulated drug delivery devices, in terms of optimizing the design of the device to achieve a desired drug release profile.

Dissolution of (U,Th)O2 heterogeneous mixed oxides

Heterogeneous U1-xThxO2 polished pellets were prepared through sintering of oxides obtained from hydroxide precursors. Mixing several homogeneous U1-xThxO2 powders with various stoichiometries allowed the preparation of a panel of heterogeneous sintered pellets with a matrix-inclusions type microstructure. The characterization of the polished pellets was performed by X-EDS. From image analysis of large cartographies of the pellets, the distribution and amount of each type of heterogeneity was evaluated. To follow the chemical durability of the prepared materials, the pellets were submitted to dissolution tests in 2 and 4 mol.L−1 HNO3 at 60 and 90 °C. The obtained dissolution rates of the materials highlighted the need to access a more detailed microscopic study due to the presence of enriched dissolution residues at the end of the experiments. The heterogeneities were simulated by using powders heated at 1600 °C to isolate their specific dissolution behaviour. The sintered powders surrogates dissolved extremely slowly in solution. However, the normalized dissolution rates increased when HNO2 catalytic species were introduced in the solution. Another set of experiments obtained by varying the incorporation rates in heterogeneities showed a decrease of the dissolution rate with increasing incorporation rate of Th-enriched heterogeneities. This effect is counterintuitive as Th-enriched heterogeneities are not supposed to dissolve during the first instants of the dissolution. Microscopic study based on operando monitoring of the solid/liquid interface highlighted preferential dissolution zones with a dissolution front in the matrix and the refractory character of the heterogeneities. Finally, the collected residues of dissolution were also characterized. They showed slight dissolution progress with the formation of dissolution pits, preferential attacks of the grain boundaries and a mechanism resembling the cracking core model of dissolution. This work offers a first study of the dissolution of heterogeneous U1-xThxO2 mixed oxides with a matrix-inclusion type microstructure.

Landslides in the Remolinos gypsum escarpment (NE Spain): controls imposed by stratigraphy, fluvial erosion, and interstratal salt dissolution

Dissolution of karst rocks (evaporites and carbonates) can cause significant mechanical weakening, but its preparatory role for landslide development has been scarcely explored. Fluvial valleys carved in gypsum bedrock typically display prominent escarpments with numerous landslides and perched valleys indicative of rapid retreat rate. The stratigraphic and cartographic analysis of the 37-km-long Remolinos gypsum escarpment in the Ebro Valley (NE Spain) reveals that landslide types are controlled by the lithological succession: (1) rotational slides in sections with mudstones and marls at the base; (2) rock-slope collapses (massive rock-falls) where the cliff includes halite packages at the foot; and (3) relatively small rock-falls and topples being the main failures affecting cliffs entirely made by gypsum. Fluvial undercutting by the highly mobile Ebro River is the main process that controls the spatial and temporal distribution of slope instability. Geomorphic and chronological evidence supports that the abandonment in 1574 of the El Castellar village was at least partially motivated by a shift in the river channel toward the escarpment and the consequent landslide activity. Several lines of evidence support the concept whereby interstratal salt dissolution (halite and glauberite), here designated as subsurface solutional undermining, play a significant preparatory role for landslide development: (1) dissolution of salt close to the scarp by the inward advance of dissolution fronts and subsidence of the overlying strata; (2) collapsed fault blocks with no offset across the grabens; and (3) brine seepages and extensive efflorescences and precipitates of Na-sulfates and halite.

Reactive-infiltration instability in a Hele-Shaw cell influenced by initial aperture and flow rate

We experimentally investigate dissolution morphologies in a radial Hele-Shaw cell. We observe a unique phenomenon where the dissolution front shifts from stable to unstable and uncover the role of buoyancy-driven convection in forming radial stripes (dissolution ``flower'') on the solid surface. We propose a phase diagram to predict the transitions of dissolution patterns.

Evaluation of transport properties of deteriorated concrete due to calcium leaching with coupled CT image analysis and random walk simulation

Concrete may deteriorate when chronically in contact with water due to the leaching of calcium ions. This study conducted a natural diffusion test for calcium ions with a minute cylindrical specimen of 3 mm in diameter and 6 mm in height to determine leaching at 20 and 80 °C in 33 days. One piece of limestone as aggregate was inserted inside each specimen to investigate the effect of the interfacial transition zone (ITZ). Changes in mass transfer in the leaching and non-leaching regions in bulk cement paste were evaluated using synchrotron X-ray computed tomography (CT) in a micrometer order. A deeper dissolution front of Ca(OH)2 inside the specimen was observed for a higher temperature leaching test. Random walk simulation was performed to obtain diffusion parameters. Results showed that the calcium diffusion coefficient of non-deteriorated ITZ is about ten times as high as that of the non-leaching region. For the leaching region, the diffusion coefficient is about 50 times and 100 times as high as that of the non-leaching region at 20 °C and 80 °C, respectively. In addition, the Ca(OH)2 dissolution front appeared deeper inside the specimen in the direction where aggregate is close or exposed to the dissolution front because of ITZ.

The Effect of Iron- and Calcium-Rich Waste Rock’s Acid Baking Conditions on the Rare-Earth Extraction

The work investigates the effect of sulfuric acid baking on rare earth element (REE) extraction from two waste rock samples from a phosphate mine. The role of different mineralogical assemblages and the degree of alteration (i.e., weathering), and the behavior of the main impurities–iron, phosphorus, and calcium–on REE extraction are emphasized. For both samples, the sulfuric acid baking at 25 °C, during 15 min, H2SO4:sample (w/w) mass ratio of 0.45:1 is the best condition for achieving the selective leaching of REE. For the iron rich-sample, the increase in temperature reduces REE extraction and increases iron dissolution. The corresponding sulfuric acid consumed by goethite (α-FeOOH) from 25 °C to 160 °C acid baking is ten times higher than that required for the monazite (REEPO4) reaction. Conversely, higher REE and lower iron extraction are observed by increasing (sulfuric acid/sample) mass ratio (0.95:1). Due to the high sulfuric concentration during dissolution, a local saturation zone close to the dissolution front caused the precipitation of iron oxyhydroxides. The calcium-rich sample shows lower REE extraction by leaching (63% maximum) mainly due to the entrapment of REE-bearing minerals by a gypsum layer, and lanthanide’s uptake by calcium sulfate compounds formed during leaching. The results were discussed with the help of a detailed characterization of the residues.

Effects of Hydrostatic Dissolution and Seepage on the Transport and Mechanical Properties of Glauberite

During the development of urban underground space in Chengdu, China, it was found that glauberite rocks in the Guankou formation of the Cretaceous system had extensive dissolution and exerted a serious impact on the safety of the project. At present, research on the transport and mechanical properties of glauberite under hydrostatic conditions in this area is limited. In this paper, the effects of hydrostatic dissolution and seepage on the transport and mechanical properties of glauberite are studied. The results show that the concentration of aqueous solution increases step by step with the increase in the dissolution time of glauberite in still water, indicating that the forward movement of the dissolution front of glauberite rock is not a continuous process and has intermittent characteristics. The dissolution and infiltration of mirabilite seriously deteriorates the physical structure of mirabilite, resulting in a decrease in elastic modulus and an increase in axial deformation, and a decrease in mechanical properties. There are a dissolution layer, dissolution front and undissolved area in the karst infiltration of calcium and mirabilite in the hydrostatic solution, so the mechanism of the calcium and mirabilite karst dissolution process is determined. Because of the dissolution characteristics of mirabilite, underground space development should prevent the uneven settlement of mirabilite, ground collapse, pit and chamber water gushing, corrosive groundwater and other geological problems.

Modeling and verification of non-linear mineral dissolution processes with buoyancy effects

A new methodology for the simulation of salt cavity development by dissolution is presented, verified and qualitatively validated by experiments. Starting from an initial cavity, the simulator models the injection of fresh water, natural and forced convection of the brine, and the evolution of the cavity walls due to dissolution. The nonlinear model couples brine mass and momentum conservation (governed by incompressible Navier–Stokes equations) with the buoyancy effect due to the brine density variations. Vortex generation and density-driven brine plume rise demonstrate the impact of complex brine flow patterns on the dissolution front evolution. A new explicit interface tracking strategy is employed to investigate the dissolution front movement and an improved smoothing algorithm to enhance the model robustness, contributing to low computational cost and stable simulation for the long-term dissolution process simulation. The proposed model is verified by conducting spatial and temporal convergence studies and qualitatively validated using lab-scale experiments. The agreement between experiments and simulations of horizontal and vertical dissolution cases demonstrates the utility of the model. The simulation results indicate that the rising plume of brine results in a “morning glory” shape cavity under a vertical dissolution scenario and a significant difference between upper and lower fronts dissolution rates for the horizontal dissolution case. The coupling effect of eddy development and cavity shape evolution is also discussed. This work furthers the understanding of the interaction between brine transport in an initially-formed cavity and dissolution patterns of the cavity boundaries, driven by gravity and convective flows.

Multiscale physical–chemical analysis of the impact of fracture networks on weathering: Application to nickel redistribution in the formation of Ni-laterite ores, New Caledonia

Supergene processes related to downward water migration and dissolution of primary minerals in the New Caledonian peridotites result in Ni enrichment at the bottom of the lateritic profile near bedrock. However, the combined effects of relief, lateral fluid flow, and complex inherited discontinuity networks filled by serpentine generate a more complex Ni distribution than a simple flat horizon. In surficial environments, fluid flow and mass transfer are not limited to the vertical scale; they can also be related to lateral fluid circulation and local drainage along damage zones in the vicinity of faults. In this study, we present new structural, petrophysical and geochemical data for core samples to shed light on the impact of a fracture network on the alteration and progression of the Ni-enrichment front during weathering. The analysis of element redistribution by XRF mapping coupled with fracture extraction from computed tomography (CT) establishes that the serpentine fracture network comprises sets of sub-orthogonal fractures whose orientations are potentially determined by pre-existing magmatic foliation. The progression of the olivine dissolution front leads to the redistribution and concentration of Ni into the serpentine fracture network as secondary Mg-Ni talc-like phases. The increase in porosity from < 1 % in the bedrock to > 10 % in the saprock is mainly driven by the formation of nanopores. Nanoporosity may control the development of the weathering front and the redistribution of Ni by small-scale diffusion. Structural and geochemical characteristics identified at the sample scale are analogous to those observed on the larger scale of the outcrop and deposit. Scale invariance in the structural organization and geochemical evolution indicates the potential upscaling of the processes involved in the redistribution of Ni.

A novel algorithm for implementing perturbations in computational simulations of chemical dissolution‐front instability problems within fluid‐saturated porous media

AbstractThis paper deals with how to implement perturbations in the computational simulations of chemical dissolution‐front instability (CDFI) problems in fluid‐saturated porous media. On the basis of theoretical analysis, it is found that the application of a perturbation to the chemical dissolution front is equivalent to the application of an alternative perturbation to the dimensionless pore‐fluid normal velocity (relative to the planar chemical dissolution front) in the chemical dissolution zone, where the chemical dissolution front is located. This avoids the difficulty to find the spatial coordinates of the chemical dissolution front locations in the computational simulations of CDFI problems. Based on this new finding, a novel algorithm for implementing perturbations in the computational simulations of CDFI problems is proposed. The key point of the proposed algorithm is that the perturbed pore‐fluid normal velocity (relative to the planar chemical dissolution front) is used to directly replace the original pore‐fluid normal velocity (relative to the planar chemical dissolution front) in the related mathematical governing equations (MGEs), so that the proposed algorithm works for the porosity‐velocity‐concentration scheme when it is used to solve CDFI problems in fluid‐saturated porous media. In addition, the related theoretical analysis in this study has answered the previous unanswered question why the application of a perturbation to porosity works in the porosity‐pressure‐concentration scheme but does not work in the porosity‐velocity‐concentration scheme for solving the same CDFI problems in fluid‐saturated porous media. Through solving two illustrative examples with two different distributions of initial porosity, in which one is homogeneous and another is heterogeneous in the chemical dissolution system, the validity and usefulness of the proposed algorithm for implementing perturbations in the computational simulations of CDFI problems have been demonstrated.

Oxidative Dissolution of Arsenic-Bearing Sulfide Minerals in Groundwater: Impact of Hydrochemical and Hydrodynamic Conditions on Arsenic Release and Surface Evolution.

The dissolution of sulfide minerals can lead to hazardous arsenic levels in groundwater. This study investigates the oxidative dissolution of natural As-bearing sulfide minerals and the related release of arsenic under flow-through conditions. Column experiments were performed using reactive As-bearing sulfide minerals (arsenopyrite and löllingite) embedded in a sandy matrix and injecting oxic solutions into the initially anoxic porous media to trigger the mineral dissolution. Noninvasive oxygen measurements, analyses of ionic species at the outlet, and scanning electron microscopy allowed tracking the propagation of the oxidative dissolution fronts, the mineral dissolution progress, and the change in mineral surface composition. Process-based reactive transport simulations were performed to quantitatively interpret the geochemical processes. The experimental and modeling outcomes show that pore-water acidity exerts a key control on the dissolution of sulfide minerals and arsenic release since it determines the precipitation of secondary mineral phases causing the sequestration of arsenic and the passivation of the reactive mineral surfaces. The impact of surface passivation strongly depends on the flow velocity and on the spatial distribution of the reactive minerals. These results highlight the fundamental interplay of reactive mineral distribution and hydrochemical and hydrodynamic conditions on the mobilization of arsenic from sulfide minerals in flow-through systems.

Petrophysical initialization of core-scale reactive transport simulations on Indiana limestones: Pore-scale characterization, spatial autocorrelations, and representative elementary volume analysis

Initializations of the petrophysical parameters significantly affect the results of reactive transport simulations on unstable dissolution fronts. As the phenomenon arises from the inherent heterogeneity of the rocks, heterogenous initialization of the petrophysical fields is needed to model such a phenomenon. While modeling of unstable dissolution fronts has been extensively studied in the past, the geostatistical information required to initialize the heterogeneous petrophysical fields is usually assumed and still missing. The objective of this paper is to acquire such information for Indiana limestones on a core-scale. This is done by combining high resolution tomography with pore scale calculations to determine: i) the rock minimum representative volume (REV), ii) the frequency distributions of the petrophysical parameters, namely; porosity, permeability, and reactive surface area, iii) the relationships between the petrophysical parameters, and iv) the rock spatial correlation model and lengths. The results obtained should help reduce the uncertainties associated with petrophysical initialization of core-scale reactive transport simulations of carbonate rocks in general, and Indiana limestones in particular.

Diagenetic dissolution, maghemitization and sulphidization of magnetic minerals in rapidly deposited gas hydrate bearing sediments from the Bay of Bengal

We conducted a comprehensive rock magnetic investigation complemented by a scanning electron microscopy analyses on a 148.8 m sediment core (NGHP-01-20A) from the methane-hydrate bearing site in the Bay of Bengal to systematically evaluate how magnetic minerals selectively respond to a range of diagenetic processes in the sulfidic and methanic sediments. For diagenetic analysis, we defined five distinct sediment magnetic zones (I–V) based on the sediment magnetic signatures. Rock magnetic property is mainly carried by complex magnetic mineral assemblages of detrital (titanomagnetite, silicate hosted magnetic inclusions), altered (titanomaghemite, titanohematite) and fine-grained diagenetic (pyrite) and authigenic (greigite) iron sulfide minerals. Three distinct bands of enhanced magnetic susceptibility in Z-II, Z-III and Z-V mainly comprised of detrital magnetite-rich minerals delivered by the peninsular river systems as a result of higher sedimentation events in the Krishna-Godavari (K-G) basin. Progressive diagenetic dissolution of primary iron oxide and consequent formation of iron sulfide in the uppermost sulfidic zone (Z-I) is clearly mirrored in the magnetic susceptibility (χlf) profile. Presence of moderately altered coarse-grained detrital Fe–Ti particles in the deeper methanic and magnetically enhanced zones (Z-II, Z-III, Z-V) suggest that sediment diagenesis at this site was significantly constrained by the multiple events of rapid sedimentation which might have restricted the complete dissolution of the primary minerals. Decline in magnetic grain size diagnostic proxy (ARM/IRM2.5T) in the uppermost sulfidic zones (Z-I, Z-II) can be attributed to the preferential dissolution of fine-grained magnetite. Further, downcore increases could be linked with the authigenic formation of fine-grained magnetite in methanic zones (Z-III to Z-V). Ferrimagnetic iron sulfide (greigite) indicative (SIRM/χlf) parameter showed sudden rise in Z-II and remain fairly constant throughout, suggesting the presence of authigenic greigite. Scanning electron microscopy in-line with energy dispersive X-ray spectroscopy analyses of magnetic particles from different sediment magnetic zones revealed a range of ferrimagnetic (titanomagnetite, titanomaghemite), antiferromagnetic (titanohematite) iron oxides and iron sulfide (pyrite). Detrital titanomagnetite with angular, irregular, spherical and well-defined octahedral with micron and submicron sized particles mainly derived from Deccan Volcanic Province (DVP) dominates the rock magnetic signal of bulk sediments in the studied core. We noticed several evidence of diagenetic dissolution, sulphidization and maghemitization of magnetic particles in the studied sediment core. Few nanometre-sized detrital magnetic particles occur as inclusions within the silicate minerals and remains protected against the sulfidic dissolution fronts through geologic times. Optical microscopy revealed the dominance of diagenetic pyrite occurring as overgrowth on the ferrimagnetic particles. We demonstrate that the rockmagnetic methods in combination with focussed electron microscope analyses provide valuable insights into the mineralogy, genesis and state of preservation of magnetic particles in sulfidic and methanic environments and thereby enhances the interpretative value of rock magnetic proxies.

Reactive Transport Model of Gypsum Karstification in Physically and Chemically Heterogeneous Fractured Media

Gypsum dissolution leads to the development of karstic features within much shorter timescales than in other sedimentary rocks, potentially leading to rapid deterioration of groundwater quality and increasing the risk of catastrophes caused by subsidence. Here, we present a 2-D reactive transport model to evaluate gypsum karstification in physically and chemically heterogeneous systems. The model considers a low-permeability rock matrix composed mainly of gypsum and a discontinuity (fracture), which acts as a preferential water pathway. Several scenarios are analyzed and simulated to investigate the relevance for gypsum karstification of: (1) the dynamic update of flow and transport parameters due to porosity changes; (2) the spatial distribution of minerals in the rock matrix; (3) the time evolution of water inflows through the boundaries of the model; (4) the functions relating permeability, k, to porosity, ϕ. The average porosity of the matrix after 1000 years of simulation increases from 0.045 to 0.29 when flow, transport, and chemical parameters and the water inflows through the boundary are dynamically updated according to the porosity changes. On the contrary, the porosity of the matrix hardly changes when the porosity feedback effect is not considered, while its average increases to 0.13 if the water inflow occurs through the discontinuity. Moreover, the dissolution of small amounts of highly soluble sulfate minerals plays a major role in the development of additional fractures. The increase in hydraulic conductivity is largest for the power law with an exponent of n = 5, as well as the Kozeny-Carman and the modified Fair-atch k-ϕ relationships. The gypsum dissolution front propagates into the matrix faster when the power law with n = 2 and 3 and the Verma–Pruess k-ϕ relationships are used.

Nonuniform Collective Dissolution of Bubbles in Regular Pore Networks

Understanding the evolution of solute concentration gradients underpins the prediction of porous media processes limited by mass transfer. Here, we present the development of a mathematical model that describes the dissolution of spherical bubbles in two-dimensional regular pore networks. The model is solved numerically for lattices with up to 169 bubbles by evaluating the role of pore network connectivity, vacant lattice sites and the initial bubble size distribution. In dense lattices, diffusive shielding prolongs the average dissolution time of the lattice, and the strength of the phenomenon depends on the network connectivity. The extension of the final dissolution time relative to the unbounded (bulk) case follows the power-law function, {B^k/ell }, where the constant ell is the inter-bubble spacing, B is the number of bubbles, and the exponent k depends on the network connectivity. The solute concentration field is both the consequence and a factor affecting bubble dissolution or growth. The geometry of the pore network perturbs the inward propagation of the dissolution front and can generate vacant sites within the bubble lattice. This effect is enhanced by increasing the lattice size and decreasing the network connectivity, yielding strongly nonuniform solute concentration fields. Sparse bubble lattices experience decreased collective effects, but they feature a more complex evolution, because the solute concentration field is nonuniform from the outset.

Mechanism of droplet motion and in-plane nanowire formation with and without electromigration

Au deposition on Si(110) at temperature higher than 633 K leads to the formation of elongated liquid nano-droplets. In this work we show that under an electric field, the droplets move along the [1–10] axis towards the positive electrode by electromigration. During the motion, they dissolve the substrate forming a hole underneath and a nanowire behind them. We develop a model highlighting that the driving force of these processes is bound to the respect (i) of the Au-Si bulk chemical equilibrium and (ii) of the correct balance of surface/interfacial energies. The motion takes place by means of sudden jumps with length of the order of a few μm and by small readjustments of the order of some nm of the droplet front and back edges. With respect to experiments without electric field, electromigration changes the droplet motion by widening the droplet dissolution front and by facilitating droplet jumps.

The effect of halogens (F, Cl) on the near-liquidus crystallinity of a hydrous trachyte melt

Abstract The effect of F and Cl on the liquidus temperature of a hydrous (~3.5–4 wt% H2O) trachytic melt (~66 wt% SiO2) at 925 to 990 °C and at 100 MPa has been experimentally investigated. We employed a novel disequilibrium approach involving diffusion couple experiments with the two-diffusion couple end-members differing solely in halogen concentrations. A shift of the liquidus temperature by ~50 °C was observed between a halogen-poor and halogen-enriched melt. Each experiment spanned the entire range of F and Cl concentrations between the two end-member compositions. We determined the halogen concentrations at the transition from crystal-bearing to crystal-free melt. These concentrations correspond to the liquidus halogen concentrations of the melt at each experimental temperature. We demonstrate that there is a limiting halogen concentration (~0.19–0.52 wt% F; ~0.07–0.24 wt% Cl), below which the melt crystallizes spherulitic clinopyroxene during heating to the run temperature. At high temperatures, upon diffusion of F and Cl into the halogen-poor melt, those crystals dissolve, leaving behind a dissolution front parallel to the diffusion interface. We propose that the dissolution is a consequence of F and Cl complexing with some of the main cationic components of clinopyroxene (Mg, Fe, Ca), thereby destabilizing this phase. Thus, the experimental dissolution of clinopyroxene is a manifestation of a liquidus depression caused by increased halogen content. Our results show that the liquidus shifts at a rate of ~1575(379) K/mol% of F and Cl in the melt, which is a minimum estimate, assuming both halogens equally drive dissolution. This liquidus depression is valid for a range of halogen concentrations (~0.06–0.87 wt% F; ~0.06–0.36 wt% Cl) and the experimental temperatures. Our findings illustrate that the degassing of halogens during or prior to an eruption can enhance crystallization in the melt and therefore influence magma physical properties that may ultimately affect eruption style.

Analytical Solutions of Carbonate Acidizing in Radial Flow

The flow of reactive fluids into porous media, a phenomenon known as reactive infiltration, is important in natural and engineered systems. While most of the studies in this area cover theoretical and experimental analyses in linear acid flow, the present work concentrates on radial flow conditions from a wellbore in the field and on finding exact analytical solutions to moving boundary problems of the uniform dissolution front. Closed-form solutions are obtained for the transient convection–diffusion which allow the demarcation of the range of applicability of the quasi-static limit. The fluid velocity dependency of the diffusion–dispersion coefficient is also examined by comparing results from analytical solutions from constant and velocity-dependent coefficients. These contributions form the basis for linear stability analyses to describe acid fingering encountered in reservoir stimulation.