Preservation of Fe isotope heterogeneities during diagenesis and metamorphism of banded iron formation

We present the iron isotope composition of primary, diagenetic and metamorphic minerals in five samples from the contact metamorphosed Biwabik Iron Formation. These samples attained peak metamorphic temperatures of <200, <340, ∼500, <550, and <740°C respectively. δ⁵⁶Fe of bulk layers ranges from −0.8 to +0.8‰; in some samples the layers may differ by >1‰ on the millimeter scale. Minerals in the lowest grade samples consistently show a sequence in which δ⁵⁶Fe of magnetite > silicate ≥ carbonate. The inter-mineral Fe isotope differences vary in a fashion that cannot be reconciled with theoretical temperature-dependent fractionation factors. Textural evidence reveals that most, if not all, magnetite in the Biwabik Formation is diagenetic, not primary, and that there was tremendous element mobility during diagenesis. The short duration of contact metamorphism allowed diagenetic magnetite compositions to be preserved throughout prograde metamorphism until at least the appearance of olivine. Magnetite compositions therefore act as an isotope record of the environment in which these sediments formed. Larger-scale fluid flow and longer timescales may allow equilibration of Fe isotopes in regionally metamorphosed rocks to lower temperatures than in contact metamorphic environments, but weakly regionally metamorphosed rocks may preserve small-scale Fe isotopic heterogeneities like those observed in the Biwabik Iron Formation. Importantly, Fe isotope compositions that are characteristic of chemical sedimentation or hydrothermal processes are preserved at low grade in the form of large inter-mineral variations, and at high grade in the form of unique bulk rock compositions. This observation confirms earlier work that has suggested that Fe isotopes can be used to identify sedimentary processes in the Precambrian rock record. An erratum to this article can be found at     

Obtaining equilibrium oxygen isotope fractionations from rocks: theory and examples

A generalized approach for retrieving equilibrium isotope fractionations from natural rocks is proposed in which models of prograde reaction histories and retrograde diffusional exchange are used to identify coexisting minerals with similar isotope closure temperatures. Examples using literature data and new analyses from 32 natural amphibolite-facies schists demonstrate both the feasibility and limitations of obtaining equilibrium oxygen isotope fractionations from minerals in natural rocks. By screening samples according to the theoretical models, natural data are shown to have highly consistent mineral fractionations (±2σ reproducibilities of ±0.16 to 0.54‰) that within uncertainty reproduce experimental determinations among the minerals quartz, biotite, muscovite, and calcic amphibole. This correspondence indicates that the proposed theoretically-based selection criteria improve the likelihood of measuring equilibrium fractionations. The new data further corroborate the expected progressive enrichment of δ¹⁸O in the orthosilicates with increasing Al+Si relative to Fe+Mg: Δ(Ky-Grt) ∼1.05‰, Δ(St-Grt) ∼0.6‰, and Δ(St-Cld) ∼0.3‰ at 525–575 °C. In contrast, typical samples that fail to satisfy screening criteria exhibit fractionations involving quartz, biotite, and amphibole that are strongly disequilibrium because of exchange during cooling. Theoretical screening of samples prior to isotope analysis allows robust, independent assessment of theoretical and experimental determinations of equilibrium isotope fractionations. Received: 14 January 1997 / Accepted: 9 March 1998     

Timescales and mechanisms of fluid infiltration in a marble: an ion microprobe study

Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 ¹⁸O/¹⁶O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in ¹⁸O and Sr compared to PLC, and is much more ¹⁸O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of ¹⁸O-depleted (metamorphic or magmatic) fluid (initial δ¹⁸O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10⁻⁸ m², from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼10³ to ∼10⁴ years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of ¹⁸O/¹⁶O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ¹⁸O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998     

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.     

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     

Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

The origin of high δ<Superscript>18</Superscript>O zircons: marbles,megacrysts, and metamorphism

The oxygen isotope ratios (δ¹⁸O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ¹⁸O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ¹⁸O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ¹⁸O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ¹⁸O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ¹⁸O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ¹⁸O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ¹⁸O source for the high δ¹⁸O zircons. Predicted equilibrium values of Δ¹⁸O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ¹⁸O marble will have high δ¹⁸O. The high δ¹⁸O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ¹⁸O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid_(external)/rock); the lower δ¹⁸O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ¹⁸O. High δ¹⁸O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ¹⁸O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ¹⁸O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.     

Contrasting stable isotope behavior between calcite and dolomite marbles,Lone Mountain,Nevada

 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ¹³C values from+3.1 to +1.4 ‰ (PDB) and high δ¹⁸O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ¹³C values from –3.3 to –3.6‰ and low δ¹⁸O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ¹⁸O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ¹⁸O values from +2.0 to +9.3‰. The δ¹⁸O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ¹⁸O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ¹³C values and low δ¹⁸O values of calcite and dolomite, and depleted δ¹⁸O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low ¹⁸O meteoric fluids lowered the δ¹⁸O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in ¹⁸O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ¹³C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995     

Contact metamorphism in the Los Santos W skarn (NW Spain)

Summary The intrusion of the Lower Permian Los Santos-Valdelacasa granitoids in the Los Santos area caused contact metamorphism of Later Vendian-Lower Cambrian metasediments. High grade mineral assemblages are confined to a 7 km wide contact aureole. Contact metamorphism was accompanied by intense metasomatism and development of skarns, and it generated the following mineral assemblages: diopside, forsterite, phlogopite (±clintonite) and humites and spinel-bearing assemblages or diopside, grossular, vesuvianite ± wollastonite in the marbles, depending on the bulk rock composition. Cordierite, K-feldspar, andalusite and, locally, sillimanite appear in the metapelitic rocks. Mineral assemblages of marbles and hornfelses indicate pressure conditions ranging from 0.2 to 0.25 GPa and maximum temperatures between 630 and 640 °C. ¹³C and ¹⁸O depletions in calcite marbles are consistent with hydrothermal fluid–rock interaction during metamorphism. Calcites are depleted in both ¹⁸O (δ¹⁸O = 12.74‰) and ¹³C (δ¹³C = −5.47‰) relative to dolomite of unmetamorphosed dolostone (δ¹⁸O = 20.79‰ and δ¹³C = −1.52‰). The δ¹³C variation can be interpreted in terms of Rayleigh distillation during continuous CO₂ fluid removal from the carbonates. The δ¹⁸O values reflect hydrothermal exchange with an externally derived fluid. Microthermometric analyses of fluid inclusions from vesuvianite indicate that the fluid was water dominated with minor contents of CO₂ (±CH₄ ± N₂) suggesting a metamorphic origin. Fluorine-bearing minerals such as chondrodite, norbergite and F-rich phlogopite indicate that contact metamorphism was accompanied by fluorine metasomatism. Metasomatism was more intense in the inner-central portion of the contact aureole, where access to fluids was extensive. The irregular geometry of the contact with small aplitic intrusives between the metasediments and the Variscan granitoids probably served as pathways for fluid circulation.     

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

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

Isotopic and chemical intra-shell variations in low-Mg calcite of rudist bivalves (Mollusca-Hippuritacea): disequilibrium fractionations and late Cretaceous seasonality

 Isotopic (δ¹³C, δ¹⁸O) and elemental (Mg, Sr, Mn, Fe) compositions were analysed in sclerochronological profiles of several shells of late Cretaceous rudist bivalves from Greece, Turkey, Somalia and the Arabian Peninsula. The preservation of original compositions of low-Mg calcite of outer shell layers is indicated by constant and high Sr, generally low Fe and Mn, and the preservation of fibrous-prismatic ultrastructures. Cyclic variations in δ¹⁸O and Mg are interpreted to reflect seasonal temperature/salinity cycles and, thus, annual growth increments. In shells of Torreites, amplitudes of correlated δ¹³C and δ¹⁸O cycles cannot be related to reasonable palaeotemperatures or salinity. This isotopic pattern reflects vital fractionations of an extent which is unknown from modern bivalves. In contrast, almost identical ranges and amplitudes of δ¹⁸O cycles are observed in 13 shells of five species from Santonian-Campanian localities in central Greece and northern Turkey, suggesting that seasonal variations in environmental conditions were recorded without significant vital fractionations. The effect of seasonal salinity changes on δ¹⁸O of the shells is evaluated, and mean palaeotemperatures are constrained within the range of 30–32.5  °C. The annual range of temperature was estimated to be 7  °C, assuming a constant salinity. This agrees with other isotopic proxies of Late Cretaceous palaeotemperatures, and with global circulation models which predict higher low-latitude sea-surface temperatures than the present ones. Received: 12 February 1998 / Accepted: 24 May 1999     

Metamorphic alteration,mineral paragenesis and geochemical re-equilibration of early Archean quartz–amphibole–pyroxene gneiss from Akilia,Southwest Greenland

Quartz–amphibole–pyroxene gneiss from the island of Akilia, Southwest Greenland has been claimed to contain the earliest traces of life on Earth in the form of biogenic carbonaceous matter encapsulated as inclusions in apatite crystals. Various lines of evidence, including petrography, geochronology, field relations, and geochemistry, have, however, been presented that challenge this interpretation. Textural relationships and geochemical signatures in this controversial gneiss presented here manifest a complex, spatially variable metamorphic history that includes granulite- and amphibolite-facies overprints and metasomatism. A peak metamorphic, granulite-facies, quartz–orthopyroxene–clinopyroxene–amphibole–magnetite assemblage is preserved in only a few centimeter-scale layers within the 5-m-thick, quartz–amphibole–pyroxene gneiss unit. Calcite veinlets that appear to postdate the peak metamorphism occur in pyroxene. The quartz–amphibole–pyroxene gneiss unit has subsequently experienced isochemical (except hydration) amphibolite-facies alteration during which pyroxenes were retrogressed to amphiboles and magnetite, and calcite was consumed. Parts of the quartz–amphibole–pyroxene gneiss that contain texturally late hornblende have experienced metasomatic alteration by Al-carrying fluids. These fluids controlled the alteration of pyroxenes and amphiboles to hornblende, and modified the trace-element composition by remobilizing LREE and Eu. Apatite has variable REE composition and ⁸⁷Sr/⁸⁶Sr in the quartz–amphibole–pyroxene gneiss, but on the local scale (cm) is in equilibrium with co-existing silicates. Effective recrystallization of apatite crystals as well as co-existing silicates during several stages of the metamorphic history makes the intact preservation of diagenetic apatite with encapsulated primary carbonaceous matter implausible. Hence, it is highly unlikely that Akilia apatite could serve as repository of the earliest traces of life on Earth.     

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

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

Mineralogical and stable isotope studies of gold–arsenic mineralisation in the Sams Creek peralkaline porphyritic granite, South Island, New Zealand

At Sams Creek, a gold-bearing, peralkaline granite porphyry dyke, which has a 7 km strike length and is up to 60 m in thickness, intrudes camptonite lamprophyre dykes and lower greenschist facies metapelites and quartzites of the Late Ordovician Wangapeka formation. The lamprophyre dykes occur as thin (< 3 m) slivers along the contacts of the granite dyke. δ¹⁸O_magma values (+5 to +8‰, VSMOW) of the A-type granite suggest derivation from a primitive source, with an insignificant mature crustal contribution. Hydrothermal gold–sulphide mineralisation is confined to the granite and adjacent lamprophyre; metapelite country rocks have only weak hydrothermal alteration. Three stages of hydrothermal alteration have been identified in the granite: Stage I alteration (high fO₂) consisting of magnetite–siderite±biotite; Stage II consisting of thin quartz–pyrite veinlets; and Stage III (low fO₂) consisting of sulphides, quartz and siderite veins, and pervasive silicification. The lamprophyre is altered to an ankerite–chlorite–sericite assemblage. Stage III sulphide veins are composed of arsenopyrite + pyrite ± galena ± sphalerite ± gold ± chalcopyrite ± pyrrhotite ± rutile ± graphite. Three phases of deformation have affected the area, and the mineralised veins and the granite and lamprophyre dykes have been deformed by two phases of folding, the youngest of which is Early Cretaceous. Locally preserved early-formed fluid inclusions are either carbonic, showing two- or three-phases at room temperature (liquid CO₂-CH₄ + liquid H₂O ± CO₂ vapour) or two-phase liquid-rich aqueous inclusions, some of which contain clathrates. Salinities of the aqueous inclusions are in the range of 1.4 to 7.6 wt% NaCl equiv. Final homogenisation temperatures (Th) of the carbonic inclusions indicate minimum trapping temperatures of 320 to 355°C, which are not too different from vein formation temperatures of 340–380°C estimated from quartz–albite stable isotope thermometry. δ¹⁸O values of Stage II and III vein quartz range from +12 and +17‰ and have a bimodal distribution (+14.5 and +16‰) with Stage II vein quartz accounting for the lower values. Siderite in Stage III veins have δ¹⁸O (+12 to +16‰) and δ¹³C values (−5‰, relative to VPDB), unlike those from Wangapeka Formation metasediments (δ¹³C_{bulk carbon} values of −24 to −19‰) and underlying Arthur Marble marine carbonates (δ¹⁸O = +25‰ and δ¹³C = 0‰). Calculated δ¹⁸O_water (+8 to +11‰, at 340°C) and (−5‰) values from vein quartz and siderite are consistent with a magmatic hydrothermal source, but a metamorphic hydrothermal origin cannot be excluded. δ³⁴S values of sulphides range from +5 to +10‰ (relative to CDT) and also have a bimodal distribution (modes at +6 and +9‰, correlated with Stage II and Stage III mineralisation, respectively). The δ³⁴S values of pyrite from the Arthur Marble marine carbonates (range from +3 to +13‰) and Wangapeka Formation (range from −4 to +9.5‰) indicate that they are potential sources of sulphur for sulphides in the Sams Creek veins. Another possible source of the sulphur is the lithospheric mantle which has positive values up to +14‰. Ages of the granite, lamprophyre, alteration/mineralisation, and deformation in the region are not well constrained, which makes it difficult to identify sources of mineralisation with respect to timing. Our mineralogical and stable isotope data does not exclude a metamorphic source, but we consider that the source of the mineralisation can best be explained by a magmatic hydrothermal source. Assuming that the hydrothermal fluids were sourced from crystallisation of the Sams Creek granite or an underlying magma chamber, then the Sams Creek gold deposit appears to be a hybrid between those described as reduced granite Au–Bi deposits and alkaline intrusive-hosted Au–Mo–Cu deposits.     

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

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

Variscan amphibolite-facies rocks from the Kurtoğlu metamorphic complex (Gümüşhane area,Eastern Pontides,Turkey)

The Kurtoğlu metamorphic complex, that forms part of the pre-Liassic basement of the Sakarya zone in northern Turkey, consists of at least two tectonic units. Blueschist-facies rocks of unknown metamorphic age in the southern part of the complex are tectonically overlain by Variscan low-pressure high-temperature metamorphic rocks. The latter comprise mica schists and fine-grained gneisses, cut by metaleucogranitic dikes, as well as migmatitic biotite gneisses and subordinate amphibolite intercalations. Structural data indicate that metamorphism and penetrative deformation occurred after dyke intrusion. Peak metamorphic conditions of the mica schists, fine-grained gneisses and metaleucogranites are estimated to ∼650°C and ∼0.4 GPa, based on phase relationships in the system NCKFMASH, Fe–Mg partitioning between garnet and biotite as well as garnet-aluminosilicate-quartz-plagioclase (GASP) and garnet-plagioclase-biotite-quartz (GBPQ) barometry. Peak temperatures of the migmatitic biotite gneisses and amphibolite intercalations are not well constrained but might have been significantly higher (690–740°C), as suggested from hornblende-plagioclase thermometry. ⁴⁰Ar–³⁹Ar incremental dating on muscovite and biotite fractions from the mica schists and fine-grained gneisses yielded plateau ages of ∼323 Ma. Significantly older model ages of ∼329 and ∼337 Ma were obtained on muscovite fractions from two metaleucogranite samples. These fractions contain both relict igneous and newly formed metamorphic muscovite.     

Coupling of oceanic and continental crust during Eocene eclogite-facies metamorphism: evidence from the Monte Rosa nappe,western Alps

High precision U–Pb geochronology of rutile from quartz–carbonate–white mica–rutile veins that are hosted within eclogite and schist of the Monte Rosa nappe, western Alps, Italy, indicate that the Monte Rosa nappe was at eclogite-facies metamorphic conditions at 42.6 ± 0.6 Ma. The sample area [Indren glacier, Furgg zone; Dal Piaz (2001) Geology of the Monte Rosa massif: historical review and personal comments. SMPM] consists of eclogite boudins that are exposed inside a south-plunging overturned synform within micaceous schist. Associated with the eclogite and schist are quartz–carbonate–white mica–rutile veins that formed in tension cracks in the eclogite and along the contact between eclogite and surrounding schist. Intrusion of the veins at about 42.6 Ma occurred at eclogite-facies metamorphic conditions (480–570°C, >1.3–1.4 GPa) based on textural relations, oxygen isotope thermometry, and geothermobarometry. The timing of eclogite-facies metamorphism in the Monte Rosa nappe determined in this study is identical to that of the Gran Paradiso nappe [Meffan-Main et al. (2004) J Metamorphic Geol 22:261–281], confirming that these two units have shared the same Alpine metamorphic history. Furthermore, the Gran Paradiso and Monte Rosa nappes underwent eclogite-facies metamorphism within the same time interval as the structurally overlying Zermatt-Saas ophiolite [∼50–40 Ma; e.g., Amato et al. (1999) Earth Planet Sci Lett 171:425–438; Mayer et al. (1999) Eur Union Geosci 10:809 (abstract); Lapen et al. (2003) Earth Planet Sci Lett 215:57–72]. The nearly identical P–T–t histories of the Gran Paradiso, Monte Rosa, and Zermatt-Saas units suggest that these units shared a common Alpine tectonic and metamorphic history. The close spatial and temporal associations between high pressure (HP) ophiolite and continental crust during Alpine orogeny indicates that the HP internal basement nappes in the western Alps may have played a key role in exhumation and preservation of the ophiolitic rocks through buoyancy-driven uplift. Coupling of oceanic and continental crust may therefore be critical in preventing permanent loss of oceanic crust to the mantle.     

Stable isotope and fluid inclusion evidence for the origin of the Brandberg West area Sn–W vein deposits, NW Namibia

The Brandberg West region of NW Namibia is dominated by poly-deformed turbidites and carbonate rocks of the Neoproterozoic Damara Supergoup, which have been regionally metamorphosed to greenschist facies and thermally metamorphosed up to mid-amphibolite facies by Neoproterozoic granite plutons. The meta-sedimentary rocks host Damaran-age hydrothermal quartz vein-hosted Sn–W mineralization at Brandberg West and numerous nearby smaller deposits. Fluid inclusion microthermometric studies of the vein quartz suggests that the ore-forming fluids at the Brandberg West mine were CO₂-bearing aqueous fluids represented by the NaCl–CaCl₂–H₂O–CO₂ system with moderate salinity (mean=8.6 wt% NaCl_equivalent).Temperatures determined using oxygen isotope thermometry are 415–521°C (quartz–muscovite), 392–447°C (quartz–cassiterite), and 444–490°C (quartz–hematite). At Brandberg West, the oxygen isotope ratios of quartz veins and siliciclastic host rocks in the mineralized area are lower than those in the rocks and veins of the surrounding areas suggesting that pervasive fluid–rock interaction occurred during mineralization. The O- and H-isotope data of quartz–muscovite veins and fluid inclusions indicate that the ore fluids were dominantly of magmatic origin, implying that mineralization occurred above a shallow granite pluton. Simple mass balance calculations suggest water/rock ratios of 1.88 (closed system) and 1.01 (open system). The CO₂ component of the fluid inclusions had similar δ ¹³C to the carbonate rocks intercalated with the turbidites. It is most likely that mineralization at Brandberg West was caused by a combination of an impermeable marble barrier and interaction of the fluids with the marble. The minor deposits in the area have quartz veins with higher δ ¹⁸O values, which is consistent with these deposits being similar geological environments exposed at higher erosion levels.     

Oxygen and hydrogen isotopic composition of Alpine and pre-Alpine minerals of the Swiss Central Alps

The rocks of the Swiss Central Alps consist of pre-Mesozoic and Mesozoic rocks which were metamorphosed during the Alpine orogeny. Eightysix samples from this area have been analyzed for their isotopic composition (310 mineral phases for their ¹⁸O values and 99 mineral phases for their D values).The mineral phases of pre-Mesozoic and Mesozoic rocks differ significantly in their stable isotope composition. The minerals in pre-Mesozoic rocks display a rather uniform oxygen and hydrogen isotope composition indicative of large-scale homogenization with magmatic fluids. The mineral phases of Mesozoic rocks, on the other hand, show a large variation in their isotopic composition, their ¹⁸O values are heavier, and their D values are isotopically lighter than the pre-Mesozoic phases. These data indicate the lack of a large-scale water supply to the gneissic cores of the Penninic nappes during Alpine metamorphism.Equilibrium conditions, as indicated by concordant oxygen isotope temperatures, are attained in several samples; disequilibrium, however, is more frequently observed, mainly in the central part of the Lepontin area. The pre-Mesozoic rocks recrystallized during Alpine metamorphism. This process was accompanied by partial reequilibration of the oxygen isotopes, and took place in a closed system. In the pre-Mesozoic rocks, the oxygen isotope fractionations, therefore, reflect the temperatures at the time of this recrystallization which, in many cases, is not the maximum temperature of Alpine metamorphism. There is strong evidence that oxygen isotope ratios are frozen during the progressive phase of a metamorphic event.Oxygen isotope fractionations indicate temperatures of Alpine metamorphism ranging from 500 ° C near Andermatt to 700 ° C near the Bergell granite.     

Reconstruction of Antarctic climate change using ice core proxy records from the coastal Dronning Maud Land,East Antarctica

Antarctic ice core records have provided unprecedented information on past climatic changes and forcing factors on decadal to millennial timescales. The glaciochemical and stable isotope records of a shallow ice core from the coastal Dronning Maud Land (East Antarctica) were used here to reconstruct the coastal Antarctic environmental variability during the past ∼470 years. Sea salt ion data indicate a significant additional contribution of chloride ions compared to sea water values, possibly through atmospheric scavenging. The nitrate (NO₃ ⁻) profile exhibit significant temporal shifts than that of the sulphate (SO₄ ²⁻), with a major shift around 1750 AD. The changes in NO₃ ⁻ record are synchronous with the proxy record of solar activity (¹⁰Be profile from a South Pole ice core), suggesting enhanced NO₃ ⁻ values during periods of reduced solar activity like the Dalton Minimum (∼1790–1830 AD) and Maunder Minimum (∼1640–1710 AD). The δ¹⁸O records reveal that the more negative δ¹⁸O values were coeval with several events of increased NO₃ ⁻ concentrations, suggesting enhanced preservation of NO₃ ⁻ during periods of reduced air temperatures. The δ¹⁸O and δD records of the core also suggest significant short-term and long-tem variability with more negative values indicating relatively lower air temperatures prior to 1715 AD. The δ¹⁸O records also revealed a significant warming of 2.7°C for the past 470 years, with a warming of ∼0.6°C per century.