Tourmaline geochemistry and δ<Superscript>11</Superscript>B variations as a guide to fluid–rock interaction in the Habachtal emerald deposit,Tauern Window,Austria

Tourmalines from the Habachtal emerald deposit in the Eastern Alps formed together with emerald in a ductile shear zone during blackwall metasomatism between pelitic country rocks and a serpentinite body. Electron microprobe and secondary ion mass spectrometric (SIMS) analyses provide a record of chemical and B-isotope variations in tourmalines which represent an idealized profile from metapelites into the blackwall sequence of biotite and chlorite schists. Tourmaline is intermediate schorl-dravite in the country rock and become increasingly dravitic in the blackwall zones, while F and Cr contents increase and Al drops. Metasomatic tourmaline from blackwall zones is typically zoned optically and chemically, with rim compositions rich in Mg, Ti, Ca and F compared with the cores. The total range in δ¹¹B values is −13.8 to −5.1‰ and the within-sample variations are typically 3–5‰. Both of these ranges are beyond the reach of closed-system fractionation at the estimated 500–550°C conditions of formation, and at least two boron components with contrasting isotopic composition are indicated. A key observation from tourmaline core analyses is a systematic shift in δ¹¹B from the country rock (−14 to −10‰) to the inner blackwall zones (−9 to −5‰). We suggest that two separate fluids were channeled and partially mixed in the Habachtal shear zone during blackwall alteration and tourmaline-emerald mineralization. A regional metamorphic fluid carried isotopically light boron as observed in the metapelite country rocks. The other fluid is derived from the serpentinite association and has isotopically heavier boron typical for MORB or altered oceanic crust. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hydrothermal gold mineralization at the Hira Buddini gold mine,India: constraints on fluid evolution and fluid sources from boron isotopic compositions of tourmaline

We determined the boron isotope and chemical compositions of tourmaline from the Hira Buddini gold deposit within the Archean Hutti-Maski greenstone belt in southern India to investigate the evolution of the hydrothermal system and to constrain its fluid sources. Tourmaline is a minor but widespread constituent in the inner and distal alteration zones of metabasaltic and metadacite host rocks associated with the hydrothermal gold mineralization. The Hira Buddini tourmaline belongs to the dravite–schorl series with variations in Al, Fe/(Fe+Mg), Ca, Ti, and Cr contents that can be related to their host lithology. The total range of δ¹¹B values determined is extreme, from −13.3‰ to +9.0‰, but 95% of the values are between −4 and +9‰. The boron isotope compositions of metabasalt-hosted tourmaline show a bimodal distribution with peak δ¹¹B values at about −2‰ and +6‰. The wide range and bimodal distribution of boron isotope ratios in tourmaline require an origin from at least two isotopically distinct fluid sources, which entered the hydrothermal system separately and were subsequently mixed. The estimated δ¹¹B values of the hydrothermal fluids, based on the peak tourmaline compositions and a mineralization temperature of 550°C, are around +1 and +10‰. The isotopically lighter of the two fluids is consistent with boron released by metamorphic devolatilization reactions from the greenstone lithologies, whereas the ¹¹B-rich fluid is attributed to degassing of I-type granitic magmas that intruded the greenstone sequence, providing heat and fluids to the hydrothermal system. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Detrital,metamorphic and metasomatic tourmaline in high-pressure metasediments from Syros (Greece): intra-grain boron isotope patterns determined by secondary-ion mass spectrometry

The boron isotopic composition of zoned tourmaline in two metasediments from the island of Syros, determined by secondary-ion mass spectrometry (SIMS), reflects the sedimentary and metamorphic record of the rocks. Tourmaline from a silicate-bearing marble contains small (≤20 μm) detrital cores with highly variable δ ¹¹B values (−10.7 to +3.6‰), pointing to a heterogeneous protolith derived from multiple sources. The sedimentary B isotopic record survived the entire metamorphic cycle with peak temperatures of ∼500°C. Prograde to peak metamorphic rims are homogeneous and similar among all analysed grains (δ ¹¹B ≈ +0.9‰). The varying δ ¹¹B values of detrital cores in the siliceous marble demonstrate that in situ B isotope analysis of tourmaline by SIMS is a potentially powerful tool for provenance studies not only in sediments but also in metasediments. A meta-tuffitic blueschist bears abundant tourmaline with dravitic cores of detrital or authigenic origin (δ ¹¹B ≈ −3.3‰), and prograde to peak metamorphic overgrowth zones (−1.6‰). Fe-rich rims, formed during influx of B-bearing fluids under retrograde conditions, show strongly increasing δ ¹¹B values (up to +7.7‰) towards the margins of the grains. The δ ¹¹B values of metamorphic tourmaline from Syros, formed in mixed terrigenous–marine sediments, reflect the B signal blended from these two different sources, and was probably not altered by dehydration during subduction.     

Tourmaline breakdown in a pelitic system: implications for boron cycling through subduction zones

Pressure–temperature conditions of tourmaline breakdown in a metapelite were determined by high-pressure experiments at 700–900°C and 4–6 GPa. These experiments produced an eclogite–facies assemblage of garnet, clinopyroxene, phengite, coesite, kyanite and rare rutile. The modal proportions of tourmaline clearly decreased between 4.5 and 5 GPa at 700°C, between 4 and 4.5 GPa at 800°C, and between 800 and 850°C at 4 GPa, with tourmaline that survived the higher temperature conditions appearing corroded and thus metastable. Decreases in the modal abundance of tourmaline are accompanied by decreasing modal abundance of coesite, and increasing that of clinopyroxene, garnet and kyanite; the boron content of phengite increases significantly. These changes suggest that, with increasing pressure and temperature, tourmaline reacts with coesite to produce clinopyroxene, garnet, kyanite, and boron-bearing phengite and fluid. Our results suggest that: (1) tourmaline breakdown occurs at lower pressures and temperatures in SiO₂-saturated systems than in SiO₂-undersaturated systems. (2) In even cold subduction zones, subducting sediments should release boron-rich fluids by tourmaline breakdown before reaching depths of 150 km, and (3) even after tourmaline breakdown, a significant amount of boron partitioned into phengite could be stored in deeply subducted sediments.     

Epithermal mineralization and ore controls of the Shasta Au-Ag deposit, Toodoggone District, British Columbia, Canada

The Shasta gold-silver deposit, British Columbia, Canada, is an adularia-sericite-type epithermal deposit in which deposition of precious metals coincided with the transition of quartz- to calcite-dominant gangue. Mineralization is associated with stockwork-breccia zones in potassically altered dacitic lapilli tuffs and flows, and consists of pyrite, sphalerite, chalcopyrite, galena, acanthite, electrum and native silver. Pre- and post-ore veins consist solely of quartz and calcite, respectively. Fluid inclusion microthermometry indicates that ore minerals were deposited between 280 ° and 225 °C, from a relatively dilute hydrothermal fluid (˜1.5 wt.% NaCl equivalent). Abundant vapor-rich inclusions in ore-stage calcite are consistent with boiling. Oxygen and hydrogen isotopic data (δ¹⁸O_fluid = −1.5 to −4.1‰; δD_fluid = −148 to −171‰) suggest that the fluid had a meteoric origin, but was ¹⁸O-enriched by interaction with volcanic wallrocks. Initial (˜280 °C) fluid pH and log f O₂ conditions are estimated at 5.3 to 6.0, and −32.5 to −33 bar, respectively; during ore deposition, the fluid became more alkaline and oxidizing. Ore deposition at Shasta is attributed to localization of meteoric hydrothermal fluids by extensional faults; mineralization was controlled by boiling in response to hydraulic brecciation. Calcite and base metal sulfides precipitated due to the increase in pH that accompanied boiling, and the associated decrease in H₂S concentration led to precipitation of gold and silver. Received: 23 February 1995 / Accepted: 16 April 1996     

Source and evolution of ore-forming hydrothermal fluids in the northern Iberian Pyrite Belt massive sulphide deposits (SW Spain): evidence from fluid inclusions and stable isotopes

A fluid inclusion and stable isotopic study has been undertaken on some massive sulphide deposits (Aguas Teñidas Este, Concepción, San Miguel, San Telmo and Cueva de la Mora) located in the northern Iberian Pyrite Belt. The isotopic analyses were mainly performed on quartz, chlorite, carbonate and whole rock samples from the stockworks and altered footwall zones of the deposits, and also on some fluid inclusion waters. Homogenization temperatures of fluid inclusions in quartz mostly range from 120 to 280 °C. Salinity of most fluid inclusions ranges from 2 to 14 wt% NaCl equiv. A few cases with T _h=80–110 °C and salinity of 16–24 wt% NaCl equiv., have been also recognized. In addition, fluid inclusions from the Soloviejo Mn–Fe-jaspers (160–190 °C and ˜6 wt% NaCl equiv.) and some Late to Post-Hercynian quartz veins (130–270 °C and ˜4 wt% NaCl equiv.) were also studied. Isotopic results indicate that fluids in equilibrium with measured quartz (d ¹⁸O _fluid ˜–2 to 4‰), chlorites (d ¹⁸O _fluid ˜8–14‰, dD _fluid ˜–45 to –27‰), whole rocks (d ¹⁸O _fluid ˜4–7‰, dD _fluid ˜–15 to –10‰), and carbonates (d ¹⁸O _ankerite ˜14.5–16‰, d ¹³C _fluid =–11 to –5‰) evolved isotopically during the lifetime of the hydrothermal systems, following a waxing/waning cycle at different temperatures and water/rock ratios. The results (fluid inclusions, d ¹⁸O, dD and d ¹³C values) point to a highly evolved seawater, along with a variable (but significant) contribution of other fluid reservoirs such as magmatic and/or deep metamorphic waters, as the most probable sources for the ore-forming fluids. These fluids interacted with the underlying volcanic and sedimentary rocks during convective circulation through the upper crust.     

A fluid inclusion and stable isotope study of 200 Ma of fluid evolution in the Galway Granite, Connemara, Ireland

Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H₂O-CO₂-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V₁) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ¹⁸O across the batholith (9.5 ± 0.4‰n = 12) suggests V₁ precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V₁ indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H₂O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ¹⁸O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V₂) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H₂O-NaCl-CaCl₂-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ¹⁸O (−3 to + 1.2‰), δ¹³C_CO2 (−19 to 0‰) and δ³⁴S_sulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V₃). Correlations of salinity, temperature, δD and δ¹⁸O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ¹⁸O (1.2–2.5‰), high-δ¹³C_CO2 (> −4‰), low-δ³⁴S_sulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ¹⁸O (−5.4 to −3‰), low-δ¹³C (<−10‰), high-δ³⁴S_sulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V₃ veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997     

Temperature-dependent isotopic fractionation of lithium between clinopyroxene and high-pressure hydrous fluids

The fractionation of lithium isotopes between synthetic spodumene as representative of Li-bearing clinopyroxene and Cl- and OH-bearing aqueous fluids was experimentally determined between 500 and 900°C at 2.0 GPa. In all the experiments, ⁷Li was preferentially partitioned into the fluid. The fractionation is temperature dependent and approximated by the equation Δ⁷Li_{(clinopyroxene–fluid)}=−4.61×(1,000/T [K]) + 2.48; R ²=0.86. Significant Li isotopic fractionation of about 1.0‰ exists even at high temperatures of 900°C. Using neutral and weakly basic fluids revealed that the amount of fractionation is not different. The Li isotopic fractionation between altered basalt and hot spring water (350°C) in natural samples is in good agreement with our experimentally determined fractionation curve. The data confirm earlier speculations drawn from the Li isotopic record of dehydrated metamorphic rocks that fluids expelled from a dehydrating slab carry heavier Li into the mantle wedge, and that a light Li component is introduced into the deeper mantle. Li and Li isotopes are redistributed among wedge minerals as fluids travel across the wedge into hotter regions of arc magma production. This modifies the Li isotopic characteristics of slab-derived fluids erasing their source memory, and explains the absence of cross-arc variations of Li isotopes in arc basalts.     

Boron recycling in the continental crust of the central Andes from the Palaeozoic to Mesozoic, NW Argentina

Whole-rock chemical composition and ¹¹B/¹⁰B isotope ratios in tourmaline was investigated to study the geochemical recycling of boron during the evolution of the Andean basement from the Palaeozoic to Mesozoic. In the basement (Cambrian to Ordovician high-grade paragneisses, migmatites and orthogneisses, the Eocambrian Puncoviscana Formation, and Paleozoic-Mesozoic granitoid igneous rocks) whole-rock B contents are generally below 100 ppm, but B contents of ˜1 wt% are found in cogenetic aplite and pegmatite dikes and in tourmaline–quartz rocks. In the metasedimentary rocks, no systematic variation in B content because of metamorphic grade and no correlation of B with other incompatible elements are apparent. Tourmalines from the high-grade metamorphic basement yield δ¹¹B values ranging from −11.2 to −6.8‰ and isotope fractionation during migmatisation was small. Metamorphic tourmalines from the Puncoviscana Formation have δ¹¹B values between −6.3 and −5.8‰. The calculated (corrected for fractionation) δ¹¹B values of −6 to −2‰ for the sedimentary protolith of the metamorphic basement indicate a continental B source with subordinate marine input. Tourmalines from Palaeozoic and Mesozoic granitoids display an identical range of δ¹¹B values from −12 to −5.3‰ and indicate a similarly homogeneous B source throughout time. Tourmalines from pegmatites and tourmaline–quartz rocks record the average δ¹¹B values of the parental granitic magma. We assume that B in the Palaeozoic and Mesozoic granitoids is derived from the local metamorphic basement supporting the hypothesis that recycling of the lower Palaeozoic crust is the dominant process in granitic magma formation from Palaeozoic to Mesozoic. Received: 15 December 1999 / Accepted: 11 July 2000     

Genesis of the Assif El Mal Zn–Pb (Cu,Ag) vein deposit. An extension-related Mesozoic vein system in the High Atlas of Morocco. Structural,mineralogical, and geochemical evidence

The Assif El Mal Zn–Pb (Cu–Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn–Pb (Cu–Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid–vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit T _h mean values ranging from 104°C to 198°C. Final ice-melting temperatures range from −8.1°C to −12.8°C, corresponding to salinities of ∼15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75°C to 150°C. The δ¹⁸O and δD fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low δ¹³C_VPDB values ranging from −7.5‰ to −7.7‰ indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn–Pb (Cu–Ag) veins. The calculated δ³⁴S_H2S values for reduced sulfur (22.5‰ to 24.3‰) are most likely from reduction of SO₄ ²⁻ in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO₂ which ultimately led to precipitation of saddle dolomite with isotopically light carbon. Lead isotope compositions are consistent with fluid–rock interaction that leached metals from the immediate Cambro-Ordovician volcaniclastic and metasedimentary sequence or from the underlying Paleo-Neoproterozoic crustal basement. Geological constraints suggest that the vein system of Assif El Mal formed during the Jurassic opening of the central Atlantic Ocean.     

Synthesis of Ca-tourmaline in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl

Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)₂ and CaCl₂-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg₃- Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, and oxy-Mg-foitite, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg₃(MgAl₅)(Si₆O₁₈)(BO₃)₃(OH)₃(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al₂□Mg₋₂Ca₋₁ and AlMg₋₁H₋₁. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca²⁺ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.

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Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al ₂ O ₃ -SiO ₂ -B ₂ O ₃ -H ₂ O-HCl Im System CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)₂ and CaCl₂-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, und Oxy-Mg-Foitit, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg₃(MgAl₅) (Si₆O₁₈)(BO₃)₃(OH)₃(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al₂□Mg₋₂Ca₋₁ und AlMg₋₁H₋₁. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca²⁺ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

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Received July 24, 1998;/revised version accepted October 21, 1999     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

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

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

Geology and geochemistry of telluride-bearing Au deposits in the Pingyi area, Western Shandong, China

Summary Telluride-bearing gold deposits of the Pingyi area, western Shandong, China, are located on the southeastern margin of the North China Craton. There are two main types of deposits: (i) mineralized cryptoexplosive breccia, e.g., Guilaizhuang; and (ii) stratified, finely-disseminated mineralization hosted in carbonate rocks, e.g., Lifanggou and Mofanggou deposits. In Guilaizhuang, the cryptoexplosive breccia is formed within rocks of the Tongshi complex and Ordovician dolomite. The mineralization is controlled by an E–W-trending listric fault. Stratified orebodies of the Lifanggou and Mofanggou deposits are placed along a NE-trending, secondary detachment zone. They are hosted within dolomitic limestone, micrite and dolomite of the Early-Middle Cambrian Changqing Group. The mineralization in the ore districts is considered to be related to the Early Jurassic Tongshi magmatic complex that formed in a continental arc setting on the margin of the North China Craton. The host rocks are porphyritic and consist predominantly of medium- to fine-grained diorite and pyroxene (hornblende)-bearing monzonite. SHRIMP U–Pb zircon dating of diorites give a ²⁰⁶Pb/²³⁸U weighted mean age of 175.7 ± 3.8 Ma. This is interpreted as representing the crystallization age of the Tongshi magmatic complex. Considering the contact relationships between the magmatic and host sedimentary rocks, as well as the genetic link with the deposits, we conclude that this age is relevant also for the formation of mineralization in the Pingyi area. We hence consider that the deposits formed in the Jurassic. The principal gold minerals are native gold, electrum and calaverite. Wall-rock alteration comprises pyritization, fluoritization, silicification, carbonatization and chloritization. Fluid inclusion studies indicate that all the analyzed inclusions are of two-phase vapor–liquid NaCl–H₂O type. Homogenization temperatures of the fluid inclusions vary from 103 °C to 250 °C, and the ice melting temperatures range from −2.5 °C to −13.5 °C, corresponding to a salinity range of 4.65 to 17.26 wt.% NaCl equiv. The δ³⁴S values of pyrite associated with gold mineralization exhibit a narrow range of −0.71 to + 2.99‰, implying that the sulfur was probably derived from the mantle and/or dioritic magma. The δ¹³C_PDB values of the fluid inclusions in calcite range from −7.3 to 0.0‰. The δ¹⁸O_SMOW values of vein quartz and calcite range from 11.5 to 21.5‰, corresponding to δ¹⁸O_fluid values of −1.1 to 10.9‰; δD values of the fluid inclusions vary between −70 and −48‰. The isotope data for all three deposits suggest mixing of ore-forming fluids derived from the mantle and/or magma with different types of fluids at shallow levels. Pressure release and boiling of the fluids, as well as fluid-rock interaction (Lifanggou and Mofanggou) and mixing of magmatically-derived fluids with meteoritic waters (Guilaizhuang) played an important role in the ore-forming processes.     

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.     

Formation of the Vysoká–Zlatno Cu–Au skarn–porphyry deposit, Slovakia

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu–Au skarn–porphyry mineralisation, related to granodiorite/quartz–diorite porphyry dyke clusters and stocks. Vysoká–Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg–Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na–Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31–70 wt.% NaCl eq. and temperatures of liquid–vapour homogenization (Th) of 186–575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1–31 wt.% NaCl eq. and Th of 320–360°C. Quartz–chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0–3 wt.% NaCl eq. and Th of 323–364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ¹⁸O_fluid 2.5–12.3‰) with a minor meteoric component. Corresponding low δD_fluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile–brittle transition. The magma chamber at ∼5–6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid–vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.     

Magmatic-dominated fluid evolution in the Jurassic Nambija gold skarn deposits (southeastern Ecuador)

The Jurassic (approximately 145 Ma) Nambija oxidized gold skarns are hosted by the Triassic volcanosedimentary Piuntza unit in the sub-Andean zone of southeastern Ecuador. The skarns consist dominantly of granditic garnet (Ad_20–98) with subordinate pyroxene (Di_46–92Hd_17–42Jo_0–19) and epidote and are spatially associated with porphyritic quartz-diorite to granodiorite intrusions. Endoskarn is developed at the intrusion margins and grades inwards into a potassic alteration zone. Exoskarn has an outer K- and Na-enriched zone in the volcanosedimentary unit. Gold mineralization is associated with the weakly developed retrograde alteration of the exoskarn and occurs mainly in sulfide-poor vugs and milky quartz veins and veinlets in association with hematite. Fluid inclusion data for the main part of the prograde stage indicate the coexistence of high-temperature (500°C to >600°C), high-salinity (up to 65 wt.% eq. NaCl), and moderate- to low-salinity aqueous-carbonic fluids interpreted to have been trapped at pressures around 100–120 MPa, corresponding to about 4-km depth. Lower-temperature (510–300°C) and moderate- to low-salinity (23–2 wt.% eq. NaCl) aqueous fluids are recorded in garnet and epidote of the end of the prograde stage. The microthermometric data (Th from 513°C to 318°C and salinity from 1.0 to 23 wt.% eq. NaCl) and δ¹⁸O values between 6.2‰ and 11.5‰ for gold-bearing milky quartz from the retrograde stage suggest that the ore-forming fluid was dominantly magmatic. Pressures during the early retrograde stage were in the range of 50–100 MPa, in line with the evidence for CO₂ effervescence and probable local boiling. The dominance of magmatic low-saline to moderately saline oxidizing fluids during the retrograde stage is consistent with the depth of the skarn system, which could have delayed the ingression of external fluids until relatively low temperatures were reached. The resulting low water-to-rock ratios explain the weak retrograde alteration and the compositional variability of chlorite, essentially controlled by host rock compositions. Gold was precipitated at this stage as a result of cooling and pH increase related to CO₂ effervescence, which both result in destabilization of gold-bearing chloride complexes. Significant ingression of external fluids took place after gold deposition only, as recorded by δ¹⁸O values of 0.4‰ to 6.2‰ for fluids depositing quartz (below 350°C) in sulfide-rich barren veins. Low-temperature (<300°C) meteoric fluids (δ¹⁸O_water between −10.0‰ and −2.0‰) are responsible for the precipitation of late comb quartz and calcite in cavities and veins and indicate mixing with cooler fluids of higher salinities (about 100°C and 25 wt.% eq. NaCl). The latter are similar to low-temperature fluids (202–74.5°C) with δ¹⁸O values of −0.5‰ to 3.1‰ and salinities in the range of 21.1 to 17.3 wt.% eq. CaCl₂, trapped in calcite of late veins and interpreted as basinal brines. Nambija represents a deep equivalent of the oxidized gold skarn class, the presence of CO₂ in the fluids being partly a consequence of the relatively deep setting at about 4-km depth. As in other Au-bearing skarn deposits, not only the prograde stage but also the gold-precipitating retrograde stage is dominated by fluids of magmatic origin.     

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

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

Tourmaline in Proterozoic Massive Sulfide Deposits from Rajasthan, India

We have analyzed the chemical composition and boron isotope composition of tourmaline from tourmalinites, granite and a quartz-tourmaline vein from the Deri ore zone and from a pegmatitic band in the Rampura-Agucha ore body. These two Proterozoic massive sulfide deposits occur in the Aravalli-Delhi orogenic belt, Rajasthan, northwest India. Tourmaline from stratiform tourmalinites closely associated with the massive sulfides in the Deri deposit have preserved their original chemical compositions despite regional and thermal metamorphism in the area. These tourmalines have low Fe/(Fe + Mg) ratios (0.19–0.30; mean 0.26) that suggest formation close to the sediment-sea water interface. The δ¹¹B values (−15.5 and −16.4‰) are compatible with boron derived from leaching of argillaceous sediments and/or felsic volcanics underlying the original massive sulfide deposit during its formation. Boron isotope compositions measured in tourmaline from a post-ore granite and quartz-tourmaline vein in the Deri deposit indicate that boron in these tourmalines was derived from the tourmalinites produced during ore formation. The boron isotope systematics of a coarse brown tourmaline crystal from a pegmatitic band on the hanging wall contact of the Rampura-Agucha deposit indicate that 45 ± 25% of the boron within the original tourmaline was lost during upper amphibolite facies regional metamorphism. Received: 3 April 1996 / Accepted: 11 April 1996