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     

Metamorphism, isotopic ages and composition of lower crustal granulite xenoliths from the Cretaceous Salta Rift, Argentina

Crustal xenoliths from basanitic dikes and necks that intruded into continental sediments of the Cretaceous Salta Rift at Quebrada de Las Conchas, Provincia Salta, Argentina were investigated to get information about the age and the chemical composition of the lower crust. Most of the xenoliths have a granitoid composition with quartz-plagioclase-garnet-rutile ± K-feldspar as major minerals. The exceedingly rare mafic xenoliths consist of plagioclase-clinopyroxene-garnet ± hornblende. All xenoliths show a well equilibrated granoblastic fabric and the minerals are compositionally unzoned. Thermobarometric calculations indicate equilibration of the mafic xenoliths in the granulite facies at temperatures of ca. 900 °C and pressures of ca. 10 kbar. The Sm-Nd mineral isochron ages are 95.1 ± 10.4 Ma, 91.5 ± 13.0 Ma, 89.0 ± 4.2 Ma (granitoid xenoliths), and 110.7 ± 23.6 Ma (mafic xenolith). These ages are in agreement with the age of basanitic volcanism (ca. 130–100 and 80–75 Ma) and are interpreted as minimum ages of metamorphism. Lower crustal temperature at the time given by the isochrons was above the closure temperature of the Sm-Nd system (>600–700 °C). The Sm-Nd and Rb-Sr isotopic signatures (¹⁴⁷Sm/¹⁴⁴Nd = 0.1225–0.1608; ¹⁴³Nd/¹⁴⁴Nd_{t 0} = 0.512000–0.512324; ⁸⁷Rb/⁸⁶Sr = 0.099–0.172; ⁸⁷Sr/⁸⁶Sr_{t 0} = 0.708188–0.7143161) and common lead isotopic signatures (²⁰⁶Pb/²⁰⁴Pb = 18.43–18.48; ²⁰⁷Pb/²⁰⁴Pb = 15.62–15.70; ²⁰⁸Pb/²⁰⁴Pb = 38.22 –38.97) of the granitoid xenoliths are indistinguishable from the isotopic composition of the Early Paleozoic metamorphic basement from NW Argentina, apart from the lower ²⁰⁸Pb/²⁰⁴Pb ratio of the basement. The Sm-Nd depleted mantle model ages of ca. 1.8 Ga from granitoid xenoliths and Early Paleozoic basement point to a similar Proterozoic protolith. Time constraints, the well equilibrated granulite fabric, P-T conditions and lack of chemical zoning of minerals point to a high temperature in a crust of nearly normal thickness at ca. 90 Ma and to a prominent thermal anomaly in the lithosphere. The composition of the xenoliths is similar to the composition of the Early Paleozoic basement in the Andes of NW Argentina and northern Chile. A thick mafic lower crust seems unlikely considering low abundance of mafic xenoliths and the predominance of granitoid xenoliths. Received: 21 July 1998 / Accepted: 27 October 1998     

Hydrothermal carbonates in altered wall rocks at the Uwamuki Kuroko deposits, Japan

Magnesite, siderite and dolomite are characteristic alteration minerals occurring in Miocene hanging wall rocks of dacitic composition which host the Kuroko orebodies. These carbonates generally occur in a more stratigraphically upper horizon than chlorite alteration zone surrounding the orebodies. The Mg/(Mg+Fe) ratios of the carbonates decrease from the central alteration zone to marginal zone. The Mg/(Mg+Fe) ratios of carbonates and chlorite positively correlate. The δ¹⁸O and δ¹³C values of magnesite, siderite and dolomite positively correlate with each other and lie between the igneous and marine carbonate values. The petrographic, isotopic and fluid inclusion characteristics and thermochemical modelling calculations indicate that magnesite and dolomite formed in the central zone close to the orebodies due to the interaction of hydrothermal solutions with the biogenic marine carbonates. Calcite formed further from the orebodies from hydrothermal fluids which did not contain a biogenic marine carbon component. The compositional and textural relationships indicate that superimposed alterations (chlorite alteration and carbonate alteration) occurred in hanging wall rocks. The mode of occurrences and the Mg/(Mg+Fe) ratios of magnesite and dolomite occurring in hanging wallrocks are useful in the exploration for concealed volcanogenic massive sulfide-sulfate deposits. Received: 9 September 1997 / Accepted: 23 September 1997     

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     

Petrographic and geochemical arguments for hydrothermal formation of the Ouenza siderite deposit (NE Algeria)

The Ouenza siderite deposit is located proximal to evaporitic diapirs of Triassic age. Mineralization occurs mainly in Aptian neritic limestones which host important iron concentrations (120–150 MT) and minor Pb, Zn, Cu, Ba and F occurrences. The iron ore consists of iron carbonate minerals which have been oxidized partially to hematite. Fine-grained ankerite and siderite replace limestones, whereas sparry ankerite and siderite were emplaced in veins. Limited variation in the chemical and isotopic compositions of ankerite and siderite were observed, which indicate that they precipitated from the same fluid. Stable isotope compositions (δ¹⁸O and δ¹³C) of iron carbonates and limestones allow estimation of the isotopic composition of the mineralizing fluid and precipitation temperature: δ¹⁸O = 7.5‰ SMOW, T = 100–120 °C. Later deposition of Pb, Zn, Cu, Ba and F minerals is controlled by fractures oriented NE–SW and SE–NW. Fluid inclusion studies of quartz yield salinities of 18–22 wt.% equivalent NaCl and homogenization temperatures between 150 and 180 °C. These values are similar to those of Mississippi Valley type deposits which are associated with basinal brines. Received: 4 January 1996 / Accepted: 17 July 1996     

Oxygen isotopes composition of sapphires from the French Massif Central: implications for the origin of gem corundum in basaltic fields

Alluvial and colluvial gem sapphires are common in the basaltic fields of the French Massif Central (FMC) but sapphire-bearing xenoliths are very rare, found only in the Menet trachytic cone in Cantal. The O-isotope composition of the sapphires ranges between 4.4 and 13.9‰. Two distinct groups have been defined: the first with a restricted isotopic range between 4.4 and 6.8‰ (n = 22; mean δ¹⁸O = 5.6 ± 0.7‰), falls within the worldwide range defined for blue-green-yellow sapphires related to basaltic gem fields (3.0 < δ¹⁸O < 8.2‰, n = 150), and overlaps the ranges defined for magmatic sapphires in syenite (4.4 < δ¹⁸O < 8.3‰, n = 29). A second group, with an isotopic range between 7.6 and 13.9‰ (n = 9), suggests a metamorphic sapphire source such as biotite schist in gneisses or skarns. The δ¹⁸O values of 4.4–4.5‰ for the blue sapphire-bearing anorthoclasite xenolith from Menet is lower than the δ¹⁸O values obtained for anorthoclase (7.7–7.9‰), but suggest that these sapphires were derived from an igneous reservoir in the subcontinental spinel lherzolitic mantle of the FMC. The presence of inclusions of columbite-group minerals, pyrochlore, Nb-bearing rutile, and thorite in these sapphires provides an additional argument for a magmatic origin. In the FMC lithospheric mantle, felsic melts crystallized to form anorthoclasites, the most evolved peraluminous variant of the alkaline basaltic melt. The O-isotopic compositions of the first group suggests that these sapphires crystallized from felsic magmas under upper mantle conditions. The second group of isotopic values, typified for example by the Le Bras sapphire with a δ¹⁸O of 13.9‰, indicates that metamorphic sapphires from granulites were transported to the surface by basaltic magma.     

Distribution of oxygen isotopes in rocks and minerals from the critical zone of the Ioko-Dovyren pluton

The oxygen isotopic composition was studied in minerals and rocks from the critical zone of the Ioko-Dovyren layered pluton. The δ¹⁸O values vary from +5.4 to +6.1‰ in rocks, from +4.8 to +5.8‰ in olivine, from +5.5 to 6.5‰ in pyroxene, and from +5.8 to +6.9‰ in plagioclase and fall into the interval of mantle values for continental mafic and ultramafic rocks. A decrease in δ¹⁸O could have been caused by penetration of meteoric water. Postmagmatic (retrograde) oxygen isotopic redistribution in the slowly cooling rocks is responsible for disturbance of oxygen isotope equilibria in the coexisting minerals, which were crystallized from the same magma at a high temperature. The nonequilibrium oxygen isotopic composition in the associated minerals and calculated temperature of the final isotopic equilibration do not contradict the model of “fluid” formation of low-sulfide PGE mineralization in the Ioko-Dovyren layered pluton.     

Petrology, isotope geochemistry and chemical budgets of oceanic gabbros-seawater interactions in the Equatorial Atlantic

 Petrological and chemical variations, as well as oxygen and strontium isotopic data are presented for metagabbros from the Romanche and Vema fracture zones. These rocks were affected by several types and degrees of alterations ranging from slight hydrothermal alteration to complete amphibolitization. Five major kinds of alteration processes ranging from late-magmatic deuteric alteration (stage I) to low temperature (<150 °C) alteration (stage V) were identified. Water-rock interactions between 300 and 650 °C are the most dominant interactions resulting in the most prevailing secondary mineralogical assemblages which characterize the amphibolite and/or greenschist facies (amphibole ± plagioclase ± epidote ± titanite ± chlorite ± prehnite). Hydrothermal alteration of these gabbroic rocks results in isotopic exchanges between rocks and seawater-derived fluids. These exchanges lead to decrease of gabbroic δ¹⁸O toward values as low as +3.9‰, and larger Sr isotopic variations than other oceanic gabbroic rocks (⁸⁷Sr/⁸⁶Sr ratios shift to 0.7029–0.7051). Calculation of a chemical budget indicates that metagabbros are hydrated and enriched in Fe and probably in Mg and Cl, while Si, Ca and Ti are released to the hydrothermal fluids. In addition to metamorphic recrystallization and geochemical transformation, hydrothermal alteration of oceanic gabbros contributes to the control of the global ocean geochemistry. Received: 8 March 1999 / Accepted: 12 July 1999     

Genesis of the Sanbaqi deposit: a paleokarst-hosted uranium deposit in China

The Sanbaqi uranium deposit in Hunan Province, south China, is the largest of a group of paleokarst-hosted uranium deposits in Lower Carboniferous limestone. Mineralization is localized in cavities and fault-breccias formed by dissolution of carbonates. Four episodes of karst formation are recognized: late Triassic-early Jurassic, late Jurassic-early Cretaceous, Cretaceous-Tertiary and Recent. Field relations indicate that the main uranium mineralization is related to the second karst episode. This is supported by isotopic ages of two pitchblende samples at 129 Ma and 134 Ma, as indicated by their nearly concordant data points on concordia plot. These ages are in the time range of the early Yanshanian tectonic movements that affected southern China, and the faulting related to the movements likely triggered the mineralization process at the Sanbaqi deposit. Associated minerals include pyrite, millerite, ullmannite, niccolite, molybdenite, chalcopyrite, sphalerite, galena, calcite and dolomite. Fluid inclusion studies on calcite reveal that temperature of ore deposition was from 181° to 150 °C. The δ¹⁸O and δD values of the ore fluids range from 1.5 to 7.9 per mil and from −30.4 and −54.8 per mil, respectively. The mineralogical, fluid inclusion and isotopic data indicate that the minerlization took place in episodic pulses of hydrothermal fluids that were introduced along a set of ring faults. Mobilization and redeposition of earlier formed ore minerals in an open system added to the complexity of the paragenetic sequence. Younger episodes of mineralization occurred during the later karst events as suggested by the geological and additional pitchblende U-Pb isotopic data, during the Cretaceous-Tertiary late Yanshanian tectonic movements and recently. Finally, a comparison of the Sanbaqi uranium deposit with the uranium deposits hosted by solution collapse breccia pipes of the Colorado Plateau, USA, shows that they have many similarities. Received: 9 July 1996 / Accepted: 17 January 1997     

Transport of Pb and Sr in leaky aquifers of the Bufa del Diente contact metamorphic aureole, north-east Mexico

The Sr and Pb isotopes from the 31.6 ± 0.3 Ma (2σ) old Diente del Bufa alkali syenite, northeastern Mexico, and marbles of its contact aureole were used to trace the sources and the mobility of these metals during hydrothermal activity. Chert layers form aquifers within the marbles. The marbles represent aquitards. During fluid-wallrock reaction, the chert layers developed wollastonite rims. Early wollastonite rims have Sr and Pb isotopic compositions similar to those of their immediate host marbles, which indicates that the isotopic composition of Sr and Pb is initially buffered by the marble. Later wollastonite and other replacement minerals rimming the aquifer have Sr and Pb isotopic compositions that carry with time increasingly larger contributions from the high-salinity magmatic brine. The Sr and Pb contributions from the alkali syenite can be traced isotopically for more than 90 m away from the contact of the intrusion. In contrast, Sr and Pb originating from the alkali syenite are traceable within the marbles only for 3 to 5 cm from the aquifer-marble boundary. This distance is comparable to the spatial distribution of isotopic alterations of C and O implying that Sr and Pb were transported into the marbles through a fluid phase. The isotopic variation of Sr, Pb, C, and O across the aquifer-marble profiles reflects infiltration as a transport mechanism rather than diffusion. Because Sr and Pb are minor components in both the infiltrating fluid and the rock and because their concentrations are strongly affected by the distribution coefficients among the solid phases present, there is little correlation between the isotopic compositions of the trace elements Sr and Pb and those of C and O, which are major components in fluid and rock. Very thin meta-argillite rinds at the outer margin of the aquifer represent residual material after the dissolution of calcite. They are distinctly enriched in Rb, Sr, and U. The Rb and Sr are to some extent residual from the original limestone mineralogy, whereas U is dominantly derived from the magmatic fluid and leaked from the aquifer with the escaping immiscible CO₂-rich H₂O-CO₂ fluid that was produced by decarbonation. The ²³⁸U/²⁰⁴Pb values ranging from 100 to 250 and distinctly lowered Th/U in the meta-argillite rims (1) demonstrate that U was transported with the magmatic fluid along the aquifer and (2) imply that during unmixing of the highly saline magmatic fluid U fractionated into the CO₂-rich H₂O-CO₂ fluid from which it precipitated selectively in the meta-argillite band across the aquifer. Radioautographs demonstrate that the upper meta-argillite rim has 20 to 40 times more U than the lower rim, which implies that 20 to 40 times more CO₂-rich H₂O-CO₂ fluid has left through the upper aquifer contact. Received: 30 September 1997 / Accepted: 15 December 1997     

Lead isotopes of the carbonate-hosted Kabwe, Tsumeb, and Kipushi Pb-Zn-Cu sulphide deposits in relation to Pan African orogenesis in the Damaran-Lufilian Fold Belt of Central Africa

Lead isotope ratios of galena from the carbonate-hosted massive sulphide deposits of Kabwe (Pb-Zn) and Tsumeb (Pb-Zn-Cu) in Zambia and Namibia, respectively, have been measured and found to be homogeneous and characteristic of upper crustal source rocks. Kabwe galena has average isotope ratios of ^206/204Pb = 17.997 ± 0.007, ^207/204Pb = 15.713 ± 0.010 and ^208/204Pb = 38.410 ± 0.033. Tsumeb galena has slightly higher ^206/204Pb (18.112 ± 0.035) and slightly lower ^207/204Pb (15.674 ± 0.016) and ^208/204Pb (38.276 ± 0.073) ratios than Kabwe galena. The isotopic differences are attributed to local differences in the age and composition of the respective source rocks for Kabwe and Tsumeb. The homogeneity of the ore lead in the two epigenetic deposits suggests lead sources of uniform isotopic composition or, alternatively, thorough mixing of lead derived from sources with relatively similar isotopic compositions. Both deposits have relatively high ²³⁸U/²⁰⁴Pb ratios of 10.31 and 10.09 for Kabwe and Tsumeb galenas, respectively. These isotope ratios are considered to be typical of the upper continental crust in the Damaran-Lufilian orogenic belt, as also indicated by basement rocks and Cu-Co sulphides in stratiform Katangan metasediments which have a mean μ-value of 10.25 ± 0.12 in the Copperbelt region of Zambia and the Democratic Republic of Congo (formerly Zaire). The ²³²Th/²⁰⁴Pb isotope ratios of 43.08 and 40.42 for Kabwe and Tsumeb suggest Th-enriched source regions with ²³²Th/²³⁵U (κ-values) of 4.18 and 4.01, respectively. Model isotopic ages determined for the Kabwe (680 Ma) and Tsumeb (530 Ma) deposits indicate that the timing of the mineralisation was probably related to phases of orogenic activity associated with the Pan-African Lufilian and Damaran orogenies, respectively. Galena from the carbonate-hosted Kipushi Cu-Pb-Zn massive sulphide deposit in the Congo also has homogeneous lead isotope ratios, but its isotopic composition is comparable to that of the average global lead evolution curve for conformable massive sulphide deposits. The μ (9.84) and κ (3.69) values indicate a significant mantle component, and the isotopic age of the Kipushi deposit (456 Ma) suggests that the emplacement of the mineralisation was related to a post-tectonic phase of igneous activity in the Lufilian belt. The isotope ratios (^206/204Pb, ^207/204Pb, ^208/204Pb) of the three deposits are markedly different from the heterogeneous lead ratios of the Katangan Cu-Co stratiform mineralisation of the Copperbelt as well as those of the volcanogenic Nampundwe massive pyrite deposit in the Zambezi belt which typically define radiogenic linear trends on lead-lead plots. The host-rock dolomite of the Kabwe deposit also has homogeneous lead isotope ratios identical to the ore galena. This observation indicates contamination of the Kabwe Dolomite Formation with ore lead during mineralisation. Received: 8 September 1997 / Accepted: 21 August 1998     

Ionizing radiation-induced defects in smectite clays

 The interaction of γ-rays with smectites induces paramagnetic defects in the structure of these clay minerals. The EPR spectra of three different smectites detect the creation of structural defects and trapping of organic free radicals in the clay structure upon irradiation. The defects are assigned to positive holes or trapped electrons stabilised by existing local charge imbalances in the mineral lattice. The organic radicals are derived from organic compounds present as impurities in the crystal lattice of the clay minerals. In addition, γ-rays cause migration of small interlayer cations (such as Li⁺) into the layers, as clearly evidenced by EPR and FT-IR reflectance spectroscopies. Received: 20 April 2000 / Accepted: 2 December 2000     

Petrology, mineral and isotope geochemistry of the Sondalo gabbroic complex (Central Alps, Northern Italy): implications for the origin of post-Variscan magmatism

The origin of the Sondalo gabbroic complex has been unravelled by means of a petrological study of the least evolved rocks, troctolites to norites containing up to 20% of anhedral clinopyroxene and titanian pargasite. Pyroxenes and titanian pargasite from the troctolites have higher Mg, Al and Cr, and lower Mn than those from the norites, whereas plagioclase does not show systematic compositional variations (An ca. 65 mol%). The variation trend of anorthite content of plagioclase versus the forsterite content of olivine differs from that of arc-related gabbroic rocks. Plagioclase, clinopyroxene, orthopyroxene and titanian pargasite were analyzed for REE and selected trace elements by ion microprobe. Application of crystal/liquid partition coefficients to trace element mineral compositions suggests that the parental liquids of both troctolites and norites had tholeiitic affinity and were slightly LREE and LILE enriched relative to N-MORB. A troctolite and a norite give Sm-Nd mineral isochron ages of 300 ± 12 Ma and 280 ± 10 Ma. Plagioclase-amphibole Rb-Sr isochron ages are 266 ± 10 Ma and 269 ± 16 Ma for the same rock samples, and they are interpreted to represent cooling ages. The Nd-Sr-O isotopic compositions indicate that a substantial crustal contribution was involved in the petrogenesis of the norite, which has low ɛ_Nd(290 Ma), high ⁸⁷Sr/⁸⁶Sr(290 Ma) and high δ¹⁸O_Px (−2.6, 0.7057 and +7.9‰, respectively) compared with the troctolites. We thus conclude that the troctolite/norite association formed by concomitant fractional crystallization and crustal assimilation. The somewhat elevated δ¹⁸O_Cpx (+6.4‰) and the relatively low forsterite contents in olivine suggest that the parental liquids of the troctolites had already been evolved through an AFC type process. The ɛ_Nd(290 Ma) and ⁸⁷Sr/⁸⁶Sr(290 Ma) of these rocks (ranging from +2.8 to +4.4 and from 0.7037 to 0.7040, respectively) probably do not reflect the ɛ_Nd and Sr isotopic compositions of their mantle source, and it is thus unclear whether the primary melts were derived from a slightly enriched or from a depleted mantle source. The Sondalo gabbroic complex was most likely associated with the post-Variscan gabbroic complexes of the Alpine belt. These gabbroic complexes can be ascribed to the intrusion at different crustal levels of tholeiitic mantle-derived melts and were emplaced in the time span of 300–270 Ma. Received: 14 September 1998 / Accepted: 4 January 1999     

Planktic foraminiferal and 13C isotopic changes across the Paleocene/Eocene boundary at Possagno (Italy)

 The interval spanning the Paleocene–Eocene (P/E) transition in the Possagno section consists of 1 m of red marls, including a 4-cm-thick, dark-red "dissolution" clay, which represents the Paleocene/Eocene boundary event. The Possagno section is much more condensed than other Tethyan and North Atlantic sections previously studied; however, in this section the most significant biotic, isotopic and sedimentological events across the P/E boundary can be recognized. The Possagno section spans the following planktic foraminiferal subzones: upper part of M. gracilis Subzone, A. berggreni Subzone, A. sibaiyaensis Subzone and probably lowermost part of P. wilcoxensis Subzone. The quantitative analysis indicates a major increase of low-latitude acarininids, including compressed tropical acarininids just above the boundary clay. This acarininid incursion begins just below the boundary clay but reaches its maximum just above the clay. The planktic foraminiferal faunal turnover is gradual except for the acarininid incursion. The isotopic results show a negative excursion in ∂¹³C values at the small benthic foraminifera mass extinction event. The acarininid maximum diversity coincides with this isotopic excursion, and reflects an increase in surface seawater temperature. Despite being very condensed, the Possagno section allows us to further confirm that the different biotic, isotopic and sedimentological events recognized in the Spanish sections (Alamedilla, Campo, Caravaca, Zumaya) are not local in nature and allows the establishment of a detailed chronostratigraphic framework to define the P/E boundary stratotype. Received: 8 April 1998 / Accepted: 12 April 1999     

Ore lead and sulphur isotope pattern from the low-temperature veins of the Catalonian Coastal Ranges (NE Spain)

The lead isotopic composition of galenas from low-temperature veins of the Catalonian Coastal Ranges (NE Spain) displays a small but distinct range of values: 18.318 ≤²⁰⁶Pb/²⁰⁴Pb ≤ 18.678; 15.678 ≤²⁰⁷Pb/²⁰⁴Pb ≤ 15.767 and 38.534 ≤ ²⁰⁸Pb/²⁰⁴Pb ≤ 39.189. The data define a linear trend in the ²⁰⁸Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb diagram that can be interpreted in terms of mixing of lead from different reservoirs. The lead appears to be derived from a solution that preferentially leached granites of Late-Hercynian age. Sulphur isotopic compositions of the galenas range from −8.5 to + 7.3‰ but variations in a single deposit are small (1–2‰), pointing to different sources of sulphur. In a δ³⁴S versus ²⁰⁶Pb/²⁰⁴Pb plot no clear correlation trends appear. Lead isotope data from deposits of similar characteristics situated within the Hercynian orogenic belt as the Linares-La Carolina district (S Spain) and the Inglesiente-Sulcis area (Sardinia) show slight differences indicating a source area of similar lead isotopic composition. In the CCR and Linares-La Carolina districts, the main source of lead is related to the Hercynian granites of each area, although small contributions from metasediments cannot be ruled out. The contribution of lead from metasedimentary rocks is particularly seen in the Sardinian (Hercynian vein-type) ores. Received: 8 August 1996 / Accepted: 5 December 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     

Hydrogeologic and hydrochemical framework of the shallow groundwater system in the southern Voltaian Sedimentary Basin, Ghana

 The southern Voltaian Sedimentary Basin underlies an area of about 5000 km² in east-central Ghana. Groundwater in the basin occurs in fractures in highly consolidated siliciclastic aquifers overlain by a thin unsaturated zone. Aquifer parameters were evaluated from available aquifer-test data on 28 shallow wells in the basin. Hydraulic-conductivity values range from 0.04–3.6 m/d and are about two orders of magnitude greater than the hydraulic conductivity calculated using Darcy's Law and the average groundwater velocity estimated from carbon-14 dating. Linear-regression analysis of the transmissivity and specific-capacity data allowed the establishment of an empirical relationship between log transmissivity and log specific capacity for the underlying aquifers. Groundwater chemistry in the basin is controlled by the weathering of albitic plagioclase feldspar. The weathering rates of various minerals were estimated using ¹⁴C-derived average velocity in the basin. The weathering rate of albite was calculated to be 2.16 μmol L^–1 yr^–1 with the resulting formation of 3.3 μmol L^–1 yr^–1 of kaolinite and 0.047 μmol L^–1 yr^–1 of calcite. The low porosity and permeability of the aquifers in the basin are attributed to the precipitation of secondary minerals on fracture surfaces and interlayer pore spaces. Received, September 1997 Revised, July 1998, August 1998 Accepted, August 1998     

Formation of chlorite during thrust fault reactivation. Record of fluid origin and P–T conditions in the Monte Perdido thrust fault (southern Pyrenees)

The chemical and isotopic compositions of clay minerals such as illite and chlorite are commonly used to quantify diagenetic and low-grade metamorphic conditions, an approach that is also used in the present study of the Monte Perdido thrust fault from the South Pyrenean fold-and-thrust belt. The Monte Perdido thrust fault is a shallow thrust juxtaposing upper Cretaceous–Paleocene platform carbonates and Lower Eocene marls and turbidites from the Jaca basin. The core zone of the fault, about 6 m thick, consists of intensely deformed clay-bearing rocks bounded by major shear surfaces. Illite and chlorite are the main hydrous minerals in the fault zone. Illite is oriented along cleavage planes while chlorite formed along shear veins (<50 μm in thickness). Authigenic chlorite provides essential information about the origin of fluids and their temperature. δ¹⁸O and δD values of newly formed chlorite support equilibration with sedimentary interstitial water, directly derived from the local hanging wall and footwall during deformation. Given the absence of large-scale fluid flow, the mineralization observed in the thrust faults records the P–T conditions of thrust activity. Temperatures of chlorite formation of about 240°C are obtained via two independent methods: chlorite compositional thermometers and oxygen isotope fractionation between cogenetic chlorite and quartz. Burial depth conditions of 7 km are determined for the Monte Perdido thrust reactivation, coupling calculated temperature and fluid inclusion isochores. The present study demonstrates that both isotopic and thermodynamic methods applied to clay minerals formed in thrust fault are useful to help constrain diagenetic and low-grade metamorphic conditions.     

Sulfur, lead and helium isotopic compositions of sulfide minerals from the Dachang Sn-polymetallic ore district in South China: implication for ore genesis

Summary The Dachang Sn-polymetallic ore district is one of the largest tin producing districts in China. Its origin has long been in dispute between magmatic-hydrothermal replacement and submarine exhalative-hydrothermal origin. The Dachang ore district comprises several types of ore deposits, including the Lamo magmatogenic skarn deposit near a granite intrusion, the Changpo-Tongkeng bedded and vein-type sulfide deposit, and the Gaofeng massive sulfide deposit. Sulfide minerals from the Lamo skarn ores show δ³⁴S values in the range between −3 and +4‰ with a mean close to zero, suggesting a major magmatic sulfur source that likely was the intrusive Longxianggai granite. Sulfide minerals from the Gaofeng massive ores show higher δ³⁴S values between +5 and +12‰, whereas sulfide minerals from the Changpo-Tongkeng bedded ores display lighter δ³⁴S values between −7 and −0.2‰. The difference in the sulfur isotope ranges in the two deposits can be interpreted by different degrees of inorganic thermochemcial reduction of marine sulfate using a one-step batch separation fractionation model. Sulfur isotopic compositions from the vein-type ores at Changpo-Tongkeng vary widely from −8 to +4‰, but most of the data cluster around −2.9‰, which is close to that of bedded ores (−3.6‰). The sulfur in vein-type ores might be derived from bedded ores or it represents a mixture of magmatic- and sedimentary-derived sulfur. Pb isotopic compositions of sulfide minerals in the Dachang ore district reveal a difference between massive and bedded ores, with the massive ores displaying more radiogenic Pb isotope ratios. Correlations of ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb or ²⁰⁸Pb/²⁰⁴Pb for the massive and bedded ores are interpreted as two-component mixing of Pb leached from sedimentary host rocks and from deep-seated Precambrian basement rocks composed of metamorphosed volcano-sedimentary rocks. Pb isotopic compositions of sulfide minerals from vein-type ores overlap with those of bedded sulfides. Similar to the sulfur, the lead in vein-type ores might be derived from bedded ores. Skarn ores at Lamo show very limited variations in Pb isotopic compositions, which may reflect a major magmatic-hydrothermal lead source. Helium isotope data of fluid inclusions trapped in sulfides indicate that He in the massive and bedded ores has a different origin than He in fluorite of granite-related veins. The ³He/⁴He ratios of 1.2–2.9 Ra of fluid inclusions from sulfides at Gaofeng and Changpo-Tongkeng imply a contribution of mantle-derived fluids. Overall our data support a submarine exhalative-hydrothermal origin for the massive and bedded ore types at Dachang. Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material     

Zircon ages for high pressure granulites from South Bohemia, Czech Republic, and their connection to Carboniferous high temperature processes

Petrological and isotopic investigations were undertaken on high pressure granulites of granitic to mafic composition from the Prachatice and Blansky les granulite complexes of southern Bohemia, Czech Republic. The predominant felsic granulites are quartz + ternary feldspar (now mesoperthite)-rich rocks containing minor garnet, kyanite and rutile, and most show a characteristic mylonitic fabric formed during retrogression along the exhumation path. Three high temperature reaction stages at distinctly different pressures are recognized. Rare layers of intermediate to mafic composition, containing clinopyroxene, best record a primary high pressure–high temperature stage (>15 kbar, >900 °C), and a well-defined overprint at medium pressure granulite facies conditions (6–8 kbar, 700–800 °C) during which orthopyroxene (+plagioclase) formed from garnet and clinopyroxene. A further high temperature overprint at lower pressure (ca. 4 kbar) is reflected in the development of cordierite- and/or andalusite-bearing partial-melt patches in some felsic granulites. Conventionally separated zircons from the granulites were measured on a SHRIMP II ion microprobe. Near-spherical, multifaceted grains interpreted to be metamorphic, and short prismatic grains from the cordierite-bearing melt patch, are all concordant and yielded indistinguishable results producing an average age, for 83 individual grain spots, of 339.8 ± 2.6 Ma (2σ). Metamorphic grains from a meta-granodiorite associated with the granulites gave the same age (339.6 ± 3.1 Ma, mean of 9), whereas inherited magmatic grains of the same sample yielded 367.8 ± 1.4 Ma. A mean age of 469.3 ± 3.8 Ma was obtained for two short prismatic concordant grains in one of the granulites, whereas several of the rounded grains with ca. 340 Ma metamorphic zircon overgrowths had much older (²⁰⁷Pb/²⁰⁶Pb minimum ages up to 1771 Ma) discordant cores. In addition to analysis of conventionally separated grains, ion-microprobe measurements were also made on zircons extracted from thin sections (drilled-out, mounted and repolished) such that a direct relationship between the dated zircons and petrographic position could be made. Identical results were obtained from both preparation methods, thus showing that the considerable advantage in petrological control is not offset by any appreciable lack of precision when compared to conventionally prepared ion-microprobe samples. All these isotopic results are identical to those previously obtained by conventional multigrain and single-grain evaporation techniques, but rather than allowing a greater resolution of the age of the petrographically obvious different metamorphic stages the results document, for the first time, the apparent short time scale for high, medium and low pressure metamorphism in the granulites. The short time period between the 340 Ma age for the high pressure granulites, as derived here and from studies of similar rocks elsewhere in the European Variscides, and the 320–330 Ma ages for regional low pressure–high temperature metamorphism, migmatization and granite magmatism, strongly suggests an important link between these two high temperature processes. Received: 25 February 1999 / Accepted: 27 September 1999