Two types of gneisses associated with eclogite at Shuanghe in the Dabie terrane: carbon isotope, zircon U–Pb dating and oxygen isotope

There are two types of gneisses, biotite paragneiss and granitic orthogneiss, to be closely associated with UHP eclogite at Shuanghe in the Dabie terrane. Both concentration and isotope composition of bulk carbon in apatite and host gneisses were determined by the EA-MS online technique. Structural carbonate within the apatite was detected by the XRD and FTIR techniques. Significant ¹³C-depletion was observed in the apatite with δ¹³C values of −28.6‰ to −22.3‰ and the carbon concentrations of 0.70–4.98 wt.% CO₂ despite a large variation in δ¹⁸O from −4.3‰ to +10.6‰ for these gneisses. There is significant heterogeneity in both δ¹³C and δ¹⁸O within the gneisses on the scale of several tens meters, pointing to the presence of secondary processes after the UHP metamorphism. Considerable amounts of carbonate carbon occur in some of the gneisses that were also depleted in ¹³C primarily, but subjected to overprint of ¹³C-rich CO₂-bearing fluid after the UHP metamorphism. The ¹³C-depleted carbon in the gneisses is interpreted to be inherited from their precursors that suffered meteoric–hydrothermal alteration before plate subduction. Both low δ¹³C values and structural carbonate in the apatite suggest the presence of ¹³C-poor CO₂ in the UHP metamorphic fluid. The ¹³C-poor CO₂ is undoubtedly derived from oxidation of organic matter in the subsurface fluid during the prograde UHP metamorphism.

Zircons from two samples of the granitic orthogneiss exhibit low δ¹⁸O values of −4.1‰ to −1.1‰, demonstrating that its protolith was significantly depleted in ¹⁸O prior to magma crystallization. U–Pb discordia datings for the ¹⁸O-depleted zircons yield Neoproterozoic ages of 724–768 Ma for the protolith of the granitic orthogneiss, consistent with protolith ages of most eclogites and orthogneisses from the other regions in the Dabie–Sulu orogen. Therefore, the meteoric–hydrothermal alteration is directly dated to occur at mid-Neoproterozoic, and may be correlated with the Rodinia supercontinental breakup and the snowball Earth event. It is thus deduced that the igneous protolith of the granitic orthogneiss and some eclogites would intrude into the older sequences composing the sedimentary protoliths of the biotite paragneiss and some eclogites along the northern margin of the Yangtze plate at mid-Neoproterozoic, and drove local meteoric–hydrothermal circulation systems in which both ¹³C- and ¹⁸O-depleted fluid interacted with the protoliths of these UHP rocks now exposed in the Dabie terrane.     

Permeability generation and resetting of tracers during metamorphic fluid flow: implications for advection-dispersion models

Advection-dispersion fluid flow models implicitly assume that the infiltrating fluid flows through an already fluid-saturated medium. However, whether rocks contain a fluid depends on their reaction history, and whether any initial fluid escapes. The behaviour of different rocks may be illustrated using hypothetical marble compositions. Marbles with diverse chemistries (e.g. calcite + dolomite + quartz) are relatively reactive, and will generally produce a fluid during heating. By contrast, marbles with more restricted chemistries (e.g. calcite + quartz or calcite-only) may not. If the rock is not fluid bearing when fluid infiltration commences, mineralogical reactions may produce a reaction-enhanced permeability in calcite + dolomite + quartz or calcite + quartz, but not in calcite-only marbles. The permeability production controls the pattern of mineralogical, isotopic, and geochemical resetting during fluid flow. Tracers retarded behind the mineralogical fronts will probably be reset as predicted by the advection-dispersion models; however, tracers that are expected to be reset ahead of the mineralogical fronts cannot progress beyond the permeability generating reaction. In the case of very unreactive lithologies (e.g. pure calcite marbles, cherts, and quartzites), the first reaction to affect the rocks may be a metasomatic one ahead of which there is little pervasive resetting of any tracer. Centimetre-scale layering may lead to the formation of self-perpetuating fluid channels in rocks that are not fluid saturated due to the juxtaposition of reactants. Such layered rocks may show patterns of mineralogical resetting that are not predicted by advection-dispersion models. Patterns of mineralogical and isotopic resetting in marbles from a number of terrains, for example: Chillagoe, Marulan South, Reynolds Range (Australia); Adirondack Mountains, Old Woman Mountains, Notch Peak (USA); and Stephen Cross Quarry (Canada) vary as predicted by these models. Received: 3 February 1997 / Accepted: 26 June 1997     

Isotopic constraints on time scales and mechanisms of slab material transport in the mantle wedge: evidence from the Simcoe mantle xenoliths, Washington, USA

Spinel harzburgite and websterite mantle xenoliths from Simcoe volcano in southern Washington represent fragments of mantle lithosphere from the back-arc side of the Cascade arc front. Previous studies have shown that metasomatism by either silica-rich fluids or hydrous melts crystallized phlogopite, imparted high oxygen fugacities (0.3 to 1.4 log units above QFM), and more radiogenic Os isotopic compositions on these peridotites. These features are consistent with part or all of the metasomatic agent being derived from the Juan de Fuca slab. New Re–Os, Sm–Nd, Sr, and U–Th–Pb isotopic data shed further light on the origin and composition of the metasomatic agent. The clinopyroxenes from the xenoliths have correlated Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb=18.63–19.55, ²⁰⁷Pb/²⁰⁴Pb=15.56–15.63, ²⁰⁸Pb/²⁰⁴Pb=38.22–38.87). The most radiogenic Pb isotopic compositions extend beyond the most radiogenic Pb isotopic compositions for the Cascade arc lavas and display a shallower trend. Mixtures between Juan de Fuca basalts and pelagic or terrigenous sediments would result in Pb isotopic compositions that are not radiogenic enough in ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb at the high ²⁰⁶Pb/²⁰⁴Pb end of this array. Therefore, models for rapid transfer of components from the slab to the mantle lithosphere are not viable in this case. Instead, a multi-stage model is preferred. In the first stage, the slab component is transferred via fluid or melt into, and reacts with the hanging wall mantle. This results in a residual slab depleted in Pb relative to U and Th, and consequent high U/Pb and Th/Pb. Additional dehydration or melting of the slab imparts this chemical signature to the peridotite in the hanging wall. In the second stage, the hybridized hanging wall peridotite evolves for tens of million years until corner flow drags it down to deeper levels in the mantle wedge where melting occurs in response to higher temperatures. In the third stage, this melt migrates upward where it metasomatizes the mantle lithosphere represented by the Simcoe xenoliths. Trace element compositions of the clinopyroxenes, and the presence of high alkali glasses in the xenoliths, are consistent with the metasomatic agent derived from the hybridized hanging wall being alkali-rich, and possibly similar to potassic-rich lavas found in arc and back-arc settings. These data therefore demonstrate the importance of the hybridized hanging wall mantle above slabs as a source for melts which can be metasomatic agents in the upper mantle, and as a site for storage of material derived from the slab for periods of at least tens of million years.     

Graphite–sulfide deposits in Ronda and Beni Bousera peridotites (Spain and Morocco) and the origin of carbon in mantle-derived rocks

This paper describes unusual graphite–sulfide deposits in ultramafic rocks from the Serranía de Ronda (Spain) and Beni Bousera (Morocco). These deposits occur as veins, stockworks and irregular masses, ranging in size from some centimeters to a few meters in thickness. The primary mineral assemblage mainly consists of Fe–Ni–Cu sulfides (pyrrhotite, pentlandite, chalcopyrite and cubanite), graphite and chromite. Weathering occurs in some sulfide-poor deposits that consist of graphite (up to 90%), chromite and goethite. Texturally, graphite may occur as flakes or clusters of flakes and as rounded, nodule-like aggregates. Graphite is highly crystalline and shows light carbon isotopic signatures (δ¹³C≈− 15‰ to − 21‰). Occasionally, some nodule-like graphite aggregates display large isotopic zoning with heavier cubic forms (probably graphite pseudomorphs after diamond with δ¹³C up to − 3.3‰) coated by progressively lighter flakes outwards (δ¹³C up to − 15.2‰).Asthenospheric-derived melts originated the partial melting (and melt–rock reactions) of peridotites and pyroxenites generating residual melts from which the graphite–sulfide deposits were formed. These residual melts concentrated volatile components (mainly CO₂ and H₂O), as well as S, As, and chalcophile elements. Carbon was incorporated into the melts from the melt–rock reactions of graphite-bearing (formerly diamonds) garnet pyroxenites with infiltrated asthenospheric melts. Graphite-rich garnet pyroxenites formed through the UHP transformation of subducted kerogen-rich crustal material into the mantle. Thus, graphite in most of the studied occurrences has light (biogenic) carbon signatures. Locally, reaction of the light carbon in the melts with relicts of ¹³C-enriched graphitized diamonds (probably generated from hydrothermal calcite veins in the subducting oceanic crust) reacted with the partial melts to form isotopically zoned nodule-like graphite aggregates.     

Petrographical and geochemical investigation of the Triassic marbles associated with Menderes massif metamorphics,Kavaklıdere,Muğla,SW Turkey

Vast marble deposits occur in a cover sequence of the Menderes Massif, SW Turkey. Four major marble deposits are recognized in Mu?la province based on the stratigraphic levels. These are Permo-Carboniferous aged black marbles (1), Triassic aged marbles (2), Upper Cretaceous aged marbles (3), and Paleocene aged pelagic marbles (4). This study deals with Triassic aged marbles of the southern part of the Menderes Massif. The Triassic marbles from SW Turkey consist of two big marble horizons in the Çayboyu (ÇM) and Kestanecik (KM) regions. The characteristic samples are collected from different stratigraphic levels in marble deposits in the ÇM and KM horizons. Mineralogical and major, trace, and rare earth element (REE) analyses of marble, limestone, and schist were conducted on these samples to reveal their petrographical and geochemical characteristics. The ÇM horizon is represented by calcitic marble layers. Nickel, cobalt, manganese, and iron elements filled in fractures, fissures, and intergranular spaces of calcite crystals and these elements give the pinky colour to the marble from the ÇM horizon. KM marbles were deformed, metamorphosed, and recrystallized under greenschist facies P–T conditions. As a result of the metasomatic reaction of magnesium and manganese rich fluids with marbles, dolomite, and manganese, minerals such as rhodochrosite and pyrolusite have crystallized along vein walls and layers in the KM horizon. Dolomitization was determined in KM marbles, whereas ÇM marbles show the character of limestone. MgO, MnO, Fe₂O₃, Ni, and Zn contents of marbles from the KM horizon are higher than those of ÇM marbles due to metasomatic reactions. The Sr content in white coloured marbles ranges between 11.20 ppm and 112.20 ppm and this concentration reaches up to 272.70 ppm due to metasomatic reactions and fluid intake. The REE content of Triassic marbles is independent of the abundance of carbonate and the REE enrichment observed due to syn-metamorphic fluid flow. The significant negative Eu anomaly in REE patterns indicates that the protoliths of Triassic marbles are carbonate rocks of sedimentary origin.     

Stable isotope geochemistry of marbles from the coesite UHP terrains of Dabieshan and Sulu, China

Marbles from Dabieshan and Sulu, China, suffered ultra high pressure (UHP) metamorphism in the coesite–eclogite facies at approximately 700°C and 30 kbars during Triassic continental collision and subduction. The marbles range in isotopic composition from +7 to +25 δ¹⁸O_VSMOW and from 0 to +6 δ¹³C_VPDB. High δ¹³C values are representative of unmodified protoliths and are similar to those of ¹³C-enriched Sinian carbonate rocks from the Yangtze craton. High oxygen isotope ratios reflect pristine protoliths but the low values may have been caused by infiltration of low ¹⁸O meteoric water during diagenesis and dolomitization, by fracture-controlled infiltration of water during subduction, by metamorphic mineral reactions, or by a combination of these processes. No evidence of regional isotopic transport during UHP metamorphism has been found. Sampling on scales of 1 to 100 m shows marbles to be inhomogeneous in both carbon and oxygen isotopes. Only samples separated by less than 10 cm have equilibrated oxygen and carbon isotope compositions. Limited isotopic equilibration between adjacent rocks is consistent with the preservation of unaltered UHP minerals and indicates that the metamorphic fluid–rock system was rock-dominated during and following peak metamorphism. A freely flowing, pervasive fluid phase was not present during UHP metamorphism. There is no evidence of isotopic exchange between marble and the upper mantle into which it was subducted. Correlation of geochemical similarities of UHP marbles with Sinian limestones implies that the subducted edge of the Yangtze craton extends at least as far north as the coesite–eclogite facies rocks of Dabieshan. Deposition of protolith carbonates may have taken place in a cold climate either preceding or following but not coincident with Neoproterozoic glaciation.     

Gypsum as a monitor of the paleo-limnological–hydrological conditions in Lake Lisan and the Dead Sea

The isotopic composition and mass balances of sources and sinks of sulfur are used to constrain the limnological–hydrological evolution of the last glacial Lake Lisan (70–14 ka BP) and the Holocene Dead Sea. Lake Lisan deposited large amounts of primary gypsum during discrete episodes of lake level decline. This gypsum, which appears in massive or laminated forms, displays δ³⁴S values in the range of 14–28‰. In addition, Lake Lisan’s deposits (the Lisan Formation) contain thinly laminated and disseminated gypsum as well as native sulfur which display significantly lower δ³⁴S values (−26 to 1‰ and −20 to −10‰, respectively). The calculated bulk isotopic compositions of sulfur in the sources and sinks of Lake Lisan lacustrine system are similar (δ³⁴S ≈ 10‰), indicating that freshwater sulfate was the main source of sulfur to the lake. The large range in δ³⁴S found within the Lisan Formation (−26 to +28‰) is the result of bacterial sulfate reduction (BSR) within the anoxic lower water body (the monimolimnion) and bottom sediments of the lake.

Precipitation of primary gypsum from the Ca-chloride solution of Lake Lisan is limited by sulfate concentration, which could not exceed 3000 mg/l. The Upper Gypsum Unit, deposited before ca. 17–15 ka, is the thickest gypsum unit in the section and displays the highest δ³⁴S values (25–28‰). Yet, our calculations indicate that no more than a third of this Unit could have precipitated directly from the water column. This implies that during the lake level decline that instigated the precipitation of the Upper Gypsum Unit, significant amounts of dissolved sulfate had to reach the lake from external sources. We propose a mechanism that operated during cycles of high-low stands of the lakes that occupied the Dead Sea basin during the late Pleistocene. During high-stand intervals (i.e., Marine Isotopic Stages 2 and 4), lake brine underwent BSR and infiltrated the lake’s margins and adjacent strata. As lake level dropped, these brines, carrying ³⁴S-enriched sulfate, were flushed back to the shrinking lake and replenished the water column with sulfate, thereby promoting massive gypsum precipitation.

The Holocene Dead Sea precipitated relatively small amounts of primary gypsum, mainly in the form of thin laminae. δ³⁴S values of these laminae and disseminated gypsum are relatively constant (15 ± 0.7‰) and are close to present-day lake composition. This reflects the lower supply of freshwater to the lake and the limited BSR activity during the arid Holocene time and possibly during former arid interglacials in the Levant.     

Contrasting fluid evolution of granulite-facies marbles: implications for a high-T intermediate-P terrain in the Famatinian Range, San-Juan, Argentina

High-temperature, intermediate-pressure calc-silicate marbles occur in the granulite-facies terrain of the La Huerta Range in the Province of San Juan, NW-Argentina, in three bulk-compositional varieties: Type (1) dolomite-absent scapolite-wollastonite-grandite-clinopyroxene-quartz—calcite marbles; Type (2) diopside-forsterite-spinel-corundum—calcite marbles with dolomite exolution lamellae in calcite; Type (3) serpentinized forsterite-spinel-dolomite marbles. An isobaric cooling path from peak-metamorphic conditions of 860°C to 750°C at 6.5 kbar is inferred from scapolite-wollastonite-grandite reaction textures in Type (1) and is consistent with cooling after an advective heat input from related gabbroic and tonalitic intrusive bodies. Stable carbon and oxygen isotope geochemistry was used to decipher the fluid/rock evolution of the three marble types. An interpreted four-stage temperature-time-fluid flow path comprises: (1) infiltration of pre-peak-metamorphic fluids, depleted in δ¹⁸O, that caused a shift of primary sedimentary δ¹⁸O ratios to lower values (19.6–20.0); (2) syn-metamorphic fluid liberation from Type (1) marbles with evidence for processes close to batch devolatilization that caused a weak coupled ¹³C and ¹⁸O depletion during prograde metamorphism. A different devolatilization behaviour, close to Rayleigh fractionation, texturally associated with fold settings indicates that granulite-facies fluid flow was focused rather than pervasive; (3) H₂O-absent conditions were dominant when coronal grandite formed during incipient high-temperature isobaric cooling at the expense of scapolite and wollastonite in the Type (1) marbles; (4) intense post-peak- hydration of Type (2) and Type (3) marbles is the last recognizable metasomatic event. In combination, the three marble types record fluid infiltration both before and after the metamorphic peak.     

Metasomatic effects related to channelled fluid streaming through deep crust: fenites and associated carbonatites (In Ouzzal Proterozoic granulites, Hoggar, Algeria)

The In Ouzzal granulitic unit (IOGU) consists predominantly of felsic orthogneisses most of which correspond to granitoids emplaced during the Archaean, plus metasediments, including olivine-spinel marbles, of late Archaean age. All units were metamorphosed at granulite facies during the Eburnean (2 Ga). The stable isotope signature of the marbles (δ¹³C=–0.8 to –4.2‰/PDB; δ¹⁸O = 7.9 to 18.9‰/SMOW) does not record a massive streaming of C-bearing fluids during metamorphism. Most of the isotopic variation in the marbles is explained in terms of pregranulitic features. Metasomatic transformation of granulites into layered potassic syenitic rocks and emplacement of carbonate veins and breccias occurred during retrogressive granulite facies conditions. The chemistry of these rocks is comparable with that of fenites and carbonatites with high contents of (L)REEs, Th, U, F, C, Ba and Sr but, with respect to these elements, a relative depletion in Nb, Ta, Hf, Zr and Ti. The isotopic compositions of Nd (?Nd_(T)=–6.3 to –9.9), of Sr (⁸⁷Sr/⁸⁶Sr_(T)= 0.7093–0.7104), and the O isotopic composition of metasomatic clinopyroxene (δ¹⁸O = 6.9 to 8‰), all indicate that the fluid had a strong crustal imprint. On the basis of the C isotope ratios (δ¹³C =–3.5 to –9.7‰), the fluid responsible for the crystallization of carbonates and metasomatic alteration is thought to be derived from the mantle, presumably through degassing of mantle-derived magmas at depth. Intense interaction with the crust during the upward flow of the fluid may explain its chemical and isotopic signatures. The zones of metasomatic alteration in the In Ouzzal granulites may be the deep-seated equivalents of the zones of channelled circulation of carbonated fluids described at shallower levels in the crust.     

Fluid evolution in the W–Cu–Zn–Pb San Cristobal vein, Peru: fluid inclusion and stable isotope evidence

The Zn–Pb±Ag±Cu San Cristobal district is located 100 km east of Lima in the western cordillera of Peru. It is centred around the Chumpe intrusion and is composed of vein and carbonate replacement ore types. The main San Cristobal vein presents a paragenesis that can be divided into three stages: (a) an early wolframite–quartz–pyrite stage, (b) a quartz–base metal stage, and (c) a late quartz–carbonate–barite stage.

Fluid inclusions in quartz from the tungsten stage are biphase (LV) at room temperature and homogenise to the liquid phase between 146 and 257 °C. Their salinities range between 2.1 and 5.1 wt.% NaCl equiv. Rare inclusions contain an additional crystal of halite and have salinities of 46–54 wt.% NaCl equiv. Data of the first two stages show a decrease in homogenisation temperatures concomitant with a salinity decline. Fluid inclusions in quartz from the late stage homogenise at higher temperatures, between 252 and 323 °C, with salinities ranging between 4.6 and 6.7 wt.% NaCl equiv.

Hydrogen and oxygen isotope data indicate a two-stage evolution. Isotopic compositions of the fluid associated with the first two stages define a trend with constant δ¹⁸O values and decreasing δD values (δ¹⁸O=3.2‰ to 5.0‰ V-SMOW and δD=−60‰ to −112‰ V-SMOW), which is interpreted as mixing of a dominantly magmatic component with minor meteoric water that had equilibrated with the host rocks. This interpretation is supported by sulphur and lead isotopic data from previous studies. By contrast, the quartz–carbonate–barite stage bears isotopic characteristics defining a trend with a coupled decrease of δ¹⁸O and δD (δ¹⁸O=−8.1‰ to 2.5‰ V-SMOW and δD=−57‰ to −91‰ V-SMOW) and is explained by addition of meteoric water to the system and subsequent mixing with a less important magmatic component.

Different fluid origins are confirmed by laser ablation ICP-MS analyses of the triphase (LVH) and biphase (LV) primary inclusions. The concentrations of the major ore elements, i.e., W, Cu, Zn and Pb, decrease throughout the paragenesis; W, and to a lesser extent Cu, show significant variations, associated with a steep decrease in their concentration. The decreasing concentrations can be explained by mineral deposition and dilution by the meteoric fluid; differences in the rate of decrease indicate selective precipitation of W. Fluid inclusions of the quartz–carbonate stages show an abrupt increase in Ba and Sr concentrations. This is interpreted to reflect a higher volume of host rock silicate alteration, probably due to the increasing size of the fluid flow cell and is explained by the input of a third fluid of unknown origin. LA-ICP-MS analyses show that the fluids were already depleted in W and Cu before reaching the emplacement of carbonate replacement ore type, whereas Zn and Pb were still present in considerable amounts. This is again due to selective precipitation and is consistent with the interpretation that the economically interesting metals were dominantly introduced by magmatic fluids.     

Accreted fragments of the Late Cretaceous Caribbean–Colombian Plateau in Ecuador

The eastern part of the Western Cordillera of Ecuador includes fragments of an Early Cretaceous (≈123 Ma) oceanic plateau accreted around 85–80 Ma (San Juan–unit). West of this unit and in fault contact with it, another oceanic plateau sequence (Guaranda unit) is marked by the occurrence of picrites, ankaramites, basalts, dolerites and shallow level gabbros. A comparable unit is also exposed in northwestern coastal Ecuador (Pedernales unit).

Picrites have LREE-depleted patterns, high Nd_i and very low Pb isotopic ratios, suggesting that they were derived from an extremely depleted source. In contrast, the ankaramites and Mg-rich basalts are LREE-enriched and have radiogenic Pb isotopic compositions similar to the Galápagos HIMU component; their Nd_i are slightly lower than those of the picrites. Basalts, dolerites and gabbros differ from the picrites and ankaramites by flat rare earth element (REE) patterns and lower Nd; their Pb isotopic compositions are intermediate between those of the picrites and ankaramites. The ankaramites, Mg-rich basalts, and picrites differ from the lavas from the San Juan–Multitud Unit by higher Pb ratios and lower Nd_i.

The Ecuadorian and Gorgona 88–86 Ma picrites are geochemically similar. The Ecuadorian ankaramites and Mg-rich basalts share with the 92–86 Ma Mg-rich basalts of the Caribbean–Colombian Oceanic Plateau (CCOP) similar trace element and Nd and Pb isotopic chemistry. This suggests that the Pedernales and Guaranda units belong to the Late Cretaceous CCOP. The geochemical diversity of the Guaranda and Pedernales rocks illustrates the heterogeneity of the CCOP plume source and suggests a multi-stage model for the emplacement of these rocks. Stratigraphic and geological relations strongly suggest that the Guaranda unit was accreted in the late Maastrichtian (≈68–65 Ma).     

The geochemical cycle of boron: Constraints from boron isotope partitioning experiments between mica and fluid

The fractionation of boron isotopes between synthetic boromuscovite and fluid was experimentally determined at 3.0 GPa/500 °C and 3.0 GPa/700 °C. For near-neutral fluids Δ¹¹B_(mica-fluid) = δ¹¹B_(mica) − δ¹¹B_(fluid) is − 10.9 ± 1.3‰ at 500 °C, and − 6.5 ± 0.4‰ at 700 °C. This supports earlier assumptions that the main fractionation effect is due to the change from trigonal coordination of boron in neutral fluids to tetrahedrally coordinated boron in micas, clays and melts. The T-dependence of this effect is approximated by the equation Δ¹¹B_{(mica,clay,melt–neutral fluid)} = − 10.69 · (1000/T [K]) + 3.88; R² = 0.992, valid from 25 °C for fluid–clay up to about 1000 °C for fluid–silicate melt. Experiments at 0.4 GPa that used strongly basic fluids produced significantly lower fractionations with Δ¹¹B_{(mica–fluid)} of − 7.4 ± 1.0‰ at 400 °C, and − 4.8 ± 1.0‰ at 500 °C, showing the reduced fractionation effect when large amounts of boron in basic fluids are tetrahedrally coordinated. Field studies have shown that boron concentrations and ¹¹B/¹⁰B-ratios in volcanic arcs systematically decrease across the arc with increasing distance from the trench, thus reflecting the thermal structure of the subducting slab. Our experiments show that the boron isotopic signature in volcanic arcs probably results from continuous dehydration of micas along a distinct P–T range. Continuous slab dehydration and boron transport via fluid into the mantle wedge is responsible for the boron isotopic signature in volcanic arcs.     

Electron microprobe dating of monazite from high-T shear zones in the São José de Campestre Massif, NE Brazil

The easternmost domain of the Borborema Province, northeastern Brazil, presents widespread, extensional-related high-temperature metamorphism during the Brasiliano (=Pan-African) orogeny. This event reached the upper amphibolite to granulite facies and provoked generalized migmatization of Proterozoic metapelitic rocks of the Seridó Group and tonalitic to granodioritic orthogneisses of the Archean to Paleoproterozoic basement. We report new geochronological data based on electron microprobe dating of monazite from metapelitic migmatite and leuconorite within the high-T shear zones that make up the eastern continuation of the huge E–W Patos shear belt. These data were also constrained by using the Sm–Nd isotopic systematic on garnet from a syntectonic alkaline granite and two garnet-bearing leucosomes. The results suggest an age of about 578 to 574 Ma for the peak of the widespread high-T metamorphism. This event is best recorded by Sm–Nd garnet-whole rock ages. The U–Th–Pb isotopes on monazite of the metapelitic migmatite show a younger thermal event at 553 ± 10 Ma. When compared to the Sm–Nd garnet-whole rock ages, the U–Th–Pb electron probe monazite ages seem to record an event of slightly lower temperatures after the peak of the high-T metamorphism. This may reflect the difference in the isotopic behavior of the geochronological methods employed. Otherwise, the U–Th–Pb ages on monazites could indicate an event not yet very well defined. In anyway, this paper reveals the partial or even complete re-opening and resetting of the U–Th–Pb isotopic system produced by the action of low-T Ca-rich fluid.     

Mg-metasomatism and formation conditions of Mg-chlorite-muscovite-quartzphyllites (leucophyllites) of the Eastern Alps (W. Hungary) and their relations to Alpine whiteschists

The lower Austroalpine orthogneiss-micachist complex of the Sopron-Fertörákos area of W. Hungary contains Mg-chlorite-muscovite-quartzphyllites (leuco- phyllite) and Mg-chlorite-bearing kyanite quartzites whose chemical compositions differ greatly from their surrounding rocks. Formation of leucophyllites took place in shear zones and was associated with depletion in alkalies and iron and enrichment of magnesium and H₂O. Mg-zonation of relict igneous muscovites of leucophyllites and changes in the whole rock chemical compositions suggest Mg-metasomatism. Material gains and losses have been assessed using the composition-volume relationship approach. Proceeding from metagranite through transition rocks to leucophyllites, MgO, H₂O, FeO, and alkalies show continuously increasing dispersion in isocon plots with Mg-enrichment even in sheared gneiss not in contact with leucophyllite. The metasomatic processes that formed the Mg-rich rocks may be similar to those responsible for the formation of high pressure whiteschists in the Central and Western Alps. The geochemical characteristics of the Dora Maira whiteschists (Italy) and their country gneisses are very similar to those of the Sopron leucophyllites, supporting the theory that Mg-metasomatism produced the whiteschist chemistry. On the basis of oxygen isotope compositions of relict igneous muscovites, the precursor granitic rock had a δ¹⁸O value around 13‰ proving its crustal anatectic origin. The leucophyllites have whole rock oxygen isotope compositions around 8.5‰ which is in conflict with the theory of an Mg-rich sedimentary protolith. Rather, the low δ¹⁸O values reflect fluid/rock interaction with a low δ¹⁸O fluid. Quartz-mineral oxygen isotope fractionations yield a metamorphic temperature of 560 ± 30 °C which agrees with earlier estimates from mineral stabilities. Silicon contents of phengites correspond to a metamorphic pressure of ～13 GPa at this temperature indicating eclogite facies metamorphism. The fluids in equilibrium with leucophyllites had oxygen isotope compositions around 7.9‰, similar to those calculated for the ultrahigh pressure Dora Maira whiteschists (7.6‰), further supporting the genetic link between the leucophyllites and whiteschists. Hydrogen isotope compositions of mixed white mica + chlorite samples from leucophyllites range from ?40 to ?35‰, correlating with chlorite contents. The calculated endmember chlorite and white mica have δD values of ?30 and ?40‰, respectively. The similar δD values of the white micas in leucophyllites, gneisses and metagranites suggest an overall equilibration with respect to H isotopes. The calculated δD value of the fluid is approximately 0‰, suggesting a seawater origin. This conclusion was also reached for the Dora Maira whiteschists. A possible fluid source that satisfies both metasomatic and isotopic data is dehydration of hydrothermally altered oceanic crust. The mafic–ultramafic complex of the Alpine Penninic unit underlying the Austroalpine nappes is a likely candidate. The subduction and subsequent dehydration of the ophiolite series would supply the Mg-rich fluids whose migration brought about the metasomatic alteration of the overlying gneiss-micaschist complexes.     

Isotopic evidence for multiple contributions to felsic magma chambers: Gouldsboro Granite, Coastal Maine

The Gouldsboro Granite forms part of the Coastal Maine Magmatic Province, a region characterized by granitic plutons that are intimately linked temporally and petrogenetically with abundant co-existing mafic magmas. The pluton is complex and preserves a felsic magma chamber underlain by contemporaneous mafic magmas; the transition between the two now preserved as a zone of chilled mafic sheets and pillows in granite. Mafic components have highly variably isotopic compositions as a result of contamination either at depth or following injection into the magma chamber. Intermediate dikes with identical isotopic compositions to more mafic dikes suggest that closed system fractionation may be occurring in deeper level chambers prior to injection to shallower levels. The granitic portion of the pluton has the highest Nd isotopic composition (ε_Nd = + 3.0) of plutons in the region whereas the mafic lithologies have Nd isotopic compositions (ε_Nd = + 3.5) that are the lowest in the region and similar to the granite and suggestive of prolonged interactions and homogenization of the two components. Sr and Nd isotopic data for felsic enclaves are inconsistent with previously suggested models of diffusional exchange between the contemporaneous mafic magmas and the host granite to explain highly variable alkali contents. The felsic enclaves have relatively low Nd isotopic compositions (ε_Nd = + 2 – + 1) indicative of the involvement of a third, lower ε_Nd melt during granite petrogenesis, perhaps represented by pristine granitic dikes contemporaneous with the nearby Pleasant Bay Layered Intrusion. The dikes at Pleasant Bay and the felsic enclaves at Gouldsboro likely represent remnants of the silicic magmas that originally fed and replenished the overlying granitic magma chambers. The large isotopic (and chemical) contrasts between the enclaves and granitic dikes and granitic magmas may be in part a consequence of extended interactions between the granitic magmas and co-existing mafic magmas by mixing, mingling and diffusion. Alternatively, the granitic magmas may represent an additional crustal source. Using granitic rocks such as these with abundant evidence for interactions with mafic magmas complicate their use in constraining crustal sources and tectonic settings. Fine-grained dike rocks may provide more meaningful information, but must be used with caution as these may also have experienced compositional changes during mafic–felsic interactions.     

Geochemical and isotope data from the Acatlán Volcanic Field, western Trans-Mexican Volcanic Belt: Origin and evolution

The Quaternary Acatlán Volcanic Field (AVF) is located at the western edge of the Trans-Mexican Volcanic Belt (TMVB). This region is related to the subduction of the Pacific Cocos and Rivera plates beneath the North American plate since the late Miocene. AVF rocks are products of Pleistocene volcanic activity and include lava flows, domes, erupted basaltic andesite, trachyandesite, trachydacite, and rhyolite of calc–alkaline affinity. Most rocks show depletion in high field-strength elements and enrichment in large ion lithophile elements and light rare earth elements as is typical for magmas in subduction-related volcanic arcs. ⁸⁷Sr/⁸⁶Sr values range from 0.70361 to 0.70412, while Nd values vary from +2.3 to +5.2. Sr–Nd isotopic data plot along the mantle array. On the other hand, lead isotope compositions (²⁰⁶Pb/²⁰⁴Pb=18.62–18.75, ²⁰⁷Pb/²⁰⁴Pb=15.57–15.64, and ²⁰⁸Pb/²⁰⁴Pb=38.37–38.67) give evidence for combined influences of the upper mantle, fluxes derived from subducted sediments, and the upper continental crust involved in magma genesis at AVF. Additionally δ¹⁸O whole rock analyses range from +6.35‰ in black pumice to +10.9‰ in white pumice of the Acatlán Ignimbrite. A fairly good correlation is displayed between Sr as well as O isotopes and SiO₂ emphasizing the effects of crustal contamination. Compositional and isotopic data suggest that the different AVF series derived from distinct parental magmas, which were generated by partial melting of a heterogeneous mantle source.     

Lithium isotopic composition of Central American Volcanic Arc lavas: implications for modification of subarc mantle by slab-derived fluids

Li contents and isotopic compositions were determined for a suite of well-characterized basaltic lavas from the Central American Volcanic Arc (CAVA). Variable Li/Y (0.2–0.5), Li/Sc (0.1–0.4), and δ⁶Li values (+2.6 to −7.7‰) attest to significant compositional heterogeneity in the subarc mantle. Within specific arc segments, these parameters correlate strongly with each other and with a number of other constituents (e.g., K, Rb, Ba, B/La, ¹⁰Be/⁹Be, ⁸⁷Sr/⁸⁶Sr, U/Ce, and ²³⁰Th/²³²Th, among others); these correlations are particularly strong for Nicaragua samples. Coupling of this particular set of constituents is best explained in terms of addition of ‘subduction components' to the subarc mantle. Moreover, their selective enrichment with respect to relatively fluid-immobile incompatible elements signifies the dominance of fluid vs. silicate melt transport of slab components to the subarc mantle. Several interesting nuances are revealed by the Li data. First, although Li and B are strongly correlated in both Costa Rica and Nicaragua, there are systematic along-strike variations in Li/B that are consistent with these elements having different ‘fluid release patterns' from subducted slab segments. For example, Li/B is highest in Costa Rica where auxiliary evidence indicates higher subduction zone temperatures; apparently B is preferentially depleted and Li retained in the slab under warmer conditions. The same relations are reflected in Li/¹⁰Be and other subduction tracer systematics, all of which point to larger subduction contributions below Nicaragua. Yet, even Nicaragua lavas vary widely in levels of subduction enrichment. High-Ti basalts from Nejapa are the least enriched and have the highest δ⁶Li (1.4 to 2.6‰); these values are greater than in fresh MORB (ca. −4‰) and are not easily explained by additions of subducted Li because most oceanic crustal rocks and marine sediments have lower δ⁶Li than MORB (with typical values between −8 and −20‰). Thus, it appears the Nejapa data may be representative of isotopically light mantle domains. Relatively light δ⁶Li values in an undepleted spinel lherzolite (+11.3‰) from Zabargad Is. (Red Sea) and in primitive backarc basalts (−1.6 to −0.5‰) from Lau Basin support this conclusion. Considering representative fluid and mantle endmember compositions, the CAVA data are consistent with limited (up to a few percent) additions of slab-derived fluids to a heterogeneous mantle containing variably depleted and enriched domains to form the respective magma sources. In our view, the subarc mantle is heterogeneous on a small scale, but some arc sectors clearly received greater slab inputs than others.     

C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite mineralizations in the Attepe iron district (Adana, Southern Turkey)

The Attepe district consists of Precambrian, Lower–Middle Cambrian, Upper Cambrian–Lower Ordovician and Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be distinguished in the area; (i) Sedimentary Fe-sulfide in Precambrian bituminous metapelitic rocks, and Fe-oxides in Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and hematite including barite in Lower–Middle Cambrian metacarbonates of the Çaltepe Formation (HICO), (iii) karstic Fe-oxides and hydroxides essentially in the Lower–Middle Cambrian metacarbonates and the unweathered Fe-carbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable iron deposits like Attepe deposit.

Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the vein-type ores, and on calcites in the recrystallized Çaltepe Limestones to investigate the sources and formation mechanism of primary ore-forming constituents. The δ¹³C values of siderites and calcites in limestones of the Çaltepe Formation range from −10.10‰ to −8.20‰, and from −0.8‰ to 2.30‰. Both carbonate minerals show δ¹⁸O values between 17.50–18.30‰ and 16.20–23.00‰, respectively. The δ¹³C and δ¹⁸O isotopic variations do not indicate any direct or linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal processes or thermal alterations during metamorphism.

The isotopic values of barites display 32.40–38.30‰ for δ³⁴S and 12.20–14.70‰ for δ¹⁸O. The strontium isotope ratios (0.717169–0.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations in the Precambrian bituminous shales of the Attepe formation.

According to the field observations and the stable isotope data, siderites and ankerites should be formed by interaction between iron-rich hydrothermal fluids and Çaltepe limestones, whereas isotope ratios of barites indicate that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.     

Isotopic constraints on fluid/rock ratios in carbonate rocks: Barite-sulfide mineralization in the Schwaz Dolomite, Tyrol (Eastern Alps, Austria)

The significance of isotopic data on constraining the physical conditions of fluid-rock interaction and mineralization processes in carbonate rocks is discussed, based on the example of barite-tetrahedrite mineralization in Lower Devonian platform carbonates of the Western Greywacke Zone (Tyrol, Austria). Available strontium, oxygen, carbon and sulfur isotopic data are complemented with oxygen isotopic data for barite. Barites are homogeneous in δ¹⁸O_V-SMOW and δ³⁴S_CDT with values of + 15.4 and + 23.5‰, respectively. Their ⁸⁷Sr/⁸⁶Sr ratios vary between 0.7128 and 0.7113 for the first generation and between 0.7117 and 0.7123 for younger remobilization. The dolomitic host rock shows a significant variation in Sr, O and C isotopic composition between non-mineralized and mineralized zones: ⁸⁷Sr/⁸⁶Sr ratios vary between 0.7076 and 0.7133, δ¹⁸O_V-SMOW-values between +28.11 and +20.65‰, and δ¹³C_PDB-values between −1.15 and + 3.06‰. Fluid/rock volume ratios on the order of 1.3–3.2 are calculated for open-system behaviour by modelling Sr, O and C isotopic shifting capacities. The isotope data combined with other geological evidence support the following genetic model: Subsequent to synsedimentary sulfide mineralization during an Early Devonian rifting stage, collision tectonics in Carboniferous time led to the expulsion of Ba- and Sr-rich orogenic brines, which evolved from metamorphic fluids consisting essentially of H₂O and some CH₄, into an external sedimentary fold-and-thrust belt. The brines remobilized the synsedimentary sulfides, mixed with meteoric waters in the platform carbonates, reacted with evaporitic horizons and finally caused the recrystallization of dolomite and the precipitation of Sr-rich barite in structurally weak zones at 70–130°C. During the later Alpine orogeny supergene oxidation products were formed, and sulfates, sulfides and carbonates were further remobilized into late faults and fractures.     

Carbon and oxygen isotopes of Maastrichtian–Danian shallow marine carbonates: Yacoraite Formation, northwestern Argentina

The Maastrichtian–Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ¹³C, +2‰ δ¹⁸O). The top of the member reveals an isotopic shift of δ¹³C (−5‰) and δ¹⁸O (−10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (−2‰ δ¹³C, −1‰ δ¹⁸O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si–Mn–Fe–Na, low Ca–Mg–Sr). These isotopic and lithological changes relate to the Cretaceous–Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.