Oxygen bulk diffusion measurements and TEM characterization of a natural ultramylonite: implications for fluid transport in mica-bearing rocks

Oxygen bulk diffusion rates were experimentally determined in a natural ultramylonite sample ( c . 5   μ m grain size; 15–20% biotite, 20% quartz, 60–65% feldspars, and minor Fe-oxides) from the Gerrish Island shear zone, SE Maine, USA. The diffusion experiments were performed at 250–550  °C and 100  MPa water pressure. Oxygen bulk diffusion rates were determined both parallel and perpendicular to the strong foliation of the sample. The Arrhenius parameters for transport parallel to the foliation are: D _bulk0=2.0×10⁻¹¹ m² s⁻¹ and Q =30±6 kJ mol⁻¹. The bulk diffusivity perpendicular to the foliation is about a factor of 3.5 less than that parallel to the foliation with the same activation energy. The values of bulk diffusivity and activation energy obtained are consistent with ionic diffusion through a static aqueous fluid, suggesting that an interconnected fluid exists in the ultramylonite even under hydrostatic conditions. The microstructure of the ultramylonite was characterized using transmission electron microscopy (TEM). The nature and distribution of the interconnected fluid cannot be completely resolved from the TEM analysis; however, the low percentage of three-grain channels and open grain/interphase boundaries suggests that the fluid resides as a thin film on the grain surfaces. The results of this study have direct applications in many important geological settings and provide valuable insights into the observed rapid diffusion rates, strong lithological control and pervasive nature of fluid transport in mica-bearing rocks.     

Grain-boundary migration of quartz during annealing experiments at high temperatures and pressures, with implications for metamorphic geology

Annealing experiments on agate, quartz schist and metachert at 800–1000 °C, confining pressures of 400 and 800  MPa, and annealing times of 6.0×10–3.6×10⁵s revealed normal grain growth of quartz in the agate, grain-size increasing with time, but the rate of grain growth decreasing with increasing grain size.
The boundaries of agate with quartz schist and metachert migrated into the agate at the expense of fine-grained quartz in the agate. The driving force for the migration appears to be the reduction of surface energy associated with removal of fine-grained quartz in the agate. Assuming the activation energy as Q _m =11  kcal mol⁻¹, a general expression for the relationship between velocity of boundary migration ( V   ) and driving force ( P ) is where γ is the specific surface energy of quartz, R is the gas constant and T  is the absolute temperature. The velocity is relatively fast at high temperatures on a geological time-scale. The expression assists a quantitative understanding of the microstructural development of quartz at metamorphic conditions.     

Grain boundary migration of water and carbon dioxide during uplift of garnet-zone Alpine Schist, New Zealand

Abstract Deformed quartz veins in garnet-zone schist adjacent to the active Alpine Fault, New Zealand, have fluid inclusions trapped along quartz grain boundaries. Textures suggest that the inclusions formed in their present shapes during annealing of the deformed veins. Many of the inclusions are empty, but some contain carbon dioxide with densities that range from 0.16 to 0.80 g cm⁻³. No water, nitrogen or methane was detected. The inclusions are considerably more CO₂-rich than either the primary metamorphic fluid (<5% CO₂) or fluids trapped in fracture-related situations in the same, or related, rocks (<50% CO₂). Enrichment of CO₂ is inferred to have resulted from selective migration (wicking) of saline water from the inclusions along water-wet grain boundaries after cooling-induced immiscibility of a water-CO₂ mixture. Inclusion volumes changed after loss of water. Non-wetting CO₂ remained trapped in the inclusions until further percolation progressively removed CO₂ in solution. This mechanism of fluid migration dominated in ductile quartz-rich rocks near, but below, the brittle-ductile transition. At deeper levels, hydraulic fracturing is also an important mechanism for fluid migration, whereas at shallower levels advection through open fractures dominates the fluid flow regime.     

The migration of fluid-filled grain boundaries in recrystallizing synthetic bischofite: first results of in-situ high-pressure, high-temperature deformation experiments in transmitted light

The effect of fluids on recrystallization behaviour is well known; however, the detailed microscale distribution of fluid in grain boundaries and the influence of fluid on grain boundary migration are still unresolved. In this study, in‐situ deformation experiments in transmitted light microscopy were undertaken, as this allows continuous and direct observation of the whole range of processes involved in fluid‐assisted grain boundary migration. A new see‐through deformation apparatus was developed to enable the control of fluid pressure. Bischofite containing small amounts of aqueous fluid was deformed at temperatures between 50 and 90 °C, over a range of fluid pressure from 0.5 to 1 MPa, and strain rates of 5 × 10^?6 to 1 × 10^?4 s^?1. The rates of grain boundary migration were measured at different temperatures and strain rates. Detailed observations during and after the deformation illustrate the evolution of migrating fluid‐filled grain boundaries and show that the incorporation of fluids from inclusions as well as their pinch‐off is dependent on the grain boundary velocity, the thickness of the grain boundary and the size and shape of the inclusions. Direct evidence is presented for the contraction of the grain boundary fluids into isolated inclusions after equilibrium conditions are attained.     

The flow of surface-derived fluids through Alice Springs age middle-crustal ductile shear zones, Reynolds Range, central Australia

The south-east Reynolds Range, central Australia, is cut by steep north-west-trending Alice Springs age ( c. 334  Ma) shear zones that are up to hundreds of metres wide and several kilometres long with reverse senses of movement. Amphibolite facies (550–600  °C, 500–600  MPa) shear zones cut metapelites, while greenschist facies shear zones (420–535  °C, 400–650  MPa) cut metagranites. The sheared rocks commonly underwent metasomatism implying that the shear zones were the pathways of significant fluid flow. Altered granites within greenschist facies shear zones have gained Si and K but lost Ca and Na relative to their unsheared counterparts, suggesting that the fluid flowed down-temperature (and hence probably upward) through the shear zones. Time-integrated fluid fluxes calculated from silica addition are up to 2.1×10¹⁰ mol  m⁻² ( c. 4.2×10⁵  m³  m⁻²). Similar time-integrated fluid fluxes are also estimated from changes in K and Na. The sheared granitic rocks locally have δ¹⁸O values as low as 0 which is much lower than the δ¹⁸O values of the adjacent unsheared granites (7 to 9), implying that the fluid which flowed through these shear zones was derived from the surface. For the estimated time-integrated fluid fluxes, the fluids would be able to retain their isotopic signature for many tens to hundreds of kilometres. The flow of surface-derived fluids into the ductile middle crust, with subsequent expulsion upwards through the shear zones, may have been driven by seismic activity accompanying the Alice Springs deformation.     

Ore-Forming Fluid Characteristics of the Dayingezhuang Gold Deposit, Jiaodong Gold Province, China

The Dayingezhuang gold deposit is located in the central part of the Zhaoping Fault Zone, which is one of the most important gold-hosting faults in the Jiaodong gold province of China. Dayingezhuang is a typical large-scale shear zone-hosted disseminated gold deposit with superimposed silver mineralization. Fluid inclusion (FI) petrography and microthermometry, and analysis of oxygen and hydrogen isotopes for fluid inclusions were conducted to determine the characteristics of the ore-forming fluids and the processes of silver mineralization. Microthermometry data of FI indicated that ore-forming fluids are characterized by low salinity and low density. Homogenization pressures of FI are estimated at 20 × 10⁵–220 × 10⁵ Pa. The change in ore-forming fluids from K₂SO₄ type to NaCl type indicates the superposition of two hydrothermal mineralizing events. Ore-forming fluids were dominated by magmatic components in the early mineralization period, and affected by meteoric waters in the late period. Gold may have been transported as Au-S or Au-Cl complexes, whereas silver was transported as Ag-Cl complexes. Early fluid boiling and later fluid mixing are thought to be two of the main factors causing the deposition and superimposing of gold and silver to form the large deposit.     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

Permeability distribution in the Quaternary of the Upper Rhine glacio-fluvial aquifer

An extraordinarily large and geographically extensive 3D dataset has allowed us to relate permeability to detailed geological features. Permeability data derived from several thousand pumptests in Quaternary sediments (thickness < 120 m) of the Upper Rhine valley vary from K = 4.5 × 10⁻⁷ m s⁻¹ to K = 2.7 × 10⁻¹ m s⁻¹. The geometric mean of the data is K = 2.25 × 10⁻³ m s⁻¹. The permeability distribution maps for four different stratigraphic levels show that the highest values are found in sections beneath recent and historic fluvial systems. Fossil fans of small rivers from the Black Forest can be identified in the Rhine valley on the basis of the permeability pattern. The average hydraulic conductivity decreases S–N along the flow direction which corresponds to a decrease in grain-size of the fluvial sediments.     

Aeolian dune migration along the Ceará coast, north-eastern Brazil

Aeolian dune dimensions and migration rates are analysed along the Ceará coast, north-east Brazil. Dunes that are currently mobile along the Ceará coast are composed of barchans and sand sheets. The results show that barchans maintain an equilibrium form, which can be characterized by values of dimensionless shape parameters H/W and W/L , where H is the dune height, W is the wing-to-wing width and L is the dune length. Dunes are highly mobile, with average migration rates of 17·5 m year⁻¹ for barchans and 10 m year⁻¹ for sand sheets. The calculated migration rates were found to depend strongly on dune dimensions for both barchans and sand sheets, i.e. the larger the dune is, the lower the migration rate will be. This size dependence was associated with the existence of a representative common transport rate along the dune fields, which induces a different dune migration rate dependent on dune size. Finally, from the observed dune evolution, an aggregated scale aeolian sediment transport was inferred. This bulk transport rate, of the order of 90–100 m³ m⁻¹ year⁻¹, is only valid for a timescale of years to decades, which is the timescale used in dune evolution analysis.     

The interaction of migrating grain boundaries with fluid inclusions in rock analogues: the effect of wetting angle and fluid inclusion velocity

The distribution of fluids in grain boundaries, fluid inclusion morphology and kinetics have important effects on the evolution of microstructure and transport properties and should be understood for correct interpretations for studies of thermobarometry and paleorheology. We compare results of in situ annealing experiments on rock analogues in the presence of different pore fluids in transmitted light: bischofite with saturated brine, camphor with ethanol, and camphor with ethylene glycol. The solid–liquid systems vary in terms of wettability and solubility, while homologous temperatures, strain rates, annealing times, and the initial textures are similar. In agreement with earlier work and theory, we observe different types of grain boundary–fluid inclusion interaction at sufficiently low grain boundary velocity such as drag and drop, necking, and the break up into arrays of smaller inclusions. In all three systems the maximum possible velocity of a fluid inclusion being dragged by a moving grain boundary is dependent on the fluid inclusion size. We interpret this to reflect the fluid inclusion mobility, and compare the trend with theoretical models which suggest that for all three systems the rate-limiting process is bulk diffusion and not surface diffusion or solution-precipitation.     

Distribution of brine in grain boundaries during static recrystallization in wet, synthetic halite: insight from broad ion beam sectioning and SEM observation at cryogenic temperature

We report observations from room temperature static recrystallization experiments (annealing times from minutes to year) of cold-pressed, synthetic, coarse-grained, wet sodium chloride, prepared by broad ion beam polishing and SEM observations at cryogenic temperature to observe directly the brine in grain boundaries. At all stages of annealing, the majority of the brine in the samples is connected in 2D sections along grain boundaries. Another part of the brine is in isolated brine inclusion arrays along grain boundaries and in brine inclusions left behind by migrating brine-filled grain boundaries. Most of these boundaries are mobile because the aggregate is coarsening. We interpret that the boundaries without observable brine films (<15 nm) and brine inclusion arrays are healed and immobile. Evolution of grain boundary structure involves three major processes. First, dissolution on one side of the grain boundary and precipitation on the other side, resulting in grain boundary migration. Second, the development of facets formed by low-index crystallographic planes of the grains bounding the grain boundary brine. When both sides of a grain boundary are able to develop low-index facets in a thick brine film, the resulting impingement boundary is interpreted to be immobile and may prevent the new grain from migrating into a deformed neighbor. When one side of a faceted boundary consists of low-index crystallographic planes and the other side passively follows this faceted shape along irrational surfaces, the boundary is mobile. Third, the healing of grain boundary brine films, producing solid–solid grain boundaries without resolvable brine films.     

Syndeformational fluid trapping in quartz: determining the pressure-temperature conditions of deformation from fluid inclusions and the formation of pure CO2 fluid inclusions during grain-boundary migration

Abstract Observations and microthermometric data on fluid inclusions from a terrane that underwent deformation following peak metamorphic conditions show that grain-boundary migration recrystallization favours the entrapment of carbonic inclusions whereas microfracturing during brittle deformation favours the infiltration and eventual entrapment of aqueous fluids. Our results imply that pure CO₂ fluid inclusions in metamorphic rocks are likely to be the residue of deformation-recrystallization process rather than representing a primary metamorphic fluid.
Where the temperature of deformation can be deduced by other means, the densities of fluid inclusions trapped during recrystallization, which we call recrystallization-primary fluid inclusions, can be used to constrain the ambient pressure during deformation. Using these constraints, the data imply that the post-metamorphic Hercynian exhumation in Sardinia brought rocks at 300° C to within 3km of the surface. This conclusion is similar to that described for the rapidly uplifted Southern Alps in New Zealand.     

Experimental diffusion of hydrogen into synthetic fluid inclusions in quartz

Abstract Quartz-hosted, synthetic CO₂-H₂O fluid inclusions behave as open systems with respect to diffusional transfer of hydrogen during laboratory-simulated metamorphic re-equilibration at 650, 750 and 825°C and 1.5 kbar total pressure with f_O2 defined by the C-CH₄ buffer. Microthermometry and Raman spectroscopy show that the initial CO₂-H₂O inclusions become CO₂-CH₄-H₂-H_2O
inclusions after diffusive influx of hydrogen from the reducing confining medium. Measurable changes are observed in inclusion compositions after only 15 days of re-equilibration, implying significant hydrogen mobility at still lower temperatures over geological time spans. Results of synthetic inclusion re-equilibrium experiments have profound implications for the interpretation of natural fluid-inclusion data; failure to account for potential hydrogen migration in inclusions from high-temperature geological environments may lead to erroneous estimates of P-T, and/or the compositions of metamorphic fluids.     

Fluid infiltration and volume change during mid-crustal mylonitization of Proterozoic granite, King Island, Tasmania

The development of 10–30  m wide mylonite zones at mid-crustal depths in late Proterozoic granitoids on King Island, Tasmania, was associated with pervasive infiltration of low δ¹⁸O-fluids (+5 to +7) on the scale of the shear zones. Syndeformational fluid–rock interaction produced substantial differences in mineral composition and bulk rock chemistry among several adjacent shear zones which are hosted by the same granite. In a shear zone at Cape Wickham with a normal slip component, changes in whole-rock chemistry between granite and mylonites indicate a gain of Ca, and losses of K and Na during deformation, which was nearly isovolumetric. Notable losses of K, Rb and Si occurred during partial retrograde alteration of mylonites near the western margin of this shear zone. The alteration suggests a component of up-temperature fluid flow. In contrast, 3  km to the south east, in a strike-slip shear zone at Disappointment Bay, complete albitization of plagioclase was associated with Na-gain and Ca-loss. Deformation also involved losses of Mg and Fe. Up to 60% volume gain occurred during the formation of closely spaced mesoscopic to microscopic quartz veins during mylonitization. The substantial silica-gain in this, as well as in two mylonite zones further south east, is interpreted to have been associated with upward flow of aqueous fluids along these shear zones. On the basis of a gradient reaction model, minimum time-integrated fluid-fluxes of 10⁶  m³/m² are estimated for the Disappointment Bay (West) Shear Zone.     

Primary carbonate/CO2 inclusions in sapphirine-bearing granulites from central Sri Lanka

High-density CO₂-rich fluid inclusions from a sapphirine-bearing granulite (Hakurutale, Sri Lanka) have been studied by microthermometry, Raman spectrometry and SEM analysis. Based on textural evidence, two groups of inclusions can be identified: primary, negative crystal shaped inclusions (group I) and pseudo-secondary inclusions, which experienced a local, limited post-trapping modification (group II). Both groups contain magnesite as a daughter mineral, occurring in a relatively constant fluid/solid inclusion volume ratio (vol_solid =0.15 total volume). CO₂ densities for group I and II differ only slightly. Both groups contain a fluid, which was initially trapped at peak metamorphic conditions as a homogeneous (CO₂+MgCO₃) mixture. Thermodynamic calculations suggest that such a fluid (CO₂+15 vol% MgCO₃) is stable under granulite facies conditions. After trapping, magnesite separated upon cooling, while the remaining CO₂ density suffered minor re-adjustments. A model isochore based on the integration of the magnesite molar volume in the CO₂ fluid passes about 1.5–2 kbar below peak metamorphic conditions. This remaining discrepancy can be explained by the possible role of a small quantity of additional water.     

Trace Element Determination of Single Fluid Inclusions in Quartz by Laser Ablation ICP-MS

Single fluid inclusions in quartz from a Pb-Zn-Ag carbonate replacement deposit were selected for trace element determination by laser ablation ICP-MS. Spikes in element intensities were noted between first breached fluids versus subsequent analyses, suggesting that accurate element concentrations may not be determined in smaller fluid inclusions when only one analysis is obtained before the fluid is exhausted. Elemental concentrations in the fluid inclusions were determined by external standardisation using solutions sealed in microcapillary tubes. Standards and single natural inclusion analyses give repeatabilities (%RSD) of ˜ 20% for Rb and Sr. Rubidium and strontium concentrations range from 0.56-5.07 μg ml^-1 and 1.12-27.4 μg ml^-1, respectively, whereas Zn and Ag are below detection limits (< 10 ng ml^-1). The results suggest that nearly all Zn and Ag are removed by the time hydrothermal fluids precipitate gangue minerals.     

The amphibolite-granulite facies transition in West Uusimaa, S.W. Finland. A fluid inclusion study

This work presents the results of a fluid inclusion study of an amphibolite-granulite facies transition in West Uusimaa, S.W. Finland. Early fluid-inclusions in the granulite facies area are characteristically carbonic (CO₂), in contrast to predominantly aqueous early inclusions in the amphibolite facies area. These early inclusions can be related to peak metamorphic conditions (750-820°C and 3-5 kbar for peak granulite facies metamorphism). Relatively young CO₂ inclusions with low densities (<0.8g/cm³) indicate that the first part of the cooling history of the rocks was characterized by a near isothermal uplift.
N₂-CH₄ inclusions, with compositions ranging between pure CH₄ and pure N₂ (Raman spectral analysis), were found in the whole area. They are probably syn- or even pre-early inclusions. Only nearly critical homogenizing inclusions have been found (low density). Pressure estimates, based on densities of early fluid inclusions, show that the rapid transition of amphibolite towards granulite facies metamorphism is virtually isobaric. Granulite facies metamorphism in West Uusimaa is a thermal event, probably induced by the influx of hot, CO₂-bearing fluids.     

Hot contacts of garnet peridotites in middle/upper crustal levels: new constraints on the nature of the late Variscan high-T/low-P event in the Moldanubian (Central Vosges/NE France)

P–T  paths based on parageneses in the immediate vicinity of former high-temperature contact zones between mantle peridotites and granulitic country rocks of the Central Vosges (NE France) were derived by applying several conventional thermometers and thermobarometric calculations with an internally consistent dataset. The results indicate that former garnet peridotites and garnet–spinel peridotites were welded together with crustal rocks at depths corresponding to 1–1.2 GPa. The temperature of the crustal rocks was about 650–700 °C at this stage, whereas values of 1100 °C (garnet peridotites) and 800–900 °C (garnet–spinel peridotites) were calculated for the ultramafic rocks. After emplacement of the mantle rocks, exhumation of the lower crust took place to a depth corresponding to 0.2–0.3 GPa. The temperatures of the incorporated peridotite slices were still high (900–1000 °C) at this stage. This is indicated by the presence of high- T  /low- P parageneses ( c . 800 °C, 0.2–0.3 GPa) in a small (1–10 m) contact aureole around a former garnet peridotite. Crustal rocks distant to the peridotites equilibrated in the same pressure range at lower temperature (650–700 °C). High cooling rates (10²–10³ °C Ma⁻¹) were calculated for a garnet–biotite rock inclusion in the peridotites and for the crustal rocks at the contact by applying garnet–biotite diffusion modelling. Minimum rates of 0.75–7.5 cm a⁻¹ are required for vertical ascent of rock units (30 km vertical distance) derived from the crust–mantle boundary, resulting in a late Variscan (340 Ma) high- T  /low- P event.     

Andalusite-bearing veins at Vedrette di Ries (eastern Alps, Italy): fluid phase composition based on fluid inclusions

Abstract Andalusite-bearing veins formed during contact metamorphism in the aureole of the Vedrette di Ries tonalite. In the veins, quartz crystals that are completely armoured by andalusite or that occur in strain shadow areas contain three generations of fluid inclusions: low-salinity H₂O-CO₂-CH₄ mixtures with CH₄/(CO₂+ CH₄) ± 0.35 (type A); low-salinity aqueous fluids (type B); H₂O-free, CO₂-CH₄ fluids with the same carbonic speciation as A (type C). Carbonic types A and C typically have a dark appearance, which is attributed to graphite coatings on inclusion walls. Microstructural analysis of the host quartz and calculated densities indicate that type A inclusions were likely trapped during vein formation. These inclusions underwent strain-assisted re-equilibration during cooling that resulted in density increases without change of composition. After the rocks had cooled below about 350 ° C, type C inclusions appear to have formed from one of the immiscible fractions after unmixing of the H₂O-CO₂-CH₄ fluid mixtures. Aqueous type B inclusions, apparently trapped between 225 and 350 ° C, could represent an independent fluid, or could be the H₂O-rich fraction of unmixed type A fluids. Taking account of the uncertainties, the composition and density of the complex type A inclusion fluids are in good agreement with the properties of primary fluids calculated from the petrological data. The fluid inclusion data support the model of vein formation by hydrofracturing as a result of dehydration of graphitic metapelites. These new results also demonstrate the importance of considering strain in the interpretation of metamorphic fluid inclusions.     

Determination of the Absolute Hydrogen Isotopic Ratio of V-SMOW and SLAP

By mixing ¹H₂O and ²H₂O, both with accurately known purity, samples were prepared with ²H/¹H ratios close to those of the international isotopic water standards: V-SMOW and SLAP. A mass spectrometrical comparison of these calibration samples with the actual water standards revealed:
²H/¹H of V-SMOW = (155.95 ± 0.08) × 10^−6
2H/¹H of SLAP = (89.12 ± 0.07) × 10⁻⁶
δ²H_V-SMOW(SLAP) =−428.5 ± 0.5 %