Structure and properties of loaded silica contacts during pressure solution: impedance spectroscopy measurements under hydrothermal conditions

In order to investigate directly the structure and properties of grain boundaries in silicate materials undergoing pressure solution, in situ measurements of these properties are required. We report electrical impedance spectroscopy measurements, performed, under hydrothermal conditions, on individual glass–glass and glass-quartz contacts undergoing pressure solution. Resulting estimates of the average grain boundary diffusivity product ( Z = Dd_\textav C^* Z = D\delta_{\text{av}} C^{*} ) for silica transport and of the average grain boundary fluid film thickness ( d_\textav \delta_{\text{av}} ) fall in the ranges 6.3 ± 1.4 × 10⁻¹⁸ m³ s⁻¹ and 350 ± 210 nm, respectively. However, the average values for Z and d_\textav \delta_{\text{av}} obtained were likely influenced by cracking and irregular dissolution of the dissolving contact surfaces, rather than representing uniformly wetted grain boundary properties. Post-mortem SEM observations indicate that the contact surfaces were internally rough. Taken together, our data support the notion that during pressure solution of quartz, grain boundary diffusion is rapid, and interface processes (dissolution and precipitation) are more likely to be rate-limiting than diffusion.     

Hydrogen diffusion in spinel grain boundaries and consequences for chemical homogenization in hydrous peridotite

Hydrogen can be stored in the structure of nominally anhydrous minerals as point defects, and these impurities substantially modify many physical properties of Earth’s mantle minerals. However, mantle rocks are composed of mineral grains separated by grain boundaries and interphase grains boundaries. Therefore, as a potential hydrogen reservoir, grain boundaries should be given proper attention. Here, I report an experimental investigation into hydrogen diffusion through grain boundaries in polycrystalline aggregates. Sintering and diffusion experiments were performed using a gas-medium high-pressure vessel at under pressure of 300 MPa and over a temperature range of 900–1,250°C. The diffusion assembly consisted of a polycrystalline cylinder of aluminous spinel + olivine crystals with a talc cylinder as the main hydrogen source. A Ni capsule was used to buffer the oxygen fugacity at Ni–NiO. Experimental durations varied from 5 min to 5 h. The presence of hydrogen in the crystals was measured by Fourier-transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the characteristic distance. The absence or presence of hydrogen recorded by the ‘hydrogen sensor’ olivines embedded in the aggregate allows the estimation of bounds on this characteristic distance. Results presented here suggest that hydrogen effective diffusion coefficients are only one order of magnitude faster (~10⁻⁹ m²s⁻¹ at 1,000°C) than in an olivine single crystal along the [100] axis. Resulting diffusion coefficients for hydrogen in grain boundary are four orders of magnitude faster than in a single crystal, but this diffusivity is not fast enough to affect hydrogen mobility in mantle rocks with grain sizes greater than ~1 mm. Thus, very limited chemical homogenization would occur using grain boundaries diffusion in mantle hydrous peridotite for incompatible and volatile element, such as hydrogen.     

Diffusion-controlled growth of albite and pyroxene reaction rims

The growth rates of albite and pyroxene (enstatite + diopside + spinel) reaction rims were measured at 1000°C and ˜700 MPa and found to be parabolic indicating diffusion-controlled growth. The parabolic rate constants for the pyroxene (+ spinel) rims in samples with 0.5 wt% H₂O added or initially vacuum dried at 25°C and 250°C are 1.68 ± 0.09, 0.54 ± 0.05 and 0.25 ± 0.06 μm²/h, respectively. The values for albite rim growth in samples initially dried at 60°C and with 0.1 wt% H₂O added are 0.25 ± 0.04 and 0.33 ± 0.03 μm²/h, respectively. The latter values were used to derive the product of the grain boundary diffusion coefficient D′_A, where A = SiO₂, NaAlO₂, or NaAlSi₋₁, and the grain boundary thickness δ in albite. The calculated D′_SIO2δ in the albite aggregate for the situations of two different water contents are about 9.9 × 10⁻²³ and 1.4 × 10⁻²² m³ s⁻¹, respectively. Both the rate constants and the calculated D′_Aδ demonstrate that the effect of water content on the grain boundary diffusion rate in monomineralic albite and polymineralic pyroxene (+ spinel) aggregates is small, consistent with recent studies of monomineralic enstatite and forsterite rims. Received: 1 July 1995 / Accepted: 1 August 1996     

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

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

Metamorphic fluid origins in the Osborne Fe oxide–Cu–Au deposit,Australia: evidence from noble gases and halogens

The Osborne iron oxide–copper–gold (IOCG) deposit is hosted by amphibolite facies metasedimentary rocks and associated with pegmatite sheets formed by anatexis during peak metamorphism. Eleven samples of ore-related hydrothermal quartz and two pegmatitic quartz–feldspar samples contain similarly complex fluid inclusion assemblages that include variably saline (<12–65 wt% salts) aqueous and liquid carbon dioxide varieties that are typical of IOCG mineralisation. The diverse fluid inclusion types present in each of these different samples have been investigated by neutron-activated noble gas analysis using a combination of semi-selective thermal and mechanical decrepitation techniques. Ore-related quartz contains aqueous and carbonic fluid inclusions that have similar ⁴⁰Ar/³⁶Ar values of between 300 and 2,200. The highest-salinity fluid inclusions (47–65 wt% salts) have calculated ³⁶Ar concentrations of approximately 1–5 ppb, which are more variable than air-saturated water (ASW = 1.3–2.7 ppb). These fluid inclusions have extremely variable Br/Cl values of between 3.8 × 10⁻³ and 0.3 × 10⁻³, and I/Cl values of between 27 × 10⁻⁶ and 2.4 × 10⁻⁶ (all ratios are molar). Fluid inclusions in the two pegmatite samples have similar ⁴⁰Ar/³⁶Ar values of ≤1,700 and an overlapping range of Br/Cl and I/Cl values. High-salinity fluid inclusions in the pegmatite samples have 2.5–21 ppb ³⁶Ar, that overlap the range determined for ore-related samples in only one case. The fluid inclusions in both sample groups have ⁸⁴Kr/³⁶Ar and ¹²⁹Xe/³⁶Ar ratios that are mainly in the range of air and air-saturated water and are similar to mid-crustal rocks and fluids from other settings. The uniformly low ⁴⁰Ar/³⁶Ar values (<2,200) and extremely variable Br/Cl and I/Cl values do not favour a singular or dominant fluid origin from basement- or mantle-derived magmatic fluids related to A-type magmatism. Instead, the data are compatible with the involvement of metamorphic fluids that have interacted with anatectic melts to variable extents. The ‘metamorphic’ fluids probably represent a mixture of (1) inherited sedimentary pore fluids and (2) locally derived metamorphic volatilisation products. The lowest Br/Cl and I/Cl values and the ultra-high salinities are most easily explained by the dissolution of evaporites. The data demonstrate that externally derived magmatic fluids are not a ubiquitous component of IOCG ore-forming systems, but are compatible with models in which IOCG mineralisation is localised at sites of mixing between fluids of different origin. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorised users.     

Grain growth kinetics of dolomite,magnesite and calcite: a comparative study

The rates of grain growth of stoichiometric dolomite [CaMg(CO₃)₂] and magnesite (MgCO₃) have been measured at temperatures T of 700–800°C at a confining pressure P _c of 300 MPa, and compared with growth rates of calcite (CaCO₃). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO₃)₂, MgCO₃, and CaCO₃, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO₃)₂, MgCO₃, and CaCO₃, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10⁻⁵ μm³/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.     

The fidelity of melt inclusions as records of melt composition

A series of experiments created melt inclusions in plagioclase and pyroxene crystals grown from a basaltic melt at 1,150°C, 1.0 GPa to investigate diffusive fractionation during melt inclusion formation; additionally, P diffusion in a basaltic melt was measured at 1.0 GPa. Melt inclusions and melts within a few 100 microns of plagioclase–melt interfaces were analyzed for comparison with melt compositions far from the crystals. Melt inclusions and melt compositions in the boundary layer close to the crystal–melt interface were similar, but both differ significantly in incompatible element concentrations from melt found greater than approximately 200 microns away from the crystals. The compositional profiles of S, Cl, P, Fe, and Al in the boundary layers were successfully reproduced by a two-step model of rapid crystal growth followed by diffusive relaxation toward equilibrium after termination of crystal growth. Applying this model to investigate possible incompatible element enrichment in natural melt inclusions demonstrated that at growth rates high enough to create the conditions for melt inclusion formation, ∼10⁻⁹–10⁻⁸ m s⁻¹, the concentration of water in the boundary layer near the crystal was similar to that of the bulk melt because of its high diffusion coefficient, but sulfur, with a diffusivity similar to major elements and CO₂, was somewhat enriched in the boundary layer melt, and phosphorus, with its low diffusion coefficient similar to other high-field strength elements and rare earth elements, was significantly enriched. Thus, the concentrations of sulfur and phosphorus in melt inclusions may over-estimate their values in the bulk melt, and other elements with similar diffusion coefficients may also be enriched in melt inclusions relative to the bulk melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Excess heat capacity and entropy of mixing along the chlorapatite–fluorapatite binary join

The heat capacity at constant pressure, C _p, of chlorapatite [Ca₅(PO₄)₃Cl – ClAp], and fluorapatite [Ca₅(PO₄)₃F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca₃(PO₄)₂ using the CaF₂–CaCl₂ flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C _p^ClAp = 613.21 − 2,313.90T ^−0.5 − 1.87964 × 10⁷ T ⁻² + 2.79925 × 10⁹ T ⁻³ and C _p^FAp = 681.24 − 4,621.73 × T ^−0.5 − 6.38134 × 10⁶ T ⁻² + 7.38088 × 10⁸ T ⁻³ (units, J mol⁻¹ K⁻¹). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol⁻¹ K⁻¹ for chlorapatite and S° = 383.2 ± 1.5 J mol⁻¹ K⁻¹ for fluorapatite. Positive excess heat capacities of mixing, ΔC _p^ex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol⁻¹ K⁻¹ for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS ^ex, at 298 K reaches positive values of 3–4 J mol⁻¹ K⁻¹ in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty.     

Fluid Inclusion Studies of Gold Deposits in the Gezhen Shear Zone,Hainan Province,China

The Tuwaishan, Baoban, Erjia, Bumo and other gold deposits in western Hainan occur in Precambrian metamorphic clastic rocks and are structurally controlled by the Gezhen shear zone. Fluid inclusion studies have been carried out of the gold deposits mentioned above. The homogenization temperatures of the whole fluid inclusion population range from 140°C to 370°C, indicating that gold was precipitated mainly at 240–250°C. The salinities are within the range of 2.0–9.2 wt% NaCl equiv. and the pressure of formation of the deposits was estimated at about 270×10⁵−500×10⁵Pa, corresponding to a depth of about 1.1–2.0 km under lithostatic confinement. Chemical studies show that the ore fluid is of the Na⁺(K⁺)-Ca²⁺-Cl⁻(F⁻) type. Theδ ¹⁸O andδD values of the fluid vary from −2.7‰- +4.4‰ and −50‰–−87‰ Evidence developed from fluid inclusions and geological setting indicates that the ore fluid was a mixture of magmatic and meteoric-hydrothermal waters. Changes in chemical composition andδ ¹⁸O andδD of fluid inclusions from one ore field to another seem to be related with regional tectonism, metamorphism and magmatism.     

Origin of the Zálesí U–Ni–Co–As–Ag/Bi deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Zálesí vein-type deposit is hosted by Early Paleozoic high-grade metamorphic rocks on the northern margin of the Bohemian Massif. The mineralization is composed of three main stages: uraninite, arsenide, and sulfide. The mineral assemblages formed at low temperatures (~80 to 130°C, locally even lower) and low pressures (<100 bars). The salinity of the aqueous hydrothermal fluids (0 to 27 wt.% salts) and their chemical composition vary significantly. Early fluids of the oldest uraninite stage contain a small admixture of a clathrate-forming gas, possibly CO₂. Salinity correlates with oxygen isotope signature of the fluid and suggests mixing of brines [δ ¹⁸O around +2‰ relative to standard mean ocean water (SMOW)] with meteoric waters (δ ¹⁸O around −4‰ SMOW). The fluid is characterized by highly variable halogen ratios (molar Br/Cl = 0.8 × 10⁻³ to 5.3 × 10⁻³; molar I/Cl = 5.7 × 10⁻⁶ to 891 × 10⁻⁶) indicating a dominantly external origin for the brines, i.e., from evaporated seawater, which mixed with iodine-enriched halite dissolution brine. The cationic composition of these fluids indicates extensive interaction of the initial brines with their country rocks, likely associated with leaching of sulfur, carbon, and metals. The brines possibly originated from Permian–Triassic evaporites in the neighboring Polish Basin, infiltrated into the basement during post-Variscan extension and were finally expelled along faults giving rise to the vein-type mineralization. Cenozoic reactivation by low-salinity, low-δ ¹⁸O (around −10‰ SMOW) fluids of mainly meteoric origin resulted in partial replacement of primary uraninite by coffinite-like mineral aggregates.     

Low T heat capacity measurements and new entropy data for titanite (sphene): implications for thermobarometry of high-pressure rocks

The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2 ± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation of state: V _P,T  = V ₂₉₈° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K ₂₉₈ × (1 – 1.5 × 10⁻⁴ [T − 298]) + 4P)]^1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V ₂₉₈° = 5.568 J/bar, a° = 3.1 × 10⁻⁵ K⁻¹, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°_f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases. The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites and 10 kbar for ultra-high pressure titanite-bearing assemblages.     

Cl/Br ratios and stable chlorine isotope analysis of magmatic–hydrothermal fluid inclusions from Butte,Montana and Bingham Canyon,Utah

A bulk geochemical study has been carried out on fluid inclusion leachates extracted from quartz veins from porphyry Cu deposits in Butte, Montana, USA and Bingham Canyon, Utah, USA. The leachates mostly represent low-salinity magmatic–hydrothermal fluid inclusions. Their halogen ratios (Br/Cl) of fluid inclusion leachates were determined by ion chromatography, and δ³⁷Cl values of the leachates were measured by continuous-flow isotope ratio mass spectrometry. Br/Cl ratios from early pre-Main stage and later Main stage veins at Butte range from 0.60 to 1.88 × 10⁻³ M. Ratios are similar in pre-Main stage veins with sericite bearing selvages and Main stage samples ranging from 0.81 to 1.08 × 10⁻³ and from 0.92 to 1.88 × 10⁻³ M, respectively, clustering below seawater (1.54 × 10⁻³ M) and overlapping mantle values (~1–2 × 10⁻³ M). Two samples associated with early pre-Main stage potassic alteration yield distinctly lower Br/Cl ratios of 0.60 and 0.64 × 10⁻³ M. Butte δ³⁷Cl values range from −0.8‰ to −2.3‰ with no significant difference between pre-Main stage and Main stage samples. Br/Cl ratios for quartz veins from Bingham Canyon range from 0.18 to 3.68 × 10⁻³ M. Br/Cl ratios from Bingham range above and below previously reported for porphyry copper deposits. In contrast to Butte, δ³⁷Cl values for Bingham are lower, ranging from −0.9‰ to −4.1‰. In the absence of any processes which can significantly fractionate chlorine isotopes at high temperatures, we suggest that the porphyry system at Bingham, and to a lesser extent at Butte, have inherited negative chlorine isotopic signatures from the subducting slab generated at low temperatures.     

Thermal expansion behavior of Ce2Zr2O7 up to 898 K in conjunction with structural analyses by neutron diffraction

The thermal expansion of cubic pyrochlore Ce₂Zr₂O₇ has been measured from room temperature to 898 K on polycrystalline material in conjunction with structural analyses using neutron diffraction. This compound has a thermal expansion coefficient in line with the other comparable lanthanoide pyrochlore oxides. The coefficient can be expressed as α(T) = 8.418 × 10⁻⁶ + 0.9861 × 10⁻⁹ × T. The structural refinements performed for each measured temperature showed a comparable linear evolution of the Ce–O/Zr–O distances (within 0.57%).     

Fluid evolution at the Variscan front in the vicinity of the Aachen thrust

Quartz–carbonate–chlorite veins were studied in borehole samples of the RWTH-1 well in Aachen. Veins formed in Devonian rocks in the footwall of the Aachen thrust during Variscan deformation and associated fluid flow. Primary fluid inclusions indicate subsolvus unmixing of a homogenous H₂O–CO₂–CH₄–(N₂)–Na–(K)–Cl fluid into a H₂O–Na–(K)–Cl solution and a vapour-rich CO₂–(H₂O, CH₄, N₂) fluid. The aqueous end-member composition resembles that of metamorphic fluids of the Variscan front zone with salinities ranging from 4 to 7% NaCl equiv. and maximum homogenisation temperatures of close to 400°C. Pressure estimates indicate a burial depth between 4,500 and 8,000 m at geothermal gradients between 50 and 75°C/26 MPa, but pressure decrease to sublithostatic conditions is also indicated, probably as a consequence of fracture opening during episodic seismic activity. A second fluid system, mainly preserved in pseudo-secondary and secondary fluid inclusions, is characterised by fluid temperatures between 200 and 250°C and salinities of <5% NaCl equiv. Bulk stable isotope analyses of fluids released from vein quartz, calcite, and dolomite by decrepitation yielded δD_H2O values from −89 to −113 ‰, δ¹³C_CH4 from −26.9 to −28.9‰ (VPDB) and δ¹³C_CO2 from −12.8 to −23.3‰ (VPDB). The low δD and δ¹³C range of the fluids is considered to be due to interaction with cracked hydrocarbons. The second fluid influx caused partial isotope exchange and disequilibrium. It is envisaged that an initial short lived flux of hot metamorphic fluids expelled from the epizonal metamorphic domains of the Stavelot–Venn massif. The metamorphic fluid was focused along major thrust faults of the Variscan front zone such as the Aachen thrust. A second fluid influx was introduced from formation waters in the footwall of the Aachen thrust as a consequence of progressive deformation. Mixing of the cooler and lower salinity formation water with the hot metamorphic fluid during episodic fluid trapping resulted in an evolving range of physicochemical fluid inclusion characteristics.     

Grain boundary diffusion of oxygen,potassium and calcium in natural and hot-pressed feldspar aggregates

 Grain boundary diffusion rates of oxygen, potassium and calcium in fine-grained feldspar aggregates were determined experimentally. The starting materials were a natural albite rock from the Tanco pegmatite and aggregates hot-pressed from fragments of Amelia albite or Ab, Or and An composition glasses. The technique employed isotopic tracers (¹⁸O, ⁴¹K, ⁴²Ca) either evaporated onto the surface or in an aqueous solution surrounding the sample, and depth profiling using an ion microprobe (SIMS). From the depth profiles, the product of the grain boundary diffusion coefficient (D′) and effective boundary width (δ) was calculated using numerical solutions to the appropriate diffusion equation. The experimental reproducibility of D′δ is a factor of 3. A separate determination of D′ independent of δ yields an effective grain boundary width of ∼3 nm, consistent with high resolution TEM observations of a physical grain boundary width <5 nm. Oxygen (as molecular water) grain boundary diffusion rates were determined in the Ab and Or aggregates at 450°–800° C and 100 MPa (hydrothermal), potassium rates in Or aggregates at 450°–700° C both at 0.1 MPa (in air) and at 100 MPa (hydrothermal), and calcium rates in An aggregates at 700°–1100° C and 0.1 MPa (in air). Oxygen grain boundary diffusion rates are similar in all three of the Ab aggregates and in the Or aggregate. Potassium and oxygen depth profiles measured in the same samples yield different D′δ values, confirming a diffusional transport mechanism. Potassium diffusion in the Or aggregate has a greater activation energy (216 vs 78 kJ/mol) than oxygen, and the Arrhenius relations cross at ∼625° C. Potassium D′δ values in Or aggregates are about a factor of five greater in hydrothermal experiments at 100 MPa than in experiments at 0.1 MPa in air. Calcium grain boundary diffusion rates in An aggregates are 4 to 5 orders of magnitude slower than potassium in Or and have a greater (291 kJ/mol) activation energy. This suggests that differences in formal charge and/or size of diffusing species may play an important role in their relative grain boundary diffusion rates. Received: 24 December 1993 / Accepted: 16 June 1994     

Compositional changes of minerals associated with dynamic recrystallizatin

The rate of compositional and isotopic exchange between minerals may be enhanced significantly if the rock is deformed simultaneously. The enhanced exchange rate may result from a reduction in grain size (shorter distance for volume diffusion), dissolution and growth of grains by diffusion creep (pressure solution), or the movement of high-angle grain boundaries through strained grains during recrystallization in the dislocation creep regime. The migration of high-angle grain boundaries provides high diffusivity paths for the rapid exchange of components during recrystallization. The operation of the latter process has been demonstrated by deforming aggregates consisting of two plagioclases (An₁ and An₇₉) at 900°C, 1 GPa confining pressure, and a strain rate of ∼2x10^-6s^-1. The polygonal, recrystallized grains were analyzed using an analytical transmission electron microscope and have a variable but often intermediate composition. At the conditions of these experiments, the volume interdiffusion rate of NaSi/CaAl is too slow to produce any observable chemical change, and microstructural-chemical relations indicate that the contribution from diffusion creep was insignificant except for initially fine-grained (2–10 μm) aggregates. These results indicate that strain-induced recrystallization can be an effective mechanism for enhancing the kinetics of metamorphic reactions and for resetting the isotope systematics of minerals such as feldspars, pyroxenes, and amphiboles.     

Electrical conductivity of polycrystalline Mg(OH)<Subscript>2</Subscript> at 2 GPa: effect of grain boundary hydration–dehydration

The effect of intergranular water on the conductivity of polycrystalline brucite, Mg(OH)₂, was investigated using impedance spectroscopy at 2 GPa, during consecutive heating–cooling cycles in the 298–980 K range. The grain boundary hydration levels tested here span water activities from around unity (wet conditions) down to 10⁻⁴ (dry conditions) depending on temperature. Four orders of magnitude in water activity result in electrical conductivity variations for about 6–7 orders of magnitude at 2 GPa and room temperature. Wet brucite samples containing, initially, about 18 wt% of evaporable water (i.e. totally removed at temperatures below 393 K in air), display electrical conductivity values above 10⁻²–10⁻³ S/m. A.C. electrical conductivity as a function of temperature follows an Arrhenius behaviour with an activation energy of 0.11 eV. The electrical conductivity of the same polycrystalline brucite material dried beforehand at 393 K (dry conditions) is lower by about 5–6 orders of magnitude at room temperature and possesses an activation energy of 0.8–0.9 eV which is close to that of protonic diffusion in (001) brucitic planes. Above ca. 873 K, a non-reversible conductivity jump is observed which is interpreted as a water transfer from mineral bulk to grain boundaries (i.e. partial dehydration). Cooling of such partially dehydrated sample shows electrical conductivities much higher than those of the initially dry sample by 4 orders of magnitude at 500 K. Furthermore, the corresponding activation energy is decreased by a factor of about four (i.e. 0.21 eV). Buffering of the sample at low water activity has been achieved by adding CaO or MgO, two hygroscopic compounds, to the starting material. Then, sample conductivities reached the lowest values encountered in this study with the activation energy of 1.1 eV. The strong dependency of the electrical conductivity with water activity highlights the importance of the latter parameter as a controlling factor of diffusion rates in natural processes where water availability and activity may vary grandly. Water exchange between mineral bulk and mineral boundary suggests that grain boundary can be treated as an independent phase in dehydroxylation reactions.     

High-pressure X-ray diffraction study of ε-FeOOH

An in situ synchrotron X-ray diffraction study was carried out on ε-FeOOH at room temperature up to a pressure of 8.6 GPa using the energy-dispersive method. The linear compressibility was determined to be β _a  = 1.69(3) × 10⁻³ GPa⁻¹, β _b  = 2.86(6) × 10⁻³ GPa⁻¹, and β _c  = 1.73(5) × 10⁻³ GPa⁻¹. The b-axis of the unit cell is more compressible than the a and c axes. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state. The best fit was found using a room temperature isothermal bulk modulus of K ₀ = 126(3) GPa and its pressure derivative K′ = 10(1).     

Grain boundary dissolution porosity in quartzofeldspathic ultramylonites: Implications for permeability enhancement and weakening of mid-crustal shear zones

Quartzofeldspathic ultramylonites from the Alpine Fault Zone, one of the world's major, active plate boundary-scale fault zones have quartz crystallographic preferred orientations (CPO) and abundant low-angle (<10° misorientation) boundaries, typical microstructures for dislocation creep-dominated deformation. Geometrically necessary dislocation density estimates indicate mean dislocation densities of ∼10⁹ cm⁻². A significant proportion (∼30%) of grain boundaries (>10° misorientation) are decorated by faceted pores, commonly with uniformly-oriented pyramidal shapes. Only grain boundaries with >10° misorientation angles in polymineralic aggregates are decorated by pores. Mean grain boundary pore densities are ∼5 × 10⁸ cm⁻². Grain boundary pores are dissolution pits generated during syn-deformational transient grain boundary permeability, nucleating on dislocation traces at dilatant grain boundary interfaces. They have not been removed by subsequent grain boundary closure or annealing. Pore decoration could have led to grain boundary pinning, triggering a switch in the dominant deformation mechanism to grain boundary sliding, which is supported by evidence of CPO destruction in matrix quartz. Pore-decorated grain boundaries have significantly reduced surface area available for adhesion and cohesion, which would reduce the tensile and shear strength of grain boundaries, and hence, the bulk rock. Grain boundary decoration also significantly decreased the mean distance between pores, potentially facilitating dynamic permeability. Consequently, these microstructures provide a new explanation for strain weakening and evidence of fluid flow along grain boundaries in mylonites at mid-crustal conditions.     

Timescales and mechanisms of fluid infiltration in a marble: an ion microprobe study

Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 ¹⁸O/¹⁶O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in ¹⁸O and Sr compared to PLC, and is much more ¹⁸O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of ¹⁸O-depleted (metamorphic or magmatic) fluid (initial δ¹⁸O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10⁻⁸ m², from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼10³ to ∼10⁴ years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of ¹⁸O/¹⁶O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ¹⁸O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998