ALBERT

Notes: The origins and volumes of waters which mass-transport silica in sedimentary basins remain obscure. Many previous analytical studies have illustrated cases where quartz cements in sandstones originate from complex and variable fluids. By contrast we show, by using a combination of separation and analytical techniques, that in Lower Permian sandstones of the southern North Sea the cementing fluid was isotopically uniform during growth of quartz cement with a δ1BO of 19.6 + 1.0%‰ V-SMOW. In this relatively uniform fluid quartz cements grew and developed complex cathodoluminescence (CL) zonations. Petrographic data show that 8–10% quartz cement (locally 30%) was imported into this 380 km2× 180 m thick aeolian sandstone, and cement distribution controlled by depositional permeabilities. We infer a large-scale, high volume, flux of evolved meteoric fluid during 2 km deep burial, and show that complex CL zonation may arise from relatively subtle changes in water composition.

Notes: Retrograde exchange of oxygen isotopes between minerals in igneous and metamorphic rocks by means of diffusion is explored using a finite difference computer model, which predicts both the zonation profile of δ18O within grains, and the bulk δ18O value of each mineral in the rock. Apparent oxygen isotope equilibrium temperatures that would be observed in these rocks are calculated from the δ18O values of each mineral pair within the rock. In systems which cool linearly from a sufficiently high temperature or at a low enough cooling rate, such that the final oxygen isotope values are not dependent upon the initial oxygen isotope values (‘slow cooling’), the apparent oxygen isotope temperature derived for a rock composed of a single mineral pair can be shown to be simply related to the Dodson closure temperatures (Tc) for the two phases and the mode of the rock. Adding a third phase into a system which undergoes ‘slow’ cooling will cause the apparent temperature derived for the two minerals already present to differ from the simple relationship for a two-phase system. In some systems oxygen isotope reversals can be developed. If cooling is not ‘slow’, then the mineral δ18O values resulting from cooling will be partly dependent upon the initial temperature of the system concerned. The model successfully simulates the mineral δ18O values that are often observed in granitic rocks. Application of the model will help in assessing the validity of oxygen isotope thermometry in different geological settings, and allows quantitative prediction of the oxygen isotope fractionations that are developed in cooling closed systems.

Notes: The highest grade pelitic and semipelitic rocks of the Ballachulish aureole are dominantly potash feldspar + cordierite + biotite hornfelses with widely variable amounts of quartz, plagioclase, andalusite, sillimanite and corundum (together with accessory phases). On a microscopic scale these hornfelses show textural evidence of the presence of melt, whilst on a mesoscopic scale they contain a variety of leucosomes. Oxygen isotope studies have been carried out on both whole rocks and mineral separates in order to: (1) assess the sources of molten and volatile constituents and (2) determine the extents of isotopic homogenization and equilibration. Data from localities with both restricted and extensive evidence of leucosomes and melt development are compared, as well as one locality with petrographic evidence of melt incursion from the igneous complex.The whole-rock δ18O values of the leucosomes (10.5–14.9%.) are in general similar to the immediately adjacent mesosomes (9.9–14.5%.) which are typically cordierite- and feldspar-rich hornfelses. Isotopic evidence is thus consistent with an in-situ partial melt origin for the leucosomes, without the substantial addition of externally derived components. In the area of extensive melt development, the ‘chaotic zone’, it is possible there was addition of an H2O-rich fluid phase (6-13 wt%) from the igneous complex which resulted in a slight lowering of δ18O values by 0.5–1.0%.Quartz mineral separates were used to assess the degree of local isotopic homogenization. In the extensively molten area (chaotic zone) there is extensive homogenization between rock layers (quartz δ18O usually within 1.0%), whilst in less molten areas δ18O quartz has a range of c. 3.0%. The greater homogenization in the chaotic zone is attributed to the increased degree of melting and infiltration of H2O-rich fluid from the igneous complex.

Notes: The contact aureole developed in siliceous carbonates surrounding the Beinn an Dubhaich granite, Skye, shows textural and stable isotope evidence for infiltration of aqueous fluids during both prograde and retrograde metamorphism. Strongly depleted isotope compositions of reaction-product calcite correlate with high silica and fluorine contents, demonstrating a strong link between isotopic alteration and metasomatism by fluids with a significant magmatic component, even at the margins of the aureole. The oxygen and carbon isotope compositions of the carbonates form a linear cluster with a positive slope of about five, consistent with the depletion of isotope compositions by the infiltration of magmatic and/or meteoric fluids. Rayleigh fractionation during devolatilization played a minor role in determining the final isotope composition.Stable isotope compositions of coexisting calcite–dolomite pairs show varying amounts of isotopic disequilibrium, which correlate with the inferred fluid infiltration mechanism. Much of the calcite in dolostones is the product of infiltration-driven reactions along fractures, and is greatly depleted isotopically relative to the host dolomite, especially at talc grade. At higher grades the calcite–dolomite fractionation is smaller, probably due to both increased fluid–rock interaction and a greater tendency for fluid infiltration to be pervasive on the grain-scale. Limestones generally show near-equilibrium fractionation of oxygen and carbon owing to the overwhelming compositional influence of the host calcite. Veins formed during late-stage hydrothermal circulation have strongly 18O-depleted compositions relative to the host rock.No small-scale spatial patterns to the isotopic depletion were observed, but the extent of fluid infiltration was greatest in the west of the aureole. Fluid infiltration was clearly highly heterogeneous, with no evidence of a consistent flow direction. It is not possible to determine fluid fluxes or flow directions from one-dimensional flow models based on continuum flow in the Beinn an Dubhaich aureole.

Notes: Calcite and quartz veins have formed, and are forming, in steeply dipping fissures in the actively rising Alpine Schist metamorphic belt of New Zealand. The fluids that deposited these minerals were mostly under hydrostatic pressure almost down to the brittle-ductile transition, which has been raised to 5-6 km depth by rapid uplift. Some fluids were trapped under lithostatic pressures. Fluids in the fissure veins were immiscible H2O + NaCl-CO2 mixtures at 200-350d̀ C. Bulk fluid composition is 15-20 mol% CO2 and 〈4.3 total mol CH4+ N2+ Ar/100mol H2O. Water hydrogen isotopic ratio δDH2O in the fissure veins spans -29 to -68‰, δ18OH2O -0.7 to 8.5‰, and bulk carbon isotopic ratio δ13C ranges from -3.7 to -11.7‰. The oxygen and hydrogen isotopic data suggest that the water has a predominantly meteoric source, and has undergone an oxygen isotope shift as a result of interaction with the host metamorphic rock. Similar fluids were present during cooling and uplift. Dissolved carbon is not wholly derived from residual metamorphic fluids; part may be generated by oxidation of graphite.

Notes: 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 400d̀ 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.

Notes: Spheroidal dolomite crystals occur in the karstified top of a Dinantian dolomite sequence in eastern Belgium. The spheroidal dolomite crystals are best developed at the base of the karst system. The dolomite crystals are characterized by a spherulitic or dumb-bell inclusion pattern, and are overgrown by dolomite cements with a rhombohedral outline. They are considered to be bacterially related precipitates based on, (1) textural similarities with documented bacteriogenic precipitates, (2) the presence of ‘bacterial’microspheres and framboidal pyrite embedded within the dolomite, and (3) their general geological setting. The geochemical characteristics of the dolomites and associated minerals support a bacterial origin. The ubiquity of framboidal pyrite, depleted in 34S (δ34S=— 22.4 to — 25.5%oCDT), testifies to a period of bacterial sulphate reduction. The isotopic composition of the spheroidal dolomites (δ13C=— 2.4 to - 3.2%oPDB and δ18O=— 3.8 to - 3.4%oPDB) suggest a contribution from oxidized organic carbon produced during bacterial sulphate reduction. Sulphate reduction may also result in a concomitant 18O depletion if the system is nearly closed. It is however, evident from the sulphur isotopic composition of associated framboidal pyrite that the system was fairly open. The 18O depletion of the spheroidal dolomite crystals (δ18O=— 3.8 to — 3.4%oPDB) and their occurrence adjacent to, and within karst cavities suggests a mixing zone origin, with a significant proportion of freshwater in it. The rhombohedral cement-overgrowths have calculated δ18O values in the range of 0 to +5.3%oPDB, which reflect precipitation from normal to slightly evaporated contemporaneous seawater.

Notes: In topographic flat areas, sedimentary settings may vary from one outcrop to another. In these settings, calcite precipitates may yield macroscopically similar columnar features, although they are products of different sedimentary or diagenetic processes. Three columnar calcite crystal fabrics, i.e. rosettes, palisade crusts and macro-columnar crystal fans, have been differentiated near and at the contact between Upper Tournaisian dolomites and limestones along the southern margin of the Brabant-Wales Palaeohigh. Their petrographic characteristics, and geochemical and fluid inclusion data provide information on the (dia)genetic processes involved. Rosettes composed of non-luminescent columnar calcite crystal fans (1–5 cm in diameter) developed on top of one another, forming discrete horizons in repetitive sedimentary cycles. The cycles consist of three horizons: (I) a basal horizon with fragments from the underlying horizon, (II) a micrite/microspar horizon with incipient glaebules, (III) an upper horizon consisting of calcite rosettes, with desiccation features. The petrographical features and δ18O signatures of −10·0 to −5·5‰ and δ13C values of −5·5 to −3·2‰ support either evaporative growth, an evaporative pedogenic origin, or overprinting of marine precipitates. Palisade crusts, composed of a few to 10 mm long non-luminescent calcite crystals, coat palaeokarst cavities. Successive palisade growth-stages occur which are separated by thin laminae of micrite or detrital quartz, displaying a geopetal arrangement. Palisade crusts are interpreted as intra-Mississippian speleothems. This interpretation is supported by their petrographic characteristics and isotopic signature (δ18O = −8·7 to −6·5‰ and δ13C = −4·8 to −2·5‰). Macro-columnar crystals, 1–50 cm long, developed mainly perpendicular to cavity walls and dolomite clasts. Crystal growth stages in the macro-columnar crystals are missing. δ18O values vary between −16·4 and −6·8‰ and δ13C values between −5·2 and −0·9‰. These features possibly support a late diagenetic high temperature precipitation in relation to hydrothermal karstification.

Notes: Abstract The sulphide deposits of the Iberian Pyrite Belt (IPB) represent an ore province of global importance. Our study presents 113 new sulphur isotope analyses from deposits selected to represent the textural spectrum of ores. Measured 34S values range from −26 to +10‰ mostly for massive and stockwork ores, in agreement with data previously published. In situ laser 34S analyses reveals a close correlation of 34S with texture. Primary diagenetic textures are dominated by relatively low 34S (−8‰ to −2‰), whereas stockwork feeder textures are dominated by higher 34S (∼+3‰ to +5‰). Intermediate textures (mainly coarse textures in stratiform zones) have intermediate 34S, although they are mostly dominated by the high 34S component. Rare barite has a homogeneous 34S around +18‰, which is consistent with direct derivation from Lower Carboniferous seawater sulphate. A dual source of sulphide sulphur in the IPB deposits has been considered. A hydrothermal source, derived from reduction of coeval seawater sulphate in the convective systems, is represented by sulphide in the feeder zones. Here variations in 34S are caused by variations in the extent of the sulphate reduction, which governs the SO4:H2S ratio. The second end-member was derived from the bacterial reduction of coeval seawater sulphate at or near the surface, as reflected in the primary textures. A distinct geographical variation in 34S and texture from SW (more bacteriogenic and primary textures) to NE (more hydrothermal textures and 34S) which reflects a variation in the relative input of each source was likely controlled by local geological environments. Given that the sulphur isotope characteristics of the IPB deposits are unlike most VMS and Kuroko deposits, and noting the dominance of a mixed reduced sedimentary and volcanic environment, we suggest that the IPB could represent an ore style which is intermediate between volcanic and sedimentary hosted massive sulphide types.

Notes: Abstract Mo mineralization within the Galway Granite at Mace Head and Murvey, Connemara, western Ireland, has many features of classic porphyry Mo deposits including a chemically evolved I-type granite host, associated K- and Si-rich alteration, quartz vein(Mace Head) and granite-hosted (Murvey) molybdenite, chalcopyrite, pyrite and magnetite mineralization and a gangue assemblage which includes quartz, muscovite and K-feldspar. Most fluid inclusions in quartz veins homogenize in the range 100–350°C and have a salinity of 1–13 eq. wt.% NaCl. They display Th-salinity covariation consistent with a hypothesis of dilution of magmatic water by influx of meteoric water. CO2-bearing inclusions in an intensely mineralized vein at Mace Head provide an estimated minimum trapping temperature and pressure for the mineralizing fluid of 355°C and 1.2 kb and are interpreted to represent a H2O-CO2 fluid, weakly enriched in Mo, produced in a magma chamber by decompression-activated unmixing from a dense Mo-bearing NaCl-H2O-CO2 fluid. δ34S values of most sulphides range from c. 0‰ at Murvey to 3–4‰ at Mace Head and are consistent with a magmatic origin. Most quartz vein samples have δ18O of 9–10.3‰ and were precipitated from a hydrothermal fluid with δ18O of 4.6–6.7‰. Some have δ18O of 6–7‰ and reflect introduction of meteoric water along vein margins. Quartz-muscovite oxygen isotope geothermometry combined with fluid inclusion data indicate precipitation of mineralized veins in the temperature range 360–450°C and between 1 and 2 kb. Whole rock granite samples display a clear δ18O-δD trend towards the composition of Connemara meteoric waters. The mineralization is interpreted as having been produced by highlyfractionated granite magma; meteoric water interaction postdates the main mineralizing event. The differences between the Mace Head and Murvey mineralizations reflect trapping of migrating mineralizing fluid in structural traps at Mace Head and precipitation of mineralization in the granite itself at Murvey.