Oxygen and hydrogen isotope study of high-pressure metagabbros and metabasalts (Cyclades, Greece): implications for the subduction of oceanic crust

Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ¹⁸O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ¹⁸O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by ¹⁸O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δ_{glaucophane−garnet} = 1.37 ± 0.24‰ and Δ_{omphacite−garnet} = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 10⁶/T ² (in Kelvin) of A_{glaucophane−garnet} = 0.87 ± 0.15 and A_{omphacite−garnet} = 0.72 ± 0.24. A fractionation of Δ_{glaucophane–actinolite} = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999     

Oxygen and hydrogen isotope studies on minerals from alpine fissures and their gneissic host rocks,Western Tauern Window (Austria)

Fourteen cogenetic quartz-biotite pairs from gneissic wall rocks, and 22 quartz, 16 calcite, and 8 biotite samples and 1 sample of albite from fissure-filling veins in the Western Tauern Window were analyzed for their oxygen isotope composition. The δ¹⁸O values show the following ranges: (a) quartz, +6.0 in fissure in amphibolite to +10.3 in fissures in granite gneisses; (b) biotite, +2.5 to +6.7; and (c) calcite, +7.0 to +8.9. The δ¹⁸O value of albite is +7.1. Only a small variation in the hydrogen isotope composition of biotite was detected. δD values of 7 biotites from gneisses and fissure fillings varied from −54 to −59. There is no significant difference in the hydrogen isotope composition of fissure biotite and biotite from the host rock. This indicates that a common water source of probably deep-seated origin existed, with no detectable contribution from isotopically light meteoric water. Oxygen isotope fractionations between coexisting quartz and biotite of 3.5 to 7.0‰ indicate equilibrium temperatures of 640 ° to 450 ° C, respectively, using the fractionation curve of Hoernes and Friedrichsen (1978). The highest temperatures of equilibration are for the rocks at the Alpenhauptkamm, i.e., the central part of the Tauern Window. Successively lower temperatures are found to the north and to the south of the Alpenhauptkamm along a traverse through Penninic units of the Tauern Window. The metamorphism of the host rocks and the filling of fissures has occurred at the same temperature in a given sample locality.     

Oxygen and hydrogen isotope geochemistry of gneisses associated with ultrahigh pressure eclogites at Shuanghe in the Dabie Mountains

The oxygen and hydrogen isotope compositions of minerals and whole rock were determined for two types of gneiss (biotite gneiss and granitic gneiss) associated with ultrahigh pressure (UHP) eclogites in the Shuanghe district of the eastern Dabie Mountains. There are significant differences in δ¹⁸O between the two gneisses: the UHP biotite gneiss varying from −4.3‰ to 10.6‰ similar to the associated eclogites, whereas the non-UHP granitic gneiss ranges only from −3.8‰ to 1.2‰. The δD values are similar in the two gneisses with −37 to −64‰ for epidote/zoisite, −92 to −83‰ for amphibole, and −63 to −109‰ for biotite/phengite. Hydrogen isotope disequilibrium among the coexisting hydroxyl-bearing minerals is ascribed to retrograde exchange subsequent to amphibolite-facies metamorphism. Oxygen isotopic equilibrium has been preserved among various minerals in both gneisses regardless of the large variation in rock δ¹⁸O. Oxygen isotopic geothermometers yield different but regular temperatures corresponding to the closure temperatures of oxygen diffusion in the minerals. The metamorphic temperatures of both eclogite facies and amphibolite facies have been recovered in mineral pairs from the biotite gneiss. The isotopic temperatures for the granitic gneiss are mostly in accordance with amphibolite-facies metamorphism. However, high temperatures of 550 to 650 °C are obtained from those minerals resistant to retrograde oxygen isotope exchange, implying that the granitic gneiss may have experienced higher temperature metamorphism than expected from petrologic thermometers. The ¹⁸O-depletion of both gneisses is interpreted to result from meteoric-hydrothermal exchange before/during plate subduction. Therefore, the measured δ¹⁸O values of the gneisses reflect the oxygen isotope compositions of their protoliths prior to the UHP metamorphism. It is inferred that the UHP unit is in foreign contact with the non-UHP unit like a tectonic melange, but both of them experienced the two common stages of geodynamic evolution: (1) ¹⁸O-depletion prior to the UHP metamorphism, (2) uplifting since the amphibolite-facies metamorphism. Received: 5 May 1998 / Accepted: 27 August 1998     

Volcanogenic-related origin of sulfide-rich quartz veins: evidence from O and S isotopes at the Géant Dormant gold mine, Abitibi belt, Canada

The Géant Dormant gold mine is a sulfide-rich quartz vein gold deposit hosted by a volcano-sedimentary sequence and an associated felsic endogenous dome and dikes. The auriferous quartz-sulfide veins were preceded by two synvolcanic gold-bearing mineralizing events: early sulfidic seafloor-related and later disseminated pyrite in the felsic dome. This deposit differs from classical Archean auriferous quartz vein deposits by the low carbonate and high sulfide contents of the veins and by their formation prior to ductile penetrative deformation. The δ¹⁸O values of quartz associated with seafloor-related auriferous sulfides average 11.9 ± 0.6‰ (n = 3). The seafloor hydrothermal fluids had a δ¹⁸O value of 3.2‰ calculated at 250 °C. The oxygen isotope composition of quartz and chlorite from veins average 12.5 ± 0.3‰ (n = 20) and 5.9 ± 1.1‰ (n = 4) respectively. Assuming oxygen isotope equilibrium between quartz and chlorite, the veins formed at a temperature of ∼275 °C, which is consistent with the calculated temperature of 269 ± 10 °C from chlorite chemistry. The gold-bearing fluids had a δ¹⁸O value of 4.7‰ calculated at 275 °C. The δ³⁴S values of sulfides from the three gold events range from 0.6 to 2.8‰ (n = 32) and are close to magmatic values. Sulfur isotope geothermometry constrains the sulfide precipitation in the gold-bearing veins at a temperature of ∼350 °C. The similarity of the isotope data, the calculated δ¹⁸O of the mineralizing fluids and the likely seawater fluid source suggest that the three mineralizing events are genetically related to a volcanogenic hydrothermal system. The high value of the auriferous fluids (δ¹⁸O = 4.7‰) is attributed to a significant magmatic fluid contribution to the evolved seawater-dominated convective hydrothermal system. The two-stage filling of veins at increasing temperature from quartz-chlorite (275 °C) to sulfides (350 °C) may reflect the progressive maturation of volcanogenic hydrothermal systems. These results, together with field and geochemical data, suggest that formation of gold-rich volcanogenic systems require specific conditions that comprise a magmatic fluid contribution and gold from arc-related felsic rocks, coeval with the mineralizing events. This study shows that some auriferous quartz-vein orebodies in Archean terranes are formed in volcanogenic rather than mesothermal systems. Received: 12 December 1998 / Accepted: 5 July 1999     

Stable isotopes and amphibole chemistry on hydrothermally altered granitoids in the North Chilean Precordillera: a limited role for meteoric water?

Whole rock and mineral stable isotope and microprobe analyses are presented from granitoids of the North Chilean Precordillera. The Cretaceous to Tertiary plutonic rocks contain important ore deposits and frequently display compositional and textural evidence of hydrothermal alteration even in barren rocks. Deuteric alteration includes replacement of biotite and amphibole by chlorite and epidote, sericitization and saussuritization of feldspars, and uralitization of clinopyroxene and/or amphibole. While whole rock compositions are not significantly affected, compositional variations in amphiboles suggest two types of hydrothermal alteration. Hornblende with actinolitic patches and rims and tight compositional trends from hornblende to Mg-rich actinolite indicate increasing oxygen fugacity from magmatic to hydrothermal conditions. Uralitic amphiboles exhibiting irregular Mg-Fe distribution and variable Al content are interpreted as reflecting subsolidus hydration reactions at low temperatures. The δD values of hydrous silicates vary from −63 to −105‰. Most δ¹⁸O values of whole rocks are in the range of 5.7 to 7.7‰ and are considered normal for igneous rocks in the Andes. These δ¹⁸O values also coincide well with the oxygen isotope composition of geochemically similar recent volcanics from the Central Andean Volcanic Zone (δ¹⁸O = 7.0–7.4‰). Only one sample in this study (δ¹⁸O = 3.0‰) appears to be depleted by isotope exchange with light meteoric water at high temperatures. The formation of secondary minerals in all other intrusions is mainly the product of deuteric alteration. This also holds true for the sample from El Abra, the only pluton associated with mineralization. This indicates the dominant role of a magmatic rather than a meteoric fluid in the alteration of the Cretaceous and Tertiary granitoids in northern Chile. Received: 8 July 1998 / Accepted: 15 April 1999     

Ultrahigh-pressure metamorphic rocks from the Chinese Continental Scientific Drilling Project: II Oxygen isotope and fluid inclusion distributions through vertical sections

In order to reconstruct the formation and exhumation mechanisms of UHP metamorphic terrains, the Chinese Continental Scientific Drilling Program (CCSD) has been carried out in Donghai of the Dabie-Sulu ultrahigh-pressure (UHP) metamorphic belt, East China. Eclogite, gneiss, amphibolite (retrograded from eclogite), ultramafic rocks, and minor schist and quartzite have been drilled. Aiming to reveal the fluid behaviour in a vertical sequence of an UHP slab, we investigated fluid inclusion and oxygen isotope characteristics of selected drillcores from the main hole and the pilot-holes PP2 and ZK 703 of the CCSD. More than 540 laser-ablation oxygen isotope analyses on garnet, omphacite, quartz, kyanite, amphibole, phengite, rutile, epidote, amphibole, plagioclase, and biotite from various rocks in the depth range of 0–3,000 m (mainly eclogite and gneiss) show that the investigated rocks can be divided into two groups: ¹⁸O-depleted rocks (as low as δ¹⁸O = −7.4‰ for garnet) indicate interaction with cold climate meteoric waters, whereas ¹⁸O-normal rocks (with bulk δ¹⁸O > +5.6‰) have preserved the O-isotopic compositions of their protoliths. Meteoric water/rock interaction has reached depths of at least 2,700 m. Oxygen isotope equilibrium has generally been achieved. Isotopic compositions of mineral phases are homogeneous on a mm to cm scale regardless of lithology, but heterogeneous on the scale of a few metres. Oxygen isotope distributions in the vertical sections favour an “in situ” origin of the UHP metamorphic rocks. The very negative δ¹⁸O eclogites usually have higher hydroxyl-mineral contents than the normal δ¹⁸O rocks, indicating higher water content during UHP metamorphism. Fluid inclusion data suggest that rocks with depleted ¹⁸O compositions have had different fluid histories compared to those with normal δ¹⁸O values. Rocks with depleted ¹⁸O mainly have primary medium-to-high salinity inclusions in omphacite, kyanite and quartz, and abundant secondary low-salinity or pure water inclusions in quartz, indicating a high-salinity-brine-dominated fluid system during peak UHP metamorphism; no carbonic inclusions have been identified in these rocks. By contrast, primary very high-density CO₂ inclusions are commonly found in the rocks with normal δ¹⁸O values. These observations suggest that fluid and oxygen isotope composition of minerals are related and reflect variable degrees of alterations of the Dabie-Sulu UHP metamorphic rocks.     

Oxygen isotopic study of Late Mesozoic cooling of the Mount Barcroft area,central White Mountains,eastern California

The Middle Jurassic Barcroft mafic granodiorite and Late Cretaceous, ternary-minimum McAfee Creek Granite are important components of the igneous arc sited along the SW North American margin. Bulk-rock analyses of 11 samples of the metaluminous, I-type Barcroft comagmatic suite have an average δ¹⁸O value of 7.4±0.6‰ (all values±1σ). Four Barcroft specimens average ε_Nd=?3.6±1.8, ⁸⁷Sr/⁸⁶Sr=0.707±0.001. The pluton consists of petrochemically gradational, Ca-amphibole-rich gabbro/diorite, granodiorite, metadiorite, and rare alaskite–aplite; for most of the pluton, oxygen isotope exchange of quartz, feldspar(s), biotite, and Ca-amphibole accompanied local deuteric alteration. Eight specimens of slightly peraluminous granitic rocks of the muscovite-bearing McAfee Creek series have an average δ¹⁸O of 8.6±0.5‰. Four McAfee-type samples average ε_Nd=?7.8±1.7, ⁸⁷Sr/⁸⁶Sr=0.711±0.004. For both plutons, bulk-rock evidence of exchange with near-surface water is lacking, suggesting ~5–10 km cooling depths. Barcroft minerals exhibit regular oxygen isotopic partitioning from high to low δ¹⁸O in the sequence quartz>plagioclase>K-feldspar>>amphibole≥biotite. Along the SE margin of the pluton, quartz and biotite in Lower Cambrian quartzites are higher in δ¹⁸O, and show slightly larger fractionations than igneous analogues. Exchange with fluids derived from these heated, contact-metamorphosed country rocks increased bulk ¹⁸O/¹⁶O ratios of Barcroft border rocks (and constituent plagioclase+subsolidus tremolite–actinolite), especially of granitic dikes transecting the wall rocks. Oxygen isotope thermometry for seven Barcroft pluton quartz–amphibole and six quartz–biotite pairs indicate apparent subsolidus temperatures averaging 519±49 °C. Quartz–plagioclase pairs from two Barcroft granodiorites yield values of 519 and 515 °C. A quartz–biotite pair from a quartzite adjacent to the Barcroft pluton yields an apparent temperature of 511 °C, in agreement with estimates based on contact metamorphic parageneses. Except for its SE margin, Barcroft pluton silicates evidently exchanged oxygen isotopes under local deuteric conditions. Compatible with Ca-amphibole thermobarometric analyses, areal distributions for quartz–plagioclase, quartz–amphibole, and quartz–biotite pairs reveal that putative annealing temperatures are lowest in NE-trending axial portions of the Barcroft body, so it simply cooled inwards. Intrusion ~70 million years later by the McAfee Creek Granite had no discernable effect on δ¹⁸O values of Barcroft minerals and bulk rocks.     

Seeing past the effects of re-equilibration to reconstruct magmatic gradients in plutons: La Gloria Pluton, central Chilean Andes

This study of La Gloria pluton in the Chilean Andes evaluates what information about magmatic conditions can be extracted from minerals in a granitic pluton, despite lower-temperature re-equilibration. The pluton is zoned vertically from granodiorite/quartz monzodiorite to quartz monzonite at the roof, with the uppermost 1500 m showing the strongest modal and compositional trends. This mimics the pattern frequently inferred from zoning in voluminous ignimbrites: a strongly zoned cap overlying a more homogeneous main␣body. The presence of large, euhedral amphibole ± biotite at the chamber margins and roof indicate that water was concentrated there. Biotite and amphibole compositions indicate a roofward increase in magmatic f _HF, f _HCl and F/Cl ratio, analogous to pre-eruptive volatile gradients recorded in zoned ignimbrites. Hornblende that crystallized directly from the melt in the volatile-rich wall and roof zones yields total-Al solidification pressures of ˜1 kbar, consistent with the estimated 4000 m of cover at the time of emplacement. In the core of the pluton, actinolitic amphibole formed by reaction of melt with early-crystallized clinopyroxene. Plag-cpx cumulate clots in the lower level are interpreted as early crystallizing phases entrained in rising granitic magma. Cores of amphibole phenocrysts in mafic enclaves suggest initial crystallization at pressures of 2–3 kbar. Lower Ti and Al contents of rims and acicular groundmass amphibole, overlapping the composition of amphibole in the host granitoid, indicate that the enclaves equilibrated with the host at the present exposure level in the presence of interstitial melt. A roofward relative increase in fO₂ of the magma is recorded by an increasing proportion of Fe-Ti oxides as a fraction of the mafic phases, greater Mn content of ilmenite, and constant or higher Mg/(Mg+Fe) in hornblende and biotite despite declining whole-rock MgO contents. Association␣of subhedral biotite and magnetite with actinolitic amphibole in clots implies a reaction: K-Ti-hb + O₂(gas) = bi + mt + actinolitic amph + titanite. Magnetite coexisting with biotite with Fe/(Fe+Mg) = 0.34– 0.40 implies temperatures of equilibration no lower than about 720–750 °C, i.e., late-magmatic rather than subsolidus. Saturation with respect to a water-rich vapor and subsequent diffusive loss of hydrogen may have caused this oxidation trend, which resulted in the most magnesian mafic phases occurring in the most compositionally evolved rocks, opposite to trends in most zoned ignimbrites, which presumably record conditions nearer the liquidus and prior to exsolution of a water-rich vapor. Two-feldspar and Fe-Ti-oxide geothermometers record subsolidus conditions in the pluton and yield higher temperatures for samples from the roof zone, suggesting that slower cooling at deeper levels allowed these minerals to continue to equilibrate to lower temperatures. Individual minerals span wide ranges in composition at any given level of the pluton, from those appropriate for phenocrysts, to those that record conditions well below the solidus. We suggest that the shallow level and isolated position of the pluton led to rapid escape of magmatic volatiles and rapid cooling, thereby preventing development of a long-lived hydrothermal system. Resulting small water/rock ratios may account for why late-magmatic and subsolidus re-equilibration were not pervasive. Received: 23 August 1996 / Accepted: 18 October 1996     

Oxygen isotope constraints on the petrogenesis of the Sybille intrusion of the Proterozoic Laramie Anorthosite Complex

The origin of monzonitic intrusions that are associated with Proterozoic massif-type anorthosite complexes is controversial. A detailed oxygen isotope study of the Sybille intrusion, a monzonitic intrusion of the Laramie Anorthosite Complex (Wyoming), indicates that either derivation from a basaltic magma of mantle origin with a metasedimentary component (∼20%) incorporated early in its magmatic history, or a partial melt of lower crustal rocks is consistent with the data. The oxygen isotope compositions of plagioclase, pyroxene and zircon from the Sybille monzosyenite, the dominant rock type in the Sybille intrusion, were analyzed in order to establish the isotopic composition of the source of the magma. Plagioclase δ¹⁸O values range from 6.77 to 9.17‰. We interpret the higher plagioclase δ¹⁸O values (average 8.69 ± 0.30‰, n = 19) to be magmatic in origin, lower plagioclase δ¹⁸O values (average 7.51 ± 0.44‰, n = 22) to be the result of variable subsolidus alteration, and pyroxene δ¹⁸O values (average 6.34 ± 0.38‰, n = 19) to be the result of closed-system diffusional exchange during cooling. Low magnetic zircons, which have been shown to retain magmatic oxygen isotope values despite high grade metamorphism and extensive subsolidus hydrothermal alteration, have δ¹⁸O values (7.40 ± 0.24‰, n = 11) which are consistent with our interpretation of the plagioclase and pyroxene results. Oxygen isotope data from all three minerals indicate that the magmatic oxygen isotope composition of the Sybille intrusion is enriched in ¹⁸O relative to the composition of average or “normal” mantle-derived magmas. This enrichment is approximately twice the oxygen isotope enrichment that could result from closed-system fractionation, rendering a closed-system, comag- matic petrogenetic model between the Sybille intrusion and the mantle-derived anorthositic lithologies of the Laramie Anorthosite Complex improbable. Received: 7 April 1998 / Accepted: 19 January 1999     

The La Unión Au ± Cu prospect,Camagüey District,Cuba: fluid inclusion and stable isotope evidence for ore-forming processes

The Camagüey district, Cuba, is known for its epithermal precious metal deposits in a Cretaceous volcanic arc setting. Recently, the La Unión prospect was discovered in the southern part of the district, containing gold and minor copper mineralization interpreted as porphyry type. Mineralization is hosted in a 73.0 ± 1.5 Ma calc–alkaline I-type oxidized porphyry quartz diorite intrusive within volcanic and volcaniclastic rocks of the early Cretaceous Guáimaro Formation. The porphyry is affected by propylitic alteration and crosscut by a network of quartz and carbonate veinlets and veins. Chlorite, epidote, sericite, quartz, and pyrite are the main minerals in the early veins which are cut by late carbonate and zeolite veins. Late barite pseudomorphously replaces pyrite. Gold is associated with pyrite as disseminations in the altered quartz diorite and in the veins, occurring as inclusions or filling fractures in pyrite with 4 g/t Au in bulk samples, and up to 900 ppm Au in in pyrite. Fluid inclusion and oxygen isotope data are consistent with a H₂O–NaCl–(KCl) mineralizing fluid, derived from the quartz diorite magma, and trapped at least at 425°C and 1.2 kbar. This primary fluid unmixed into two fluid phases, a hypersaline aqueous fluid and a low-salinity vapor-rich fluid. Boiling during cooling may have played an important role in metal precipitation. Pyrite δ³⁴S values for the La Unión prospect range between 0.71‰ and 1.31‰, consistent with a homogeneous magmatic sulfur source. The fluids in equilibrium with the mineralized rocks have estimated δ¹⁸O values from 8‰ to 11.8‰, calculated for a temperature range of 480–505°C. The tectonic environment of the La Unión prospect, its high gold and low copper contents, the physical–chemical characteristics of the mineralizing fluids and the isotopic signature of the alteration minerals and fluids indicate that the La Unión gold mineralization is similar to the porphyry gold type, even though the ore-related epidote–chlorite alteration can be classified as propylitic and not the classic potassic and/or phyllic alteration. The low copper contents in the prospect could be due to a mineralizing fluid previously saturated in copper, which is indicated by trapped chalcopyrite crystals in high-temperature fluid inclusions. The low-temperature paragenesis, represented by carbonate, zeolite and barite, indicates epithermal overprint. The study shows the potential for other gold porphyry-type deposits in the Cretaceous volcanoplutonic arc of Cuba.     

Geology and geochemistry of the Mammoth breccia pipe,Copper Creek mining district,southeastern Arizona: evidence for a magmatic–hydrothermal origin

The Copper Creek mining district, southeastern Arizona, contains more than 500 mineralized breccia pipes, buried porphyry-style, copper-bearing stockworks, and distal lead–silver veins. The breccia pipes are hosted by the Copper Creek Granodiorite and the Glory Hole volcanic rocks. The unexposed Mammoth breccia pipe, solely recognized by drilling, has a vertical extent of 800 m and a maximum width of 180 m. The pipe consists of angular clasts of granodiorite cemented by quartz, chalcopyrite, bornite, anhydrite, and calcite. Biotite ⁴⁰Ar/³⁹Ar dates suggest a minimum age of 61.5 ± 0.7 Ma for the host Copper Creek Granodiorite and ⁴⁰Ar/³⁹Ar dates on hydrothermal sericite indicate an age of 61.0 ± 0.5 Ma for copper mineralization. Fluid inclusion studies suggest that a supercritical fluid with a salinity of approximately 10 wt.% NaCl equiv. condensed to a dilute aqueous vapor (1–2.8 wt.% NaCl equiv.) and a hypersaline brine (33.4–35.1 wt.% NaCl equiv.). Minimum trapping temperatures are 375°C and trapping depths are estimated at 2 km. Sulfur isotope fractionation of cogenetic anhydrite and chalcopyrite yields a temperature of mineralization of 469 ± 25°C. Calculated oxygen and hydrogen isotope values for fluids in equilibrium with quartz and sericite range from 10.2‰ to 13.4‰ and −60‰ to −39‰, respectively, suggesting that the mineralizing fluid was dominantly magmatic. Evidence from the stable isotope and fluid inclusion analyses suggests that the fluids responsible for Cu mineralization within the Mammoth breccia pipe exsolved from a gray porphyry phase found at the base of the breccia pipe.     

Crystallization conditions of the Wiborg rapakivi batholith, SE Finland: an evaluation of amphibole and biotite mineral chemistry

Summary The wiborgite and dark wiborgite rapakivi granite phases of the Wiborg batholith in southeastern Finland compose about 80% of the total batholith area. A new study of the dominant mafic silicate minerals, in comparison with mafic silicates from more evolved granite phases, hybridized granite and mafic magmatic enclaves provide insights into the overall petrogenesis of the Wiborg batholith. All of the mafic silicate minerals are iron-rich, reflective of the whole rock compositions. Biotite is annitic, calcic amphibole is ferro-edenite to hastingsite, and subsolidus Fe-Mg amphibole is found as accessory grunerite. Temperatures derived from amphibole-plagioclase thermometry suggest crystallization at about ∼ 740 °C. Pressure estimates derived from Al in amphibole barometry range between 2.5 and 5.4 kilobars. This is noticeably higher than the previous estimates of 1 kbar for the Wiborg batholith. Oxygen fugacity estimates from biotite suggest low fO₂ initial values and increase from FMQ to above NNO for late stage granite phases. Received February 29, 2000; revised version accepted December 27, 2000     

Imprint of meteoric water on the stable isotope compositions of igneous and secondary minerals,Kap Edvard Holm Complex,East Greenland

 Hydrogen and oxygen isotope analyses have been made of hydrous minerals in gabbros and basaltic xenoliths from the Eocene Kap Edvard Holm intrusive complex of East Greenland. The analyzed samples are of three types: (1) primary igneous hornblendes and phlogopites that crystallized from partial melts of hydrothermally altered basaltic xenoliths, (2) primary igneous hornblendes that formed during late–magmatic recrystallization of layered gabbroic cumulates, and (3) secondary actinolite, epidote and chlorite that formed during subsolidus alteration of both xenoliths and gabbros. Secondary actinolite has a δ¹⁸O value of −5.8‰ and a δD value of −158‰. These low values reflect subsolidus alteration by low–δ¹⁸O, low–δD hydrothermal fluids of meteoric origin. The δD value is lower than the −146 to −112‰ values previously reported for amphiboles from other early Tertiary meteoric–hydrothermal systems in East Greenland and Scotland, indicating that the meteoric waters at Kap Edvard Holm were isotopically lighter than typical early Tertiary meteoric waters in the North Atlantic region. This probably reflects local climatic variations caused by formation of a major topographic dome at about the time of plutonism and hydrothermal activity. The calculated isotopic composition of the meteoric water is δD=−110 ± 10‰, δ¹⁸O ≈−15‰. Igneous hornblendes and phlogopites from pegmatitic pods in hornfelsed basaltic xenoliths have δ¹⁸O values between −6.0 and −3.8‰ and δD values between −155 and −140‰. These are both much lower than typical values of fresh basalts. The oxygen isotope fractionations between pegmatitic hornblendes and surrounding hornfelsic minerals are close to equilibrium fractionations for magmatic temperatures, indicating that the pegmatites crystallized from low–δ¹⁸O partial melts of xenoliths that had been hydrothermally altered and depleted in ¹⁸O prior to stoping. The pegmatitic minerals may have crystallized with low primary δD values inherited from the altered country rocks, but these values were probably overprinted extensively by subsolidus isotopic exchange with low–δD meteoric–hydrothermal fluids. This exchange was facilitated by rapid self–diffusion of hydrogen through the crystal structures. Primary igneous hornblendes from the plutonic rocks have δ¹⁸O values between +2.0 and +3.2‰ and δD values between −166 and −146‰. The ¹⁸O fractionations between hornblendes and coexisting augites are close to equilibrium fractionations for magmatic temperatures, indicating that the hornblendes crystallized directly from the magma and subsequently underwent little or no oxygen exchange. The hornblendes may have crystallized with low primary δD values, due to contamination of the magma with altered xenolithic material, but the final δD values were probably controlled largely by subsolidus isotopic exchange. This inference is based partly on the observation that coexisting plagioclase has been extensively depleted in ¹⁸O via a mineral–fluid exchange reaction that is much slower than the hydrogen exchange reaction in hornblende. It is concluded that all hydrous minerals in the study area, whether igneous or secondary, have δD values that reflect extensive subsolidus isotopic equilibration with meteoric–hydrothermal fluids. Received: 22 March 1994 / Accepted: 26 January 1995     

Relics of eclogite facies metamorphism in the Austroalpine basement,Hochgrössen (Speik complex), Austria

Summary Retrograde eclogites and serpentinites from the Hochgr?ssen massif, Styria, are parts of the Speik complex in the Austroalpine basement nappes of the Eastern Alps. They are in tectonic contact with pre-Alpine gneisses, amphibolites, and Permo-Triassic quartz phyllites (Rannach Series). The eclogites are derived from ocean-floor basalts with affinities to mid-ocean ridge and back-arc basin basalts. Fresh eclogites are rare and contain omphacite with a maximum of 39 mol% jadeite content, garnet (Py_15–19) and amphibole. Retrograde eclogites consist of amphibole and symplectites of Na-poor clinopyroxene (5–8 mol% Jd) + albite ± amphibole. Amphiboles are classified as edenite, pargasite, tschermakite, magnesiohornblende and actinolite. In relatively fresh eclogite, edenite is a common amphibole and texturally coexists with omphacite and garnet. An average temperature of 700 °C was obtained for eclogite facies metamorphism using garnet-pyroxene thermometry. A minimum pressure of 1.5 GPa is indicated by the maximum jadeite content in omphacite. Thermobarometric calculations using the TWEEQ program for amphibole in textural equilibrium with omphacite and garnet give pressures of 1.8–2.2 GPa at 700 °C. The equilibrium assemblage of Na-poor clinopyroxene, albite, amphibole and zoisite in the symplectites gives a pressure of about 0.6–0.8 GPa at 590–640 °C. ⁴⁰Ar/³⁹Ar radiometric dating of edenitic amphibole in textural equilibrium with omphacite gave a plateau age of 397.3 ± 7.8 Ma, and probably indicates retrograde cooling through the closure temperature for amphibole (∼500 °C). The age of the high-pressure metamorphism thus must be pre-Variscan and points to one of the earliest metamorphic events in the Austroalpine nappes known to date. Received June 11, 2000; revised version accepted January 2, 2001     

Meteoric incursion and oxygen fronts in the Dalradian metamorphic belt, southwest Scotland: a new hypothesis for regional gold mobility

Post-metamorphic quartz veins which occur over hundreds of square kilometres in the biotite zone of the Dalradian metamorphic belt consist of three principal types: anhedral quartz with pyrite, anhedral quartz with hematite, and prismatic quartz with hematite or rutile. The oxide minerals in anhedral veins have formed by oxidation of pre-existing sulphides, and gold was mobilized during this oxidation. Anhedral quartz veins formed from an aqueous fluid with up to 5 wt% dissolved salts and 16 wt% CO₂ at about 300 °C. Texturally later prismatic quartz crystals formed from a compositionally similar fluid which was undergoing phase separation at the H₂O-CO₂ solvus at 160–200 °C and 500 to 1200 bars fluid pressure. Oxygen isotope ratios for quartz from the veins range from 12.0 to 15.3‰, with hematite-bearing veins generally isotopically heavier than pyrite-bearing veins. Calculated fluid oxygen isotope ratios range from + 8‰ for pyrite-bearing veins to -2‰ for late prismatic crystals. The mineralizing fluid contained a substantial component of meteoric water whose isotopic and chemical composition evolved with progressive water-rock interaction. Evolution of meteoric fluid composition involved migration of oxidation and oxygen isotope fronts in the down-flow direction as head-driven water passed through structurally controlled fractures in the schist pile. A gold solubility trough occurs for the observed fluid in the oxidation frontal zone. Gold remobilization and reprecipitation occurred progressively as the oxidation front migrated through the schist pile.     

Hornblende–garnet–plagioclase thermobarometry: a natural assemblage calibration of the thermodynamics of hornblende

Calibrations are presented for an independent set of four equilibria between end-members of garnet, hornblende, plagioclase and quartz. Thermodynamic data from a large internally-consistent thermodynamic dataset are used to determine the ΔG° of the equilibria. Then, with the known mixing properties of garnet and plagioclase, the non-ideal mixing in amphibole is derived from a set of 74 natural garnet–amphibole–plagioclase–quartz assemblages crystallised in the range 4–13 kbar and 500–800 °C. The advantage of using known thermodynamic data to calculate ΔG° is that correlated variations of composition with temperature and pressure are not manifested in fictive derived entropies and volumes, but are accounted for with non-ideal mixing terms. The amphibole is modelled using a set of ten independent end-members whose mixing parameters are in good agreement with the small amount of data available in the literature. The equilibria used to calibrate the amphibole non-ideal mixing reproduce pressures and temperatures with average absolute deviations of 1.1 kbar and 35 °C using an average pressure–temperature approach, and 0.8 kbar with an average pressure approach. The mixing data provide not only a basis for thermobarometry involving additional phases, but also for calculation of phase diagrams in complex amphibole-bearing systems. Received: 8 November 1999 / Accepted: 7 July 2000     

Phase relations in the greenschist-blueschist-amphibolite-eclogite facies in the system Na2O-CaO-FeO-MgO-Al2O3-SiO2-H2O (NCFMASH), with application to metamorphic rocks from Samos, Greece

Calculated phase equilibria among the minerals sodic amphibole, calcic amphibole, garnet, chloritoid, talc, chlorite, paragonite, margarite, omphacite, plagioclase, carpholite, zoisite/clinozoisite, lawsonite, pyrophyllite, kyanite, sillimanite, quartz and H₂O are presented for the model system Na₂O-CaO-FeO-MgO-Al₂O₃-SiO₂-H₂O (NCFMASH), which is relevant for many greenschist, blueschist, amphibolite and eclogite facies rocks. Using the activity-composition relationships for multicomponent amphiboles constrained by Will and Powell (1992), equilibria containing coexisting calcic and sodic amphiboles could be determined. The blueschist–greenschist transition reaction in the NCFMASH system, for example, is defined by the univariant reaction sodic amphibole + zoisite = calcic amphibole + chlorite + paragonite + plagioclase (+ quartz + H₂O) occurring between approximately 420 and 450 °C at 9.5 to 10 kbar. The calculated petrogenetic grid is a valuable tool for reconstructing the PT-evolution of metabasic rocks. This is shown for rocks from the island of Samos, Greece. On the basis of mineral and whole rock analyses, PT-pseudosections were calculated and, together with the observed mineral assemblages and reaction textures, are used to reconstruct PT-paths. For rocks from northern Samos, pseudomorphs after lawsonite preserved in garnet, the assemblage sodic amphibole-garnet-paragonite-chlorite-zoisite-quartz and the retrograde appearance of albitic plagioclase and the formation of calcic amphibole around sodic amphibole constrain a clockwise PT-path that reaches its thermal maximum at some 520 °C and 19 kbar. The derived PT-trajectory indicates cooling during exhumation of the rocks and is similar to paths for rocks from the western part of the Attic-Cycladic crystalline complex. Rocks from eastern Samos indicate lower pressures and are probably related to high-pressure rocks from the Menderes Massif in western Turkey. Received: 8 July 1997 / Accepted: 11 February 1998     

K-feldspar–quartz and K-feldspar–plagioclase phase boundary interactions in garnet–orthopyroxene gneiss's from the Val Strona di Omegna, Ivrea–Verbano Zone, northern Italy

A detailed study based on textural observations combined with microanalysis [back scattered electron imaging (BSE) and electron microprobe analysis (EMPA)] and microstructural data transmission electron microscopy (TEM) has been made of K-feldspar micro-veins along quartz–plagioclase phase and plagioclase–plagioclase grain boundaries in granulite facies, orthopyroxene–garnet-bearing gneiss's (700–825 °C, 6–8 kbar) from the Val Strona di Omegna, Ivrea–Verbano Zone, northern Italy. The K-feldspar micro-veins are commonly associated with quartz and plagioclase and are not found in quartz absent regions of the thin section. This association appears to represent a localised reaction texture resulting from a common high grade dehydration reaction, namely: amphibole + quartz = orthopyroxene + clinopyroxene + plagioclase + K-feldspar + H₂O, which occurred during the granulite facies metamorphism of these rocks. There are a number of lines of evidence for this. These include abundant Ti-rich biotite, which was apparently stable during granulite facies metamorphism, and total lack of amphibole, which apparently was not. Disorder between Al and Si in the K-feldspar indicates crystallisation at temperatures >500 °C. Myrmekite and albitic rim intergrowths in the K-feldspar along the K-feldspar–plagioclase interface could only have formed at temperatures >500–600 °C. Symplectic intergrowths of albite and Ca-rich plagioclase between these albitic rim intergrowths and plagioclase suggest a high temperature grain boundary reaction, which most likely occurred at the start of decompression in conjunction with a fluid phase. Relatively high dislocation densities (>2 × 10⁹ to 3 × 10⁹/cm²) in the K-feldspar suggest plastic deformation at temperatures >500 °C. We propose that this plastic deformation is linked with the extensional tectonic environment present during the mafic underplating event responsible for the granulite facies metamorphism in these rocks. Lastly, apparently active garnet grain rims associated with side inclusions of K-feldspar and quartz and an exterior K-feldspar micro-vein indicate equilibrium temperatures within 20–30 °C of the peak metamorphic temperatures estimated for the sample (770 °C). Contact between these K-feldspar micro-veins and Fe-Mg silicate minerals, such as garnet, orthopyroxene, clinopyroxene or biotite along the interface, is observed to be very clean with no signs of melt textures or alteration to sheet silicates. This lends support to the idea that these micro-veins did not originate from a melt and, if fluid induced, that the water activity of these fluids must have been relatively low. All of these lines of evidence point to a high grade origin for the K-feldspar micro-veins and support the hypothesis that they formed during the granulite facies metamorphism of the metabasite layers in an extensional tectonic environment as the consequence of localised dehydration reactions involving the breakdown of amphibole in the presence of quartz to orthopyroxene, clinopyroxene, plagioclase, K-feldspar and H₂O. It is proposed that the dehydration of the metabasite layers to an orthopyroxene–garnet-bearing gneiss over a 4-km traverse in the upper Val Strona during granulite facies metamorphism was a metasomatic event initiated by the presence of a high-grade, low H₂O activity fluid (most likely a NaCl–KCl supercritical brine), related to the magmatic underplating event responsible for the Mafic Formation; and that this dehydration event did not involve partial melting. Received: 15 February 2000 / Accepted: 26 June 2000     

Oxygen isotope thermometry in carbonatites, Fuerteventura, Canary Islands, Spain

Summary Crystallization temperatures of the oceanic carbonatites of Fuerteventura, Canary Islands, have been determined from oxygen isotope fractionations between calcite, silicate minerals (feldspar, pyroxene, biotite, and zircon) and magnetite. The measured fractionations have been interpreted in the light of late stage interactions with meteoric and/or magmatic water. Cathodoluminescence characteristics were investigated for the carbonatite minerals in order to determine the extent of alteration and to select unaltered samples. Oxygen isotope fractionations of minerals of unaltered samples yield crystallization temperatures between 450 and 960°C (average 710°C). The highest temperature is obtained from pyroxene–calcite pairs. The above range is in agreement with other carbonatite thermometric studies.This is the first study that provides oxygen isotope data coupled with a CL study on carbonatite-related zircon. The CL pictures revealed that the zircon is broken and altered in the carbonatites and in associated syenites. Regarding geological field evidences of syenite–carbonatite relationship and the close agreement of published zircon U/Pb and whole rock and biotite K/Ar and Ar–Ar age data, the most probable process is early zircon crystallization from the syenite magma and late-stage reworking during magma evolution and carbonatite segregation. The oxygen isotope fractionations between zircon and other carbonatite minerals (calcite and pyroxene) support the assumption that the zircon would correspond to the early crystallization of syenite–carbonatite magmas.     

Pleistocene recycling of copper at a porphyry system,Atacama Desert,Chile: Cu isotope evidence

We present Cu isotope data of hypogene and supergene minerals from the Late Paleocene Spence Cu-Mo porphyry in the Atacama Desert of northern Chile. Chalcopyrite displays a restricted range of δ⁶⁵Cu values within the values reported for primary porphyry Cu sulfides (+ 0.28‰ to + 0.34‰, n = 6). Supergene chalcocite samples show heavier and remarkably homogeneous δ⁶⁵Cu values, between + 3.91‰ and + 3.95‰ (n = 6), consistent with previous models of Cu leaching and enrichment in porphyry systems. Secondary Cu minerals from the oxide zone show a wider range of composition, varying from + 1.28‰ and + 1.37‰ for chrysocolla (n = 6) to very light Cu isotope signatures reported for atacamite between -5.72‰ to -6.77‰ (n = 17). These data suggest redox cycling of Cu during supergene enrichment of the Spence Cu deposit, characterized by a first stage of supergene chalcocite formation from acidic, isotopically-heavy leach fluids of meteoric origin down-flowing in a semi-arid climate (44 to ~ 15-9 Ma). Reworking of the initial supergene copper assemblage, during the Pleistocene, by rising neutral and chlorine-rich deep formation waters under well-established hyper-arid climate conditions lead to the formation of atacamite with extremely fractionated Cu compositions. Essentially coeval chrysocolla formed by dissolution of atacamite during short episodes of wetter climatic conditions occurring in the latest Pleistocene.