Evolution of mineral–fluid interfaces studied at pressure with synchrotron X-ray techniques

In situ measurements of mineral surface evolution during the process of pressure solution are possible with the high brightness of synchrotron X-ray sources. This capability has been explored through the use of newly developed reaction vessels that allow transmission of the incident and scattered X-ray beam through a low atomic weight piston. Several new vessels are described, along with details of computational algorithms that are used to simulate X-ray scattering in this unconventional geometry. Results using calcite (CaCO₃) and halite (NaCl) as reactant crystals are presented and compared to other atomic-scale measurements of surface dissolution processes. Calcite was reacted with an unsaturated fluid at 30 bars of pressure for approximately 24 h. During reaction the root mean square surface roughness (σ) evolved from 13.7 Å (± 0.5 Å) to 19.5 Å (± 1.0 Å), giving a roughening rate of: dσ/dt = +6.3 × 10^− 5 Å s^− 1. This is consistent with other measurements made with free calcite surfaces and is driven almost entirely by chemical disequilibrium. Analysis of the surface ex situ post-reaction gives an identical σ value, showing that the in situ measurements are well-constrained. Experiments also at 30 bars but in a saturated solution indicate that the calcite surface does not significantly roughen, giving the result that pressure solution of calcite at this pressure cannot be monitored in experiments of several days duration. Experiments with halite, a much more reactive phase, in saturated solutions showed the reflectivity profile to be dynamic on a time scale of hours. This experiment was left to reach equilibrium over 108 days and then re-analyzed, showing that σ had increased from 34 Å (± 2 Å) to 41 Å (± 2 Å), giving a roughening rate of: dσ/dt ≤ +6.4 × 10^− 7 Å s^− 1. This is two orders of magnitude smaller than the calcite roughening rate caused by chemical disequilibrium and provides the first direct in situ atomic-scale measurement of the rate of surface roughening due to pressure solution.     

Spinel–sapphirine–quartz bearing composite inclusion within garnet from an ultrahigh-temperature pelitic granulite: Implications for metamorphic history and P–T path

We report here a multiphase mineral inclusion composed of quartz, plagioclase, K-feldspar, sapphirine, spinel, orthopyroxene, and biotite, in porphyroblastic garnet within a pelitic granulite from Rajapalaiyam in the Madurai Granulite Block, southern India. In this unique textural association, hitherto unreported in previous studies, sapphirine shows four occurrences: (1) as anhedral mineral between spinel and quartz (Spr-1), (2) subhedral to euhedral needles mantled by quartz (Spr-2), (3) subhedral to anhedral mineral in orthopyroxene, and (4) isolated inclusion with quartz (Spr-4). Spr-1, Spr-2, and Spr-4 show direct grain contact with quartz, providing evidence for ultrahigh-temperature (UHT) metamorphism at temperatures exceeding 1000 °C. Associated orthopyroxene shows high Mg/(Fe + Mg) ratio ( 0.75) and Al₂O₃ content (up to 9.6 wt.%), also suggesting T > 1050 °C and P > 10 kbar during peak metamorphism.

Coarse spinel (Spl-1) with irregular grain morphology and adjacent quartz grains are separated by thin films of Spr-1 and K-feldspar, suggesting that Spl-1 and quartz were in equilibrium before the stability of Spr-1 + quartz. This texture implies that the P–T conditions of the rock shifted from the stability field of spinel + quartz to sapphirine + quartz. Petrogenetic grid considerations based on available data from the FMAS system favour exhumation along a counterclockwise P–T trajectory. The irregular shape of the inclusion and chemistry of the inclusion minerals are markedly different from the matrix phases suggesting the possibility that the inclusion minerals could have equilibrated from cordierite-bearing silicate-melt pockets during the garnet growth at extreme UHT conditions.     

Role of electrochemical reactions in pressure solution

Using a Surface Forces Apparatus we have measured changes in the electrical potential difference between quartz and mica surfaces that correlate with the changing quartz dissolution rate when surfaces are pressed together at relatively low pressures (2-3 atm) in aqueous electrolyte solutions of 30 mM CaCl₂ at 25 °C. No detectable dissolution or voltage potential difference is measured in symmetrical systems (e.g. mica-mica or quartz-quartz) or between dry surfaces subjected to similar pressures, indicating that the dissolution can not be attributed to a simple pressure effect, slow aging (creep), or plastic deformation of the quartz surface. In quartz-mica systems brought together under pressure or to close proximity in electrolyte solution, the onset of quartz dissolution is marked by a sudden, rapid decrease in the quartz thickness at initial rates in the range from 1 to 4 nm/min, which after several hours settles into a constant rate of approximately 0.01 nm/min (∼5 μm/yr). Concomitantly, the potential drops to a constant value once the dissolution rate has stabilized. The decrease in the decay rate is interpreted as being due to saturation of the confined aqueous film and/or to the buildup of a Stern layer on the quartz surface, and the constant rate as being due to the steady-state chemical dissolution and diffusion of the dissolving silica into the surrounding reservoir. The dissolution is ‘non-uniform’: the surfaces become rough as dissolution proceeds, with the appearance of pits in a manner analogous to corrosion. On occasions, the process of rapid dissolution followed by a gradual transition to steady dissolution repeats itself, suggesting that the pit structure and Stern layer are fragile and subject to collapse and/or expulsion from the gap. Preliminary experiments on the dissolution of multi-faceted milled quartz particles (∼1.0 μm diameter) compressed between two muscovite surfaces suggest an asymmetry in the dissolution rates at different crystallographic planes. The origin of the electrical potential is interpreted as arising from the overlapping of the electric double-layers of two dissimilar surfaces when they are forced into close proximity. This electrical potential difference, for as yet unknown reasons, appears to be the driving force for the dissolution, rather than pressure.     

Identifying when microbes biosilicify: The interconnected requirements of acidic pH, colloidal SiO2 and exposed microbial surface

This study demonstrates discernible biosilicification of natural microbial mats through batch laboratory experiments. Identification of the geochemical requirements for this process to occur includes thermodynamically favorable, but sluggish silica reaction kinetics associated with acidic conditions, and the necessity for colloidal silica rather than dissolved silicic acid species. This study provides the first results to bridge the apparent literature discrepancy between widespread, in-situ observations of microbial silicification, and the inability to demonstrate a detectable microbial impact in this process under well-constrained laboratory conditions. We compared the silica scavenging abilities of three natural microbial mats collected from Yellowstone National Park (YNP) hotsprings, relative to those of both abiotic particle (TiO₂) and solution controls at constant, near-saturated aqueous silica concentrations, while experimental pH and temperature conditions were varied, using both dissolved and colloidal SiO₂ forms. We specifically evaluated three microbial mats sampled from YNP sites all exhibiting saturation with respect to amorphous SiO₂, but possessing variable pH and temperature conditions that should reflect differential kinetics (and therefore biological opportunity) relative to silica polymerization: (1) most biologically favorable, acidic-mesophile (AM: pH 3, T = 35 °C); (2) biologically possible, but less opportune, alkaline, mesophile (ALK-M: pH 8, T = 35 °C) and (3) unlikely to be biologically favorable, alkaline-thermophile (ALK-T: pH 8, T = 80 °C). Comparison of field and laboratory results substantiates the requirements for thermodynamically favorable, but kinetically slower SiO₂ polymerization conditions. Results show that acidic moderate temperature conditions were required for an observable biosilicification impact. Moreover, they also identified for the first time, the necessity specifically for colloidal silica forms which are surface bound under acidic pH conditions, to distinguish discernible biosilicification compared to mineral particle controls. Results also highlight the important influence of mat surface characteristics in this process, specifically the extent of live, non-mineralized, exposed biological mat surface. Greater colloidal SiO₂ scavenging abilities are associated with non-mineralized microbial mat surfaces than with mineral particle surfaces or microbial mat surfaces encrusted with authigenic silica. These results are the first to demonstrate that biosilicification can be a microbially mediated, discernible geobiological process, shedding new light on the longstanding argument in the literature, and opening the door for more sensitive evaluation of this phenomenon in natural systems.     

Pressure solution in sandstones: influence of clays and dependence on temperature and stress

The enhancement of dissolution of quartz under the influence of clays has been recognized in sandstones for many years. It is well known that a grain of quartz in contact with a clay flake dissolves faster than when in contact with another grain of quartz. This phenomenon promotes silica transfer during the diagenesis of sandstones and is responsible of deformation and porosity variations. Here we make an attempt to explain the process of this rock deformation using a pressure solution mechanism.

The model of water film diffusion assumes that matter is dissolved inside the contact between two grains. The resulting solutes are transported to the pore fluid through diffusion along an adsorbed water film. Between two micas, this trapped film is thicker than between two grains of quartz. As a consequence diffusion is easier and the rate of pressure solution faster.

Experiments on pressure solution show that diffusion controls the mechanism at great depth whereas a model based on natural mica indentation indicates that kinetics is the limiting process through the precipitation rate of quartz at low depth, thus temperature is a crucial parameter. There should be a transition between thermally controlled rate and diffusion limited evolution.     

Forces and ionic transport between mica surfaces: implications for pressure solution

Using a surface forces apparatus (SFA), we have studied the interactions between mica surfaces in pure and mixed NaCl and CaCl₂ solutions at relevant geological conditions of pressure and electrolyte composition. Our results show that the short-range (0-50 Å) colloidal forces, including attractive van der Waals and ion-correlation forces, repulsive electrostatic forces, and oscillatory or monotonically repulsive hydration (surface-induced water structure-dependent) forces are involved in different stages of pressure solution. These forces depend on the type (Na⁺, Ca²⁺, and H⁺) and concentration (6-600 mM) of the cations present in the solution. Equilibrium water film thicknesses were measured as a function of the applied (normal) pressure up to 50 MPa (500 atm) and ranged from 30 to 0 Å at pressures above 10 MPa (100 atm). Measurements were also made of the rates of diffusion and exchange of ions into and out of such ultrathin films, and on the nucleation and growth of ionic crystallites on and between the surfaces, which occurred only in the presence of calcium ions. Diffusion of ions into and out of structured water films as thin as one to five water molecules (3 to 15 Å) were found to be surprisingly rapid and never less than two orders of magnitude below the diffusion in bulk water. In contrast, the rates of binding and exchange of ions to the surfaces were found to be the rate-limiting steps to adsorption and crystal formation. These findings imply that, for certain systems or conditions, pressure solution rates could be limited by surface reactions rather than by ion diffusion in thin fluid films.     

Ultra high temperature-metamorphism and its significance in the Central Indian Tectonic Zone

In the present study from the southern margin of the Central Indian Tectonic Zone, it is demonstrated how the metamorphic P–T path of ultrahigh-temperature granulite terranes can be reconstructed using the metamorphic transition in corundum granulites from early biotite melting to later FMAS solid–solid reaction. The extreme metamorphism in these rocks caused two-stage biotite melting, resulting in initial porphyroblastic garnet₁ and later sapphirine–spinel₁ incongruent solid mineral assemblages. During this process, the leucocratic and melanocratic layers in the corundum granulites evolved from an initial silica-oversaturated to a later silica-undersaturated domain. In the melanocratic layer, this allowed localized concentration of sapphirine-spinel₁ and residual sillimanite₁, producing an extremely restitic assemblage, at the culmination of peak metamorphism, BM₁. BM₁ is constrained at  1000 °C at relatively deep crustal levels (P  9 kbar) from the stability of ferroaugite in a co-metamorphosed Iron Formation granulite. During subsequent metamorphism (BM₂), the reaction path and history in the corundum granulites shifted to the restitic domain allowing reacting sapphirine, spinel₁ and sillimanite to produce coronal garnet₂–corundum assemblage via a FMAS univariant reaction. In the final stages of reaction history, biotite₂–sillimanite₂–spinel₂ assemblage was produced after garnet₂–corundum due to localized melt–crystal interaction. The metamorphic sequence, when interpreted with the help of a newly constructed, qualitative KFMASH petrogenetic grid, reveals successive stages of heating, increasing pressure and cooling around the KFMASH invariant point, [Opx,Crd], which is consistent with a counterclockwise metamorphic P–T path. The near isobaric nature of post-peak cooling (ΔT  250–300 °C) is also evident from multistage pyroxene exsolution and by the appearance of lamellar and coronal garnets in the Iron Formation granulites. This study provides the first tight constraint for ultrahigh-T metamorphism along a counter clockwise P–T trajectory in the Central Indian Tectonic zone, and has important bearing for terrane correlations in this part of East Gondwanaland. In addition, the new KFMASH grid allows evaluation of metamorphic phase relations in ultrahigh-T, corundum-bearing and corundum-absent aluminous granulites.     

Making diagenesis obey thermodynamics and kinetics: the case of quartz cementation in sandstones from offshore mid-Norway

Calculation of the quantity and distribution of quartz cement as a function of time and temperature/depth in quartzose sandstones is performed using a coupled dissolution/diffusional–transport/precipitation model. This model is based on the assumptions that the source of the silica cement is quartz surfaces adjoining mica and/or clay grains at stylolite interfaces within the sandstones, and the quantity of silica transport into and out of the sandstone by advecting fluids is negligible. Integration of the coupled mass transfer/transport equations over geologically relevant time frames is performed using the quasi-stationary state approximation. Results of calculations performed using quartz dissolution rate constants and aqueous diffusion coefficients generated from laboratory data, are in close agreement with both the overall porosity and the distribution of quartz cement in the Middle Jurassic Garn Formation only after optimizing the product of the effective surface area and quartz precipitation rate constants with the field data. When quartz precipitation rate constants are fixed to equal corresponding dissolution rate constants, the effective surface area required to match field data depends on the choice of laboratory generated quartz rate constant algorithm and ranges from 0.008 cm⁻¹ to 0.34 cm⁻¹. In either case, these reactive surface areas are ∼2 to 4 orders of magnitude lower than that computed using geometric models.     

Coesite inclusions and prograde compositional zonation of garnet in whiteschist of the HP-UHPM Kokchetav massif, Kazakhstan: a record of progressive UHP metamorphism

Coarse-grained whiteschist, containing the assemblage: garnet+kyanite+phengite+talc+quartz/coesite, is an abundant constituent of the ultrahigh-pressure metamorphic (UHPM) belt in the Kulet region of the Kokchetav massif of Kazakhstan.

Garnet displays prograde compositional zonation, with decreasing spessartine and increasing pyrope components, from core to rim. Cores were recrystallized at T=380°C (inner) to 580°C (outer) at P<10 kbar (garnet–ilmenite geothermometry, margarite+quartz stability), and mantles at T=720–760°C and P_H20=34–36 kbar (coesite+graphite stability, phengite geobarometer, KFMASH system reaction equilibria). Textural evidence indicates that rims grew during decompression and cooling, within the Qtz-stability field.

Silica inclusions (quartz and/or coesite) of various textural types within garnets display a systematic zonal distribution. Cores contain abundant inclusions of euhedral quartz (type 1 inclusions). Inner mantle regions contain inclusions of polycrystalline quartz pseudomorphs after coesite (type 2), with minute dusty micro-inclusions of chlorite, and more rarely, talc and kyanite in their cores; intense radial and concentric fractures are well developed in the garnet. Intermediate mantle regions contain bimineralic inclusions with coesite cores and palisade quartz rims (type 3), which are also surrounded by radial fractures. Subhedral inclusions of pure coesite without quartz overgrowths or radial fractures (type 4) occur in the outer part of the mantle. Garnet rims are silica-inclusion-free.

Type 1 inclusions in garnet cores represent the low-P, low-T precursor stage to UHPM recrystallization, and attest to the persistence of low-P assemblages in the coesite-stability field. Coesites in inclusion types 2, 3, and 4 are interpreted to have sequentially crystallized by net transfer reaction (kyanite+talc=garnet+coesite+H₂O), and were sequestered within the garnet with progressively decreasing amounts of intragranular aqueous fluid.

During the retrograde evolution of the rock, all three inclusion types diverged from the host garnet P–T path at the coesite–quartz equilibrium, and followed a trajectory parallel to the equilibrium boundary resulting in inclusion overpressure. Coesite in type 2 inclusions suffered rapid intragranular H₂O-catalysed transformation to quartz, and ruptured the host garnet at about 600°C (when inclusion P27 kbar, garnet host P9 kbar). Instantaneous decompression to the host garnet P–T path, passed through the kyanite+talc=chlorite+quartz reaction equilibrium, resulting in the dusty micro-assemblage in inclusion cores. Type 3 inclusions suffered a lower volumetric proportion transformation to quartz at the coesite–quartz equilibrium, and finally underwent rupture and decompression when T<400°C, facilitating coesite preservation. Type 4 coesite inclusions are interpreted to have suffered minimal transformation to quartz and proceeded to surface temperature conditions along or near the coesite–quartz equilibrium boundary.     

Multisite surface reaction versus transport control during the hydrolysis of a complex oxide

Dissolution experiments of a tholeiite basalt glass carried out at different pH and T (up to 300°C) using a rotatingdisc apparatus show that, depending on pH and T, dissolution can be controlled by one of the following steps: (1) surface reaction; (2) transport of reactants in solution; and (3) mixed reaction. The activation energies of these different processes were found to be 60, 9 and 15–50 kJ mol⁻¹, respectively. Taking account of these results, it appears likely that surface reactions are not rate limiting for the hydrolysis of most crystalline silicate minerals in hydrothermal and metamorphic processes, and that caution should be exercised when predicting rate of reactions at high temperatures solely on the basis of activation energies measured at low temperatures.

Comparison of experimental and theoretical potentiometric titrations of the basalt glass and its constituent oxides indicates that the adsorption of H⁺ and OH⁻ ions at the basalt surface is metal cation specific and that the net adsorption can be predicted from the sole knowledge of the acidity constants of the network-forming constituent oxides. We found that in the acidic pH region dissolution is promoted by the adsorption of H⁺ on al and Fe surface sites while in the basic region, dissolution is promoted by the adsorption of OH⁻ on Si sites. The combination of the two distinct types of surface sites, Al and Fe on the one hand, and Si on the other hand, results in a dissolution rate minimum at a pH-value between the pH_zpc of the two groups of oxide components. Linear regressions with a slope n=3.8 are observed both in acid and alkaline solutions in logarithmic plots of the rate of dissolution vs. the surface charge. The value of n, which represents the number of protonation or hydroxylation steps prior to metal detachment, has been found equal to the mean valence of the network-forming metals.

Combining concepts of surface coordination chemistry with transition state theory afforded characterisation of the activated complexes involved in basalt dissolution processes. From the values obtained for the thermodynamic properties of activation for basalt dissolution it is assumed that the activated complexes formed during the H₂O-promoted dissolution of the basalt glass are more tightly bonded than those formed during H⁺- or OH⁻-promoted dissolution.     

The geochemical cycle of boron: Constraints from boron isotope partitioning experiments between mica and fluid

The fractionation of boron isotopes between synthetic boromuscovite and fluid was experimentally determined at 3.0 GPa/500 °C and 3.0 GPa/700 °C. For near-neutral fluids Δ¹¹B_(mica-fluid) = δ¹¹B_(mica) − δ¹¹B_(fluid) is − 10.9 ± 1.3‰ at 500 °C, and − 6.5 ± 0.4‰ at 700 °C. This supports earlier assumptions that the main fractionation effect is due to the change from trigonal coordination of boron in neutral fluids to tetrahedrally coordinated boron in micas, clays and melts. The T-dependence of this effect is approximated by the equation Δ¹¹B_{(mica,clay,melt–neutral fluid)} = − 10.69 · (1000/T [K]) + 3.88; R² = 0.992, valid from 25 °C for fluid–clay up to about 1000 °C for fluid–silicate melt. Experiments at 0.4 GPa that used strongly basic fluids produced significantly lower fractionations with Δ¹¹B_{(mica–fluid)} of − 7.4 ± 1.0‰ at 400 °C, and − 4.8 ± 1.0‰ at 500 °C, showing the reduced fractionation effect when large amounts of boron in basic fluids are tetrahedrally coordinated. Field studies have shown that boron concentrations and ¹¹B/¹⁰B-ratios in volcanic arcs systematically decrease across the arc with increasing distance from the trench, thus reflecting the thermal structure of the subducting slab. Our experiments show that the boron isotopic signature in volcanic arcs probably results from continuous dehydration of micas along a distinct P–T range. Continuous slab dehydration and boron transport via fluid into the mantle wedge is responsible for the boron isotopic signature in volcanic arcs.     

Intermediate high-pressure exhumation of the northern segment of the Sanbagawa belt, Saruta-gawa area, central Shikoku, Japan

The retrograde chemical zonal structure of amphibole in hematite-bearing basic and quartz schists from the higher grade zone in the Saruta-gawa area of the Sanbagawa belt was studied to investigate the relationships between the prograde and retrograde P–T paths of the Sanbagawa metamorphism. This amphibole coexists with chlorite, epidote, muscovite, albite, quartz and hematite, and is composed of Al-rich core and Al-poor mantle. The core is fairly homogeneous and has a barroisitic composition. In the mantle part, ^[B]Na increases with decreasing ^[4]Al towards the margins, which have winchite–magnesioriebeckite compositions. The barroisite–winchite–magnesioriebeckite composite crystal is sometimes rimmed by actinolite and/or winchite with low ^[4]Al and ^[B]Na. The Al-rich core and Al-poor mantle are regarded as prograde and retrograde products, respectively. The retrograde mantle in the Saruta-gawa area: (1) is systematically richer in ^[B]Na [0.40–1.73 per formula unit (pfu; for O=23)] than that from the same grade zone in the Asemi-gawa area (0.19–0.78 pfu), about 8 km south of the studied area; (2) tends to be ^[B]Na-poorer (less than 1.73 pfu) than prograde sodic amphibole (up to 1.93 ^[B]Na pfu) produced in the peak temperature stage from the lower grade zone in the same and other areas; and (3) extends its compositional range towards higher ^[B]Na and lower ^[4]Al than prograde-formed amphibole from the same grade zone in the same area. These zonal characteristics imply that (1) the Saruta-gawa samples experienced retrograde metamorphism under higher P/T conditions than the Asemi-gawa samples, (2) the retrograde P–T path of the Saruta-gawa area passes on the lower pressure side of the metamorphic field gradient, and (3) the Saruta-gawa samples underwent retrograde metamorphism under higher P/T conditions than the prograde metamorphism. The higher P/T conditions of the retrograde metamorphism suggests an increasing dP/dT of the geotherm during exhumation. Retrograde P–T conditions during the formation of magnesioriebeckite can be roughly estimated at 7–8 kbar, 400–450°C based on semi-quantitative phase relations of actinolite–winchite–magnesioriebeckite–barroisite series associated with chlorite, epidote, muscovite, albite, quartz and hematite.     

The preservation of high-pressure rocks during exhumation: metagranites and metapelites

Metagranites in the NKFMASH system require external hydration during prograde high-pressure metamorphism in order to equilibrate to ambient HP conditions by producing more siliceous muscovite. Any lack of external fluid or the disappearance of biotite stops re-equilibration and thus prevents recording of high-pressure conditions. The same hydration reactions cause dehydration during exhumation. Orthogneiss from shear zones or adjacent to metapelites and metabasites will take up external fluid during subduction and record the highest P–T conditions, but will also be the first to dehydrate upon exhumation, now hydrating other lithologies and probably refuelling shearzones.

The (de)hydration behavior of Ca-bearing metagranitoids is similar to that in the Ca-free system. However, the anorthite component of plagioclase decomposes with increasing pressure to form either (clino)zoisite or a grossular-rich garnet. Both reactions are fluid-consuming. If H₂O is supplied from an external source, the garnet-bearing assemblage can record P–T conditions up to very high pressures, but dehydrates again during heating and/or decompression to form a more Fe-rich garnet and Al-rich mica(s). The garnet compositions observed in natural HP-metagranites are mostly too Fe-rich to be formed in the presence of an H₂O-rich fluid.

N(C)KFMASH metapelites generally have a more complex mineralogy and succession of mineral assemblages along a P–T path. The H₂O contained in hydrous silicates like chlorite and chloritoid is only partly released, but partly transferred to other minerals like paragonite, glaucophane or phengite during subduction and further dehydration during exhumation is common. The mineral assemblage preserved by the rock may then record P–T conditions way below those of the actual pressure and temperature peak of the path. Contouring of the P–T pseudosection of a specific metapelite composition with mode isopleths for H₂O shows which P–T conditions along a given path are the ones most likely recorded by the rock.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

P–T paths reconstruction of a collisional event: The example of the Thiviers-Payzac Unit in the Variscan French Massif Central

Because of late metamorphic and tectonic overprints, the reconstruction of prograde parts of P–T paths is often difficult. In the SW Variscan French Massif Central, the Thiviers-Payzac Unit (TPU) is the uppermost allochthon emplaced above underlying units. The TPU experienced a Barrovian metamorphism coeval with a top-to-the-NW ductile shearing (D2 event) in Early Carboniferous times (ca. 360–350 Ma). The tectonic setting of the D2 event, compression or synconvergence extension, remains unclear. Using the THERMOCALC software and the model system MnNCKFMASH, the peak P–T conditions are estimated from garnet rims and matrix minerals and the prograde evolution is deduced from garnet core compositions. The combination of these two approaches demonstrates that the TPU experienced pressure and temperature increases before reaching peak conditions at 6.6–9.0 +/− 1.2 kbar and 615–655 +/− 35 °C. This kind of P–T path shows that the regional D2 event corresponds to crustal thickening.     

The effect of Fe-oxidizing bacteria on Fe-silicate mineral dissolution

Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe²⁺ present in natural acid solutions and also may be able to utilize Fe²⁺ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe³⁺ from the available Fe in solution in microbial experiments (compared to no production of Fe³⁺ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.

Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe²⁺, Mg²⁺ and Fe³⁺ on fayalite dissolution. Neither Fe²⁺ nor Mg²⁺ had an effect on the dissolution reaction. However, Fe³⁺, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe³⁺ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe³⁺ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment.     

Dissolution rates of minerals and their relation to surface morphology

Experimentally observed dissolution rates of minerals in an aqueous solution are determined by surface reaction rates, mass transport by molecular diffusion through a diffusion boundary layer (DBL) and the morphology of the mineral’s surface. By solving the transport equation in the presence of a diffusion boundary layer for surfaces containing open pores their contribution to the observed dissolution rates can be quantified. Furthermore dissolution rates are calculated for fractal surfaces. A general solution is given. Two extremes are discussed. If the surface controlled rate constant k is small compared to the mass transport constant k_t = D/ε (ε thickness of DBL, D coefficient of diffusion), the rates are surface controlled and the entire surface contributes to the observed dissolution rate. In this case rates must be normalized to the B.E.T.-surface area. When k ? k_t the observed rates are limited by diffusion and information on k cannot be obtained. In intermediate cases a careful analysis is required. If ink bottle pores are present their contribution to the observed rates can be neglected and rates must be normalized to the geometrical envelope surface area, although in such cases the B.E.T.-surface area can be much larger.     

Coupled micro-faulting and pressure solution creep overprinted on quartz schist deformed by intracrystalline plasticity during exhumation of the Sambagawa metamorphic rocks,southwest Japan

In the Sambagawa schist, southwest Japan, while ductile deformation pervasively occurred at D₁ phase during exhumation, low-angle normal faulting was locally intensive at D₂ phase under the conditions of frictional–viscous transition of quartz (c. 300 °C) during further exhumation into the upper crustal level. Accordingly, the formation of D₂ shear bands was overprinted on type I crossed girdle quartz c-axis fabrics and microstructures formed by intracrystalline plasticity at D₁ phase in some quartz schists. The quartz c-axis fabrics became weak and finally random with increasing shear, accompanied by the decreasing degree of undulation of recrystallized quartz grain boundaries, which resulted from the increasing portion of straight grain boundaries coinciding with the interfaces between newly precipitated quartz and mica. We interpreted these facts as caused by increasing activity of pressure solution: the quartz grains were dissolved mostly at platy quartz–mica interface, and precipitated with random orientation and pinned by mica, thus having led to the obliteration of existing quartz c-axis fabrics. In the sheared quartz schist, the strength became reduced by the enhanced pressure solution creep not only due to the reduction of diffusion path length caused by increasing number of shear bands, but also to enhanced dissolution at the interphase boundaries.     

Evolution of fluids associated with metasedimentary sequences from Chaves (North Portugal)

In order to identify and characterise fluids associated with metamorphic rocks from the Chaves region (North Portugal), fluid inclusions were studied in quartz veinlets, concordant with the main foliation, in graphitic-rich and nongraphitic-rich lithologies from areas with distinct metamorphic grade. The study indicates multiple fluid circulation events with a variety of compositions, broadly within the C–H–O–N–salt system. Primary fluid inclusions in quartz contain low salinity aqueous–carbonic, H₂O–CH₄–N₂–NaCl fluids that were trapped near the peak of regional metamorphism, which occurred during or immediately after D2. The calculated P–T conditions for the western area of Chaves (CW) is P=300–350 MPa and T500 °C, and for the eastern area (CE), P=200–250 MPa and T=400–450 °C. A first generation of secondary fluid inclusions is restricted to discrete cracks at the grain boundaries of quartz and consists of low salinity aqueous–carbonic, H₂O–CO₂–CH₄–N₂–NaCl fluids. P–T conditions from the fluid inclusions indicate that they were trapped during a thermal event, probably related with the emplacement of the two-mica granites.

A second generation of secondary inclusions occurs in intergranular fractures and is characterised by two types of aqueous inclusions. One type is a low salinity, H₂O–NaCl fluid and the second consists of a high salinity, H₂O–NaCl–CaCl₂ fluid. These fluid inclusions are not related to the metamorphic process and have been trapped after D3 at relatively low P (hydrostatic)–T conditions (P<100 MPa and T<300 °C).

Both the early H₂O–CH₄–N₂–NaCl fluids in quartz from the graphitic-rich lithologies and the later H₂O–CO₂–CH₄–N₂–NaCl carbonic fluid in quartz from graphitic-rich and nongraphitic-rich lithologies seem to have a common origin and evolution. They have low salinity, probably resulting from connate waters that were diluted by the water released from mineral dehydration during metamorphism. Their main component is water, but the early H₂O–CH₄–N₂–NaCl fluids are enriched in CH₄ due to interaction with the C-rich host rocks.

From the early H₂O–CH₄–N₂–NaCl to the later aqueous–carbonic H₂O–CO₂–CH₄–N₂–NaCl fluids, there is an enrichment in CO₂ that is more significant for the fluids associated with nongraphitic-rich lithologies.

The aqueous–carbonic fluids, enriched in H₂O and CH₄, are primarily associated with graphitic-rich lithologies. However, the aqueous–carbonic CO₂-rich fluids were found in both graphitic and nongraphitic-rich units from both the CW and CE studied areas, which are of medium and low metamorphic grade, respectively.     

Pressure solution - The importance of the electrochemical surface potentials

“Pressure solution”, frequently found in clay-rich sandstone, is characterized by enhanced quartz dissolution at inter-grain contacts. The origin of pressure solution and many other related dissolution processes remains elusive. Using an Electrochemical Surface Forces Apparatus we visualized and measured the dissolution of silica glass surfaces close to an electrode surface. The dissolution rates correlate quantitatively with the electrode potential via the Butler-Volmer equation for corrosion. Our experimental results demonstrate that at low temperature, apparent pressure solution and many other mineral dissolution phenomena can be driven by electrochemical processes rather than a pressure-driven process. This finding highlights the role of electrochemical surface potentials in dissolution phenomena at dissimilar material interfaces, and provides new perspectives on pressure solution in particular and a new theoretical basis for predictive control of dissolution phenomena in general.