Comparison of mass transfer patterns, geometry and microstructures developed within and around veins allows the interpretation of processes of fluid flow during deformation, metamorphism and mineralization. A classification of vein types based on the degree of interaction with wallrock (using petrological, geochemical or isotopic indicators) can be used to identify a range of processes, from closed system behaviour in which the vein mass is derived from local wallrock, through to open system behaviour in which the vein mass is derived externally. Microstructural characteristics, such as wallrock selvages, multiple growth events recorded by vein seams and vein crystal morphology, also help to constrain mass transfer patterns during vein formation. We present a range of processes for vein formation, including: (i) the formation of closed system fibrous veins by dissolution–precipitation creep, including varieties in which tensile failure is not required; (ii) pressure- or kinetically dependent closed system segregation veins in which transfer of soluble components from wallrock to vein leaves behind a residual selvage; (iii) similar vein–selvage patterning, but with mass imbalances between vein and wallrock requiring fluid advection through both interconnected fracture networks and in the surrounding permeable rock; and (iv) the proposed formation of veins by fluid ascent in mobile hydrofractures, in which isotopic or chemical disequilibrium within and around the vein suggests that the crack and fluid within it moved essentially as one. The postulate of rapid fluid and mass transfer via such mobile hydrofractures has implications for the release of volatiles from metamorphic terrains. Also, consideration of a broad range of possible vein-forming mechanisms is highly desirable when dealing with mineral deposits found in deformed, metamorphosed rocks, because closed system veining may produce patterns that, if erroneously recognized as being open systems, could lead to false interpretations of the role of tectonic fracturing in ore genesis.

Mechanisms of fluid flow and fluid–rock interaction in fossil metamorphic hydrothermal systems inferred from vein–wallrock patterns, geometry and microstructure

Quartz grains in hydrothermally altered granites from the Isle of Skye are highly heterogeneous and not equilibrated in oxygen isotope ratio at the 20 μm scale. Ion microprobe analysis of one grain shows a gradient of 13‰ over 400 μm and a greater range in δ
18O than all quartz previously analyzed on the Isle of Skye. Other crystals from the same outcrop are homogeneous. Digitized cathodoluminescence images reveal patterns of magmatic zoning and brittle fracturing not otherwise detectable. The ion probe analysis correlates low δ
18O values on a micro-scale to one set of healed cracks. Thus, quartz exchanges oxygen isotopes primarily by solution and reprecipitation along fractures, in contrast to more reactive feldspar that appears to exchange from the grain boundary inward. Macroscopic models of isotope exchange are not realistic for these rocks; the flow of hydrothermal fluids was heterogeneous, anisotropic and crack controlled.

Ion microprobe analysis of oxygen isotope ratios in quartz from Skye granite: healed micro-cracks, fluid flow, and hydrothermal exchange

The role of grain boundaries and transient porosity in rocks as fluid pathways for reaction front propagation

Fluid-solid-solid dihedral angles in the NaCl-H2O-CO2-calcite-dolomite-magnesite system have been determined at pressures ranging from 0.5 to 7 kbar and temperatures from 450°C to 750°C. At 1 kbar and 650°C, both dolomite and magnesite exhibit a dihedral angle minimum for intermediate H2O-CO2 fluids similar to that previously determined by the present authors for calcite, but the depth of the minimum is smaller, being above the critical value of 60° for both dolomite and magnesite for all fluid compositions. Calcite-calcite-brine dihedral angles at 650°C have been determined in the pressure range 1–5 kbar. Angles decrease with increasing salt content of the fluid, tending towards a constant value of about 65° for strong brines at pressures above 2 kbar. There is a general increase of angle with increasing pressure which is most marked for strong brines. A positive correlation of angle with pressure is also observed in calcite-H2O-CO2 fluids, the position of the minimum moving towards higher angles and towards H2O-rich fluids with increasing pressure. The permeability window previously observed by the present authors at 1 kbar and intermediate fluid compositions closes at about 1.5 kbar. The results demonstrate that the permeability of carbonates to grain edge fluid flow is only possible at low pressures and for fluids of restricted H2O-CO2-NaCl compositions. However, geochemical evidence from metamorphic terrains suggests that pervasive infiltration does occur under conditions where impermeability is predicted. From examination of published studies of infiltrated carbonates we conclude that deformation plays a critical role in enhancing carbonate permeability. Possible mechanisms for this include shear-enhanced dilatancy (micro-cracking), fluid inclusion drag by deformation-controlled grain boundary migration, and dynamically maintained transient grain boundary fluid films.

P-T-X effects on equilibrium carbonate-H 2 O-CO 2 -NaCl dihedral angles: constraints on carbonate permeability and the role of deformation during fluid infiltration

The geochemistry of metamorphic quartz vein formation in Barrow’s index mineral zones north of Stonehaven, Scotland, was investigated in order to assess regional fluid flow and mass transfer. Metamorphic grade in the Dalradian metasediments increases to the north–northwest away from the Highland Boundary Fault (HBF) and associated ophiolitic rocks of the Highland Border Complex (HBC), passing through the Chlorite (Chl), Biotite (Bt), Garnet (Grt), Chloritoid (Cld), and Staurolite (St) zones. Syn-metamorphic fluid infiltration at 462±8.8 Ma (Breeding et al. in Am Mineral 89:1067, 2004) produced considerable quartz veining. Vein abundance varies from about 5 to 15 volume percent of the outcrops; veins tend to be more abundant in metapelitic layers than in metapsammitic ones. Metamorphic veins are surrounded by centimeter- to decimeter-wide zones of chemical and mineralogical alteration (selvages). Porphyroblasts, particularly Bt, Grt, Cld, and St, are typically larger in selvages than in wallrocks distal to veins. The altered selvages underwent fluid-driven addition of Na, Ca, and Sr, and loss of K, Rb, and Ba. Alteration is most intense within ∼750 m of the HBF, but is still very significant at the northern end of the field area some 2 km away. Mg/FeT (FeT=total iron) was either unchanged or increased due to alteration. Silica was added at some Chl and Bt zone localities near the HBF. Pb mass transfer was variable although Pb was added at a number of locations. Rare Earth elements (REE) were generally immobile, but light REE and possibly heavy REE were lost at one field site. The gain of Na and Ca and loss of K promoted the growth of plagioclase at the expense of micas (particularly muscovite) in selvages and wallrock inclusions throughout the field area and, probably, some calcite and/or dolomite growth directly adjacent to the HBF. The Ca gains were also critical for epidote production in the Bt zone. Gains of Ca and increases in Mg/FeT helped to stabilize Grt at the expense of Cld and St in some selvages. Hornblende and cummingtonite were discovered in strongly altered metapelitic rocks at one Cld zone locality. The metasomatism puts important constraints on the processes of mass transfer and suggests two models for regional fluid flow. In the first model, fluid flow in a direction of increasing temperature downward along the HBF added Na and Ca, and removed K from the Dalradian. In the second model, fluid flow upward from the HBC transported Na and Ca into the overlying Dalradian and, at the same time, stripped out K. The latter model is favored because it can most readily account for silica addition near the HBF, but neither model can be ruled out at present. In either case, the veins represent fractures that transmitted very large time-integrated fluid fluxes of at least ∼104 m3 (fluid)/m2 (rock). Consequently, the veins were conduits for regional fluid flow that caused considerable open-system chemical and mineralogical alteration during metamorphism.

Regional-scale fluid flow and element mobility in Barrow’s metamorphic zones, Stonehaven, Scotland

Vein-controlled retrograde infiltration of H2O-CO2 fluids into Dalradian epidote amphibolite facies rocks of the SW Scottish Highlands under greenschist facies conditions resulted in alteration of calcite-rich marble bands to dolomite and spatially associated 18O enrichment of about 10%. on a scale of metres. Fluid inclusion data indicate that the retrograde fluid was an H2O-salt mixture with a low CO2 content, and that the temperature of the fluid was about 400d C. Detailed petrographic and textural (backscattered electron imaging) studies at one garnet-grade locality show that advection of fluid into marbles proceeded by a calcite-calcite grain edge flow mechanism, while alteration of non-carbonate wall-rock is associated with veinlets and microcracks.



Stable isotopic analysis of carbonates from marble bands provides evidence for advection of isotopic fronts through carbonate wall-rocks perpendicular to dolomite veins, and fluid fluxes in the range 2.4–28.6 m3/m2 have been computed from measured advection distances. Coincidence of isotope and reaction fronts is considered to result from reaction-enhanced kinetics of isotope exchange at the reaction front. Front advection distances are related to the proportion of calcite to quartz in each marble band, with the largest advection distance occurring in nearly pure calcite matrix. This relationship indicates that fluid flow in carbonates is only possible along fluid-calcite-calcite grain edges. However, experimental constraints on dihedral angles in calcite-fluid systems require that pervasive infiltration occurred in response to calcite dissolution initiated at calcite-calcite grain junctions rather than to an open calcite pore geometry.



The regional extent of the retrograde infiltration event has been documented from the high δ18O of dolomite-ankerite carbonates from veins and host-rocks over an area of least 50 × 50 km in the SW Scottish Highlands. Isotopically exotic 18O-rich retrograde fluids have moved rapidly upwards through the crust, inducing isotopic exchange and mineral reaction in wall-rocks only where lithology, pore geometry or mineral solubilities, pressure and temperature have been appropriate for pervasive infiltration to occur.

Controls on the mechanisms of fluid infiltration and front advection during regional metamorphism: a stable isotope and textural study of retrograde Dalradian rocks of the SW Scottish Highlands

J. B. Fein

Papers

Controls on the mechanisms of fluid infiltration and front advection during regional metamorphism: a stable isotope and textural study of retrograde Dalradian rocks of the SW Scottish Highlands