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     

An <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar,Rb/Sr,and stable isotope study of micas in low-grade fold-and-thrust belt: an example from the Swiss Helvetic Alps

White micas in carbonate-rich tectonites and a few other rock types of large thrusts in the Swiss Helvetic fold-and-thrust belt have been analyzed by ⁴⁰Ar/ ³⁹Ar and Rb/Sr techniques to better constrain the timing of Alpine deformation for this region. Incremental ⁴⁰Ar/ ³⁹Ar heating experiments of 25 weakly metamorphosed (anchizone to low greenschist) samples yield plateau and staircase spectra. We interpret most of the staircase release spectra result from variable mixtures of syntectonic (neoformed) and detrital micas. The range in dates obtained within individual spectra depends primarily on the duration of mica nucleation and growth, and relative proportions of neoformed and detrital mica. Rb/Sr analyses of 12 samples yield dates of ca. 10–39 Ma (excluding one anomalously young sample). These dates are slightly younger than the ⁴⁰Ar/ ³⁹Ar total gas dates obtained for the same samples. The Rb/Sr dates were calculated using initial ⁸⁷Sr/ ⁸⁶Sr ratios obtained from the carbonate-dominated host rocks, which are higher than normal Mesozoic carbonate values due to exchange with fluids of higher ⁸⁷Sr/ ⁸⁶Sr ratios (and lower ¹⁸O/ ¹⁶O ratios). Model dates calculated using ⁸⁷Sr/ ⁸⁶Sr values typical of Mesozoic marine carbonates more closely approximate the ⁴⁰Ar/ ³⁹Ar total gas dates for most of the samples. The similarities of Rb/Sr and ⁴⁰Ar/ ³⁹Ar total gas dates are consistent with limited amounts of detrital mica in the samples. The d ¹⁸O values range from 24–15‰ (VSMOW) for 2–6 µm micas and 27–16‰ for the carbonate host rocks. The carbonate values are significantly lower than their protolith values due to localized fluid-rock interaction and fluid flow along most thrust surfaces. Although most calcite-mica pairs are not in oxygen isotope equilibrium at temperatures of ca. 200–400 °C, their isotopic fractionations are indicative of either 1) partial exchange between the minerals and a common external fluid, or 2) growth or isotopic exchange of the mica with the carbonate after the carbonate had isotopically exchanged with an external fluid. The geological significance of these results is not easily or uniquely determined, and exemplifies the difficulties inherent in dating very fine-grained micas of highly deformed tectonites in low-grade metamorphic terranes. Two generalizations can be made regarding the dates obtained from the Helvetic thrusts: 1) samples from the two highest thrusts (Mt. Gond and Sublage) have all of their ⁴⁰Ar/ ³⁹Ar steps above 20 Ma, and 2) most samples from the deepest Helvetic thrusts have steps (often accounting for more than 80% of ³⁹Ar release) between 15 and 25 Ma. These dates are consistent with the order of thrusting in the foreland-imbricating system and increase proportions of neoformed to detrital mica in the more metamorphosed hinterland and deeply buried portions of the nappe pile. Individual thrusts accommodated the majority of their displacement during their initial incorporation into the foreland-imbricating system, and some thrusts remained active or were reactivated down to 15 Ma.     

Stable and Sr-isotope evidence for fluid advection during thrusting of the glarus nappe (swiss alps)

At the Glarus thrust in the Swiss Helvetic Alps, Permian Verrucano siltstones are allochthonously superimposed over Tertiary Flysch with an intermediate, about 1 metre thin layer of intensively deformed calcmylonite of probable Mesozoic provenance. The H–O–C- and Sr-isotope compositions of minerals from the calc-mylonite and strongly mylonitized Verrucano siltstones were determined in order to assess: (1) equilibrium-disequilibrium relationships; (2) isotopic composition of the fluid phase, its provenance and water/rock ratios; (3) sources of Sr in the calc-mylonite; (4) deformation temperatures. The isotopic composition of cale-mylonite micro-samples from five sites along the thrust varies from 22 to 12 and 2 to-10 for ¹⁸O and ¹³C respectively. All samples are ¹⁸O depleted by up to 14 relative to the presumed marine Helvetic carbonate protoliths (¹⁸O=25.4±2). A pronounced geographic trend of ¹⁸O depletion from 22 in the north to 12 in the south is observed. In calc-mylonites, ⁸⁷Sr/⁸⁶Sr ratios range from typical Mesozoic marine carbonate protolith signatures (0.708±0.005) to more radiogenic values as high as 0.722. A variable contribution of radiogenic ⁸⁷Sr to the calc-mylonite is though to reflect interaction with fluids that aquired their Sr from the Hercynian granitic basement. Chlorites and muscovites from the calc-mylonite and Verrucano have uniform ¹⁸O values but display D values from-40 to-147%: the D-enriched values correspond to the primary metamorphic or formational fluids expelled during thrusting, whereas the D-depleted samples reflect selective H-isotope exchange with meteoric fluids during uplift of the Alpine belt. The isotopic composition of the calc-mylonites requires exchange with ¹⁸O—depleted, ⁸⁷Sr—enriched fluids at very high water/rock ratios. Possible sources for these are dewatering of the underlying Flysch and/or metamorphic fluids, or formation brines expelled along the thrust from greater depth. These could be derived from compaction and dewatering of the Flysch in the northern part of the thrust; in the south, however, where Verrucano is thrust over ¹⁸O-rich Mesozoic carbonates, the extreme ¹⁸O depletion of the calc-mylonite has to be explained either by fluid advection within the Verrucano hanging wall and thrust zone or alternatively by exchange with metamorphic fluids from greater depth, expelled along the thrust. Microstructural evidence (abundant veins, stylolites, breccias) suggests that fluids played an important role in deformation and strain localization. Excepting albite all major components (quartz, chlorite, muscovite, calcite) are both dynamically recrystallized and crystallized as secondary minerals in pressure shadows and syn-mylonitic veins, indicating that these minerals were potentially open to oxygen isotopic exchange during alpine metamorphism and thrust deformation. Within the mylonitized Verrucano silstones, isolated quartz-chlorite and quartz-calcite fractionations yield temperatures of around 320°C close to values obtained from calcite-dolomite thermometry (355°C±30) and in agreement with the regional lower greenschist facies metamorphism. Quartz-calcite and quartz-albite fractionations indicate slightly lower temperatures around 250°C, owing to selective lower temperature re-equilibration of the calcite and albite during post peak metamorphism.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.     

Fluid regimes in the deformation of the Helvetic nappes,Switzerland, as inferred from stable isotope data

The stable isotope composition of veins, pressure shadows, mylonites and fault breccias in allochthonous Mesozoic carbonate cover units of the Helvetic zone show evidence for concurrent closed and open system of fluid advection at different scales in the tectonic development of the Swiss Alps. Marine carbonates are isotopically uniform, independent of metamorphic grade, where ¹³C=1.5±1.5 (1 ) and ¹⁸O=25.4±2.2 (1 ). Total variations of up to 2 in ¹³C and 1.5 in ¹⁸O occur over a cm scale. Calcite in pre- (Type I) and syntectonic (Type II) vein arrays and pressure shadows are mostly in close isotopic compliance with the matrix calcite, to within ±0.5, signifying isotopic buffering of pore fluids by host rocks during deformation, and closed system redistribution of carbonate over a cm to m scale. This is consistent with microstructural evidence for pressure solution — precipitation deformation.Type III post-tectonic veins occur throughout 5 km of structural section, extend several km to the basement, and accommodate up to 15% extension. Whereas the main population of Type III veins is isotopically undistinguishable from matrix carbonates, calcite in the largest of these veins is depleted in ¹⁸O by up to 23 but acquired comparable ¹³C values. This generation of veins involved geopressurized hydrothermal fluids at 200 to 350° C where ¹⁸O H₂O=–8 to +20, representing variable mixtures of ¹⁸O enriched pore and metamorphic fluids, with ¹⁸O depleted meteoric water. Calc-mylonites ( ¹⁸O=25 to 11) at the base of the Helvetic units, and syntectonic veins from the frontal Pennine thrust are characterized by a trend of ¹⁸O depletion relative to carbonate protoliths, due to exchange with an isotopically variable reservoir ( ¹⁸O H₂O=20 to 4). The upper limiting value corresponds to carbonate-buffered pore fluid, whereas the lower value is interpreted as ¹⁸O-depleted formation brines tectonically expelled at lithostatic pressure from the crystalline basement. Carbonate breccias in one of the large scale late normal faults exchanged with infiltrating ¹⁸O-depleted meteoric surface waters ( ¹⁸O=–8 to –10).During the main ductile Alpine deformation, individual lithological units and associated tectonic vein arrays behaved as closed systems, whereas mylonites along thrust faults acted as conduits for tectonically expelled lithostatically pressured reservoirs driven over tens of km. At the latest stages, marked by 5 to 15 km uplift and brittle deformation, low ¹⁸O meteoric surface waters penetrated to depths of several km under hydrostatic gradients.     

Carbonate alteration associated with talc-chlorite mineralization in the eastern Pyrenees, with emphasis on the St. Barthelemy Massif

Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ¹⁸O values decrease down to values of 12‰ towards the contact with dolostones. This ¹⁸O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from ⁸⁷Sr/⁸⁶Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with ⁸⁷Sr/⁸⁶Sr = 0.7094 near dolomitization fronts. Dolostones have δ¹⁸O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (⁸⁷Sr/⁸⁶Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ¹⁸O values close to dolostones but substantially lower δ¹³C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with ⁸⁷Sr/⁸⁶Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ¹⁸O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.     

Stratotype of the Lower Riphean, the Burzyan Group of the Southern Urals: Lithostratigraphy, paleontology, geochronology, Sr- and C-isotopic characteristics of its carbonate rocks

The main objective of this work is the generalization of lithostratigraphic, biostratigraphic and isotopic-geochronological data characterizing carbonate rocks from type succession of the broadly acknowledged chronostratigraphic subdivision of the Lower Riphean, such as the Burzyan Group of the Southern Urals and its analogs. Using an original approach to investigation of the Rb-Sr and Pb-Pb isotopic systems in carbonates and strict criteria of their retentivity, we studied the least altered (“best”) samples of the Burzyan carbonates, which retain the ⁸⁷Sr/⁸⁶Sr ratio of the sedimentation environment. As long ago as 1550 ± 30 and 1430 ± 30 Ma, that ratio corresponded to 0.70460–0.70480 and 0.70456–0.70481. The results confirm the influx of the mantle material predominantly into the World Ocean of the Early Riphean. The influence of meteoric diagenesis was likely responsible for local declines of δ¹⁸O in the Burzyan carbonates down to the values of −2.5 to −1.5‰ V-PDB. In the “best” samples, this parameter ranges from −0.7 to 0‰, which is consistent with the assumption that δ¹⁸O values (0 ± 1‰) characterized the stasis of the carbonate carbon isotopic composition in oceanic water 2.06–1.25 Ga ago. C-isotopic data on carbonate from the Paleoproterozoic-Lower Riphean boundary formations of the Urals, India, North America and Siberia suggest that the mentioned stasis ended by the commencement of the Early Riphean ca. 1.6–1.5 Ga ago. In the least altered carbonates of the Early Riphean, the δ¹⁸O variation range corresponds to 4.0–4.5‰.     

Sr, C and O isotope systematics in the Pucará basin, central Peru

A combined Sr, O and C isotope study has been carried out in the Pucará basin, central Peru, to compare local isotopic trends of the San Vicente and Shalipayco Zn-Pb Mississippi Valley-type (MVT) deposits with regional geochemical patterns of the sedimentary host basin. Gypsum, limestone and regional replacement dolomite yield ⁸⁷Sr/⁸⁶Sr ratios that fall within or slightly below the published range of seawater ⁸⁷Sr/⁸⁶Sr values for the Lower Jurassic and the Upper Triassic. Our data indicate that the Sr isotopic composition of seawater between the Hettangian and the Toarcian may extend to lower ⁸⁷Sr/⁸⁶Sr ratios than previously published values. An ⁸⁷Sr-enrichment is noted in (1) carbonate rocks from the lowermost part of the Pucará basin, and (2) different carbonate generations at the MVT deposits. This indicates that host rocks at MVT deposits and in the lower-most part of the carbonate sequence interacted with ⁸⁷Srenriched fluids. The fluids acquired their radiogenic nature by interaction with lithologies underlying the carbonate rocks of the Pucará basin. The San Ramón granite, similar Permo-Triassic intrusions and their clastic derivatives in the Mitu Group are likely sources of radiogenic ⁸⁷Sr. The Brazilian shield and its erosion products are an additional potential source of radiogenic ⁸⁷Sr. Volcanic rocks of the Mitu Group are not a significant source for radiogenic ⁸⁷Sr; however, molasse-type sedimentary rocks and volcaniclastic rocks cannot be ruled out as a possible source of radiogenic ⁸⁷Sr. The marked enrichment in ⁸⁷Sr of carbonates toward the lower part of the Pucará Group is accompanied by only a slight decrease in ¹⁸O values and essentially no change in ¹³C values, whereas replacement dolomite and sparry carbonates at the MVT deposits display a coherent trend of progressive ⁸⁷Sr-enrichment, and ¹⁸O- and ¹³C-depletion. The depletion in ¹⁸O in carbonates from the MVT deposits are likely related to a temperature increase, possibly coupled with a ¹⁸O-enrichment of the ore-forming fluids. Progressively lower ¹³C values throughout the paragenetic sequence at the MVT deposits are interpreted as a gradually more important contribution from organically derived carbon. Quantitative calculations show that a single fluid-rock interaction model satisfactorily reproduces the marked ⁸⁷Sr-enrichment and the slight decrease in ¹⁸O values in carbonate rocks from the lower part of the Pucará Group. By contrast, the isotopic covariation trends of the MVT deposits are better reproduced by a model combining fluid mixing and fluid-rock interaction. The modelled ore-bearing fluids have a range of compositions between a hot, saline, radiogenic brine that had interacted with lithologies underlying the Pucará sequence and cooler, dilute brines possibly representing local fluids within the Pucará sequence. The composition of the local fluids varies according to the nature of the lithologies present in the neighborhood of the different MVT deposits. The proportion of the radiogenic fluid in the modelled fluid mixtures interacting with the carbonate host rocks at the MVT deposits decreases as one moves up in the stratigraphic sequence of the Pucará Group.     

Prograde and retrograde fluid-rock interaction in calc-silicates northwest of the Idaho batholith: stable isotopic evidence

Carbon and oxygen isotopic analyses of silicate and carbonate minerals indicate that isotopic compositions in metasediments of the Wallace Formation (Belt Supergroup) exposed northwest of the Idaho batholith have been affected by both prograde and retrograde fluid-rock interaction. Silicates retain isotopic fractionations that reflect equilibration at peak metamorphic temperatures. In contrast, calcite oxygen isotopic compositions range from δ¹⁸O(Calcite)=+2.3 to +18.6‰ SMOW (standard mean oceanic water) and indicate that some calcites have exchanged with low-δ¹⁸O meteorichydrothermal fluids. Values of Δ¹⁸O (Quartz-Calcite) as large as +15.5 clearly indicate that the isotopic depletion of these calcites postdates the peak of regional metamorphism. Carbon isotopic compositions of ¹⁸O-depleted calcites are not significantly shifted relative to δ¹³C values in undepleted calcites, suggesting that the retrograde fluid was carbon-poor. Petrographically, retrograde fluid-rock interaction is associated with the occurrence of fine-grained, highly-luminescent calcite overgrowths on less-luminescent, metamorphic calcites, slight to moderate argillic alteration, and pseudomorphing of scapolite porphyroblasts by fine-grained albite. Retrograde isotopic depletions may be related to shallow meteoric-hydrothermal fluid flow developed around the Idaho batholith after intrusion and rapid uplift of the terrane. Peak metamorphic isotopic compositions in the Wallace Formation reflect mineralogically heterogeneous protolith compositions and isotopic fractionation due to devolatilization and/or infiltration. Variability in oxygen isotopic compositions on the order of 4–6‰ within the same rock type can be attributed to the combined effects of inherited isotopic compositions and isotopic shifts resulting from prograde devolatilization. Isotopic and compositional heterogeneity on the scale of mm to m precludes generalization of isotopic gradients on a regional scale. The isotopic data presented here, and metamorphic fluid compositions determined in previous studies, are best reconciled with heterogeneous bulk compositions, dominantly channelized prograde and retrograde fluid flow, and locally low fluid-rock ratios.     

Hypogene Zn carbonate ores in the Angouran deposit,NW Iran

The world-class Angouran nonsulfide Zn–Pb deposit is one of the major Zn producers in Iran, with resources estimated at about 18 Mt at 28% Zn, mainly in the form of the Zn carbonate smithsonite. This study aims to characterize these carbonate ores by means of their mineralogy and geochemistry, which has also been extended to the host rocks of mineralization and other local carbonate rock types, including the prominent travertines in the Angouran district, as well as to the local spring waters. Petrographical, chemical, and stable isotope (O, H, C, Sr) data indicate that the genesis of the Zn carbonate ores at Angouran is fairly distinct from that of other “classical” nonsulfide Zn deposits that formed entirely by supergene processes. Mineralization occurred during two successive stages, with the zinc being derived from a preexisting sulfide ore body. A first, main stage of Zn carbonates (stage I carbonate ore) is associated with both preexisting and subordinate newly formed sulfides, whereas a second stage is characterized by supergene carbonates (Zn and minor Pb) coexisting with oxides and hydroxides (stage II carbonate ore). The coprecipitation of smithsonite with galena, pyrite and arsenopyrite, as well as the absence of Fe- and Mn-oxides/hydroxides and of any discernible oxidation or dissolution of the sphalerite-rich primary sulfide ore, shows that the fluids responsible for the main, stage I carbonate ores were relatively reduced and close to neutral to slightly basic pH with high fCO₂. Smithsonite δ¹⁸O_VSMOW values from stage I carbonate ore range from 18.3 to 23.6‰, while those of stage II carbonate ore show a much smaller range between 24.3 and 24.9‰. The δ¹³C values are fairly constant in smithsonite of stage I carbonate ore (3.2–6.0‰) but show a considerable spread towards lower δ¹³C_VPDB values (4.6 to −11.2‰) in stage II carbonate ore. This suggests a hypogene formation of stage I carbonate ore at Angouran from low-temperature hydrothermal fluids, probably mobilized during the waning stages of Tertiary–Quaternary volcanic activity in an environment characterized by abundant travertine systems throughout the whole region. Conversely, stage II carbonate ore is unambiguously related to supergene weathering, as evidenced by the absence of sulfides, the presence of Fe-Mn-oxides and arsenates, and by high δ¹⁸O values found in smithsonite II. The variable, but still relatively heavy carbon isotope values of supergene smithsonite II, suggests only a very minor contribution by organic soil carbon, as is generally the case in supergene nonsulfide deposits.     

Fluid flow through the sedimentary cover in northern Switzerland recorded by calcite–celestite veins (Oftringen borehole,Olten)

Abundant veins filled by calcite, celestite and pyrite were found in the core of a 719 m deep borehole drilled in Oftringen near Olten, located in the north-western Molasse basin, close to the thrust of the Folded Jura. Host rocks are calcareous marl, argillaceous limestone and limestone of the Dogger and Malm. The δ¹⁸O values of vein calcite are lower than in host rock carbonate and, together with microthermometric data from fluid inclusions in vein calcite, indicate precipitation from a seawater-dominated fluid at average temperatures of 56–68°C. Such temperatures were reached at the time of maximum burial of the sedimentary pile in the late Miocene. The depth profile of δ¹³C and ⁸⁷Sr/⁸⁶Sr values and Sr content of both whole-rock carbonate and vein calcite show marked trends towards negative δ¹³C, high ⁸⁷Sr/⁸⁶Sr, and low Sr content in the uppermost 50–150 m of the Jurassic profile (upper Oxfordian). The ⁸⁷Sr/⁸⁶Sr of vein minerals is generally higher than that of host rock carbonate, up to very high values corresponding to Burdigalian seawater (Upper Marine Molasse, Miocene), which represents the last marine incursion in the region. No evidence for internally derived radiogenic Sr (clay minerals) has been found and so an external source is required. S and O isotope composition of vein celestite and pyrite can be explained by bacterial reduction of Miocene seawater sulphate. The available data set suggests the vein mineralization precipitated from descending Burdigalian seawater and not from a fluid originating in the underlying Triassic evaporites.     

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     

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     

The Gumeshevo skarn-porphyry copper deposits in the Central Urals,Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr,Nd, C,O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (⁸⁷Sr/⁸⁶Sr)_t and (ɛ_Nd)_t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The ⁸⁷Sr/⁸⁶Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (⁸⁷Sr/⁸⁶Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ¹⁸O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ¹³C and δ¹⁸O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ³⁴S of sulfides is 0 to 2‰ (relative to CDT);⁸⁷Sr/⁸⁶Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ¹³C and ⁸⁷Sr/⁸⁶Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.     

Origin of the Rubian carbonate-hosted magnesite deposit, Galicia, NW Spain: mineralogical, REE, fluid inclusion and isotope evidence

The Rubian magnesite deposit (West Asturian—Leonese Zone, Iberian Variscan belt) is hosted by a 100-m-thick folded and metamorphosed Lower Cambrian carbonate/siliciclastic metasedimentary sequence—the Cándana Limestone Formation. It comprises upper (20-m thickness) and lower (17-m thickness) lens-shaped ore bodies separated by 55 m of slates and micaceous schists. The main (lower) magnesite ore body comprises a package of magnesite beds with dolomite-rich intercalations, sandwiched between slates and micaceous schists. In the upper ore body, the magnesite beds are thinner (centimetre scale mainly) and occur between slate beds. Mafic dolerite dykes intrude the mineralisation. The mineralisation passes eastwards into sequence of bedded dolostone (Buxan) and laminated to banded calcitic marble (Mao). These show significant Variscan extensional shearing or fold-related deformation, whereas neither Rubian dolomite nor magnesite show evidence of tectonic disturbance. This suggests that the dolomitisation and magnesite formation postdate the main Variscan deformation. In addition, the morphology of magnesite crystals and primary fluid inclusions indicate that magnesite is a neoformed hydrothermal mineral. Magnesite contains irregularly distributed dolomite inclusions (<50 μm) and these are interpreted as relics of a metasomatically replaced dolostone precursor. The total rare earth element (REE) contents of magnesite are very similar to those of Buxan dolostone but are depleted in light rare earth elements (LREE); heavy rare earth element concentrations are comparable. However, magnesite REE chondrite normalised profiles lack any characteristic anomaly indicative of marine environment. Compared with Mao calcite, magnesite is distinct in terms of both REE concentrations and patterns. Fluid inclusion studies show that the mineralising fluids were MgCl₂–NaCl–CaCl₂–H₂O aqueous brines exhibiting highly variable salinities (3.3 to 29.5 wt.% salts). This may be the result of a combination of fluid mixing, migration of pulses of variable-salinity brines and/or local dissolution and replacement processes of the host dolostone. Fluid inclusion data and comparison with other N Iberian dolostone-hosted metasomatic deposits suggest that Rubian magnesite probably formed at temperatures between 160 and 200°C. This corresponds, at hydrostatic pressure (500 bar), to a depth of formation of ~~5 km. Mineralisation-related Rubian dolomite yields δ ¹⁸O values (δ ¹⁸O: 12.0–15.4‰, mean: 14.4±1.1‰) depleted by around 5‰ compared with barren Buxan dolomite (δ ¹⁸O: 17.1–20.2‰, mean: 19.4±1.0‰). This was interpreted to reflect an influx of ¹⁸O-depleted waters accompanied by a temperature increase in a fluid-dominated system. Overlapping calculated δ ¹⁸O_fluid values (~+5‰ at 200°C) for fluids in equilibrium with Rubian dolomite and magnesite show that they were formed by the same hydrothermal system at different temperatures. In terms of δ ¹³C values, Rubian dolomite (δ ¹³C: −1.4 to 1.9‰, mean: 0.4±1.3‰) and magnesite (δ ¹³C: −2.3 to 2.4‰, mean: 0.60±1.0‰) generally exhibit more negative δ ¹³C values compared with Buxan dolomite (δ ¹³C: −0.2 to 1.9‰, mean: 0.8±0.6‰) and Mao calcite (δ ¹³C: −0.3 to 1.5‰, mean: 0.6±0.6‰), indicating progressive modification to lower δ ¹³C values through interaction with hydrothermal fluids. ⁸⁷Sr/⁸⁶Sr ratios, calculated at 290 Ma, vary from 0.70849 to 0.70976 for the Mao calcite and from 0.70538 to 0.70880 for the Buxan dolostone. The ⁸⁷Sr/⁸⁶Sr ratios in Rubian magnesite are more radiogenic and range from 0.71123 to 0.71494. The combined δ ¹⁸O–δ ¹³C and ⁸⁷Sr/⁸⁶Sr data indicate that the magnesite-related fluids were modified basinal brines that have reacted and equilibrated with intercalated siliciclastic rocks. Magnesite formation is genetically linked to regional hydrothermal dolomitisation associated with lithospheric delamination, late-Variscan high heat flow and extensional tectonics in the NW Iberian Belt. A comparison with genetic models for the Puebla de Lillo talc deposits suggests that the formation of hydrothermal replacive magnesite at Rubian resulted from a metasomatic column with magnesite forming at higher fluid/rock ratios than dolomite. In this study, magnesite generation took place via the local reaction of hydrothermal dolostone with the same hydrothermal fluids in very high permeability zones at high fluid/rock ratios (e.g. faults). It was also possibly aided by additional heat from intrusive dykes or sub-cropping igneous bodies. This would locally raise isotherms enabling a transition from the dolomite stability field to that of magnesite.Editorial handling: F. Tornos     

Carbon and oxygen isotopic composition of car- bonate cements of different phases in terrigenous siliciclastic reservoirs and significance for their origin： A case study from sandstones of the Triassic Yanchang Formation, southwestern Ordos Basin, China

Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.     

Oxygen isotope mapping of the Archean Sturgeon Lake caldera complex and VMS-related hydrothermal system, Northwestern Ontario, Canada

The hydrothermal and magmatic evolution of the Sturgeon Lake caldera complex is graphically documented by a regional-scale (525 km²) analysis of oxygen isotopes. Spatial variations in whole-rock oxygen isotope compositions provide a thermal map of the cumulative effects of multiple stages of hydrothermal metasomatism before, during, and after volcanogenic massive sulfide (VMS) mineralization. There is a progressive, upward increase in δ¹⁸O from less than 2‰ to greater than 15‰ through a 5-km-thick section above the Biedelman Bay subvolcanic intrusive complex. This isotopic trend makes it clear that at least the earlier phases of this intrusive complex were coeval with the overlying VMS-hosting cauldron succession and provided thermal energy to drive a convective hydrothermal circulation system. The sharp contrast in δ¹⁸O values between late stage phases of the Biedelman Bay intrusion and immediate hanging wall strata indicates that the main phase of VMS-related hydrothermal activity took place before late-stage resurgence in the cauldron-related magmatic activity. Mineralogical and isotopic evidence indicates the presence of both syn- and postmineralization hydrothermal activity defined by the presence of widespread semiconformable and more restricted discordant alteration zones that affect the pre- and syncauldron strata. The semiconformable alteration zones formed during early stages of hydrothermal circulation and are defined by widespread silicification and carbonatization in association with relatively high δ¹⁸O values. The discordant alteration assemblages, containing Al-silicate minerals with chloritoid and/or Fe-rich carbonate or chlorite, centered on synvolcanic faults represent restricted zones of both seawater inflow and hydrothermal fluid upflow. A rapid increase in δ¹⁸O values (∼7–9‰) over a short distance (<200 m) suggests marked cooling of hydrothermal fluid from ∼350°C to less than 130°C either just before or during discharge onto the seafloor. Late emplacement of diorite sills and a dacite dome disrupted the isotopic imprint of cauldron-stage hydrothermal activity. The abrupt lowering of δ¹⁸O values at the transition from explosive to passive volcanism (andesite flows and dacite domes) indicates postcauldron emergence. Subsequently, thrust faulting disrupted the older synvolcanic hydrothermal isotopic patterns.     

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     

Reconstructing the History of eastern and Central Florida Bay using mollusk-shell isotope records

Stable isotopic ratios of carbon and oxygen (δ¹³C and δ¹⁸O) from mollusk shells reflect the water quality characteristics of Florida Bay and can be used to characterize the great temporal variability of the bay. Values of δ¹⁸O are directly influenced by temperature and evaporation and may be related to salinity, δ¹³C values of δ¹³C are sensitive to organic and inorganic sources of carbon and are influenced by productivity. Analyses of eight mollusk species from five short-core localities across Florida Bay show large ranges in the values of δ¹³C and δ¹⁸O, and reflect the variation of the bay over decades. Samples from southwester Florida Bay have distinct δ¹³C values relative to samples collected in northeastern Florida Bay, and intermediate localities have intermediate values.¹³C values of δ¹³C grade from marine in the southwest bay to more estuarine in the northeast. Long cores (>1m), with excellent chronologies were analyzed from central and eastern Florida Bay. Preliminary analyses ofBrachiodontes exustus andTransenella spp. from the cores showed that both δ¹³C and δ¹⁸O changed during the first part of the twentieth century. After a century of relative stability during the 1800s, δ¹³C decreased between about 1910 and 1940, then stabilized at these new values for the next five decades. The magnitude of the reduction in δ¹³C values increased toward the northeast. Using a carbon budget model, reduced δ¹³C values are interpreted as resulting from decreased circulation in the bay, probably associated with decreased freshwater flow into the Bay. Mollusk shell δ¹⁸O values display several negative excursions during the 1800s, suggesting that the bay was less evaporitic than during the twentieth century. The isotope records indicate a fundamental change took place in Florida Bay circulation early in the twentieth century. The timing of the change links it to railroad building and early drainage efforts in South Florida rather than to flood control and water management measures initiated after World War II.     

Oxygen isotope evidence for subduction and rift-related mantle metasomatism beneath the Colorado Plateau–Rio Grande rift transition

Spinel lherzolite and pyroxenite xenoliths from the Rio Puerco Volcanic Field, New Mexico, were analyzed for oxygen isotope ratios by laser fluorination. In lherzolites, olivine δ¹⁸O values are high (+5.5‰), whereas δ¹⁸O values for pyroxenes are low (cpx=+5.1‰; opx=+5.4‰) compared to average mantle values. Pyroxenite δ¹⁸O values (cpx=+5.0‰; opx=+5.3‰) are similar to those of the lherzolites and are also lower than typical mantle oxygen isotope compositions. Texturally and chemically primary calcite in pyroxenite xenoliths is far from isotopic equilibrium with other phases, with δ¹⁸O values of +21‰. The isotopic characteristics of the pyroxenite xenoliths are consistent with a petrogenetic origin from mixing of lherzolitic mantle with slab-derived silicate and carbonatite melts. The anomalously low δ¹⁸O in the pyroxenes reflects metasomatism by a silicate melt from subducted altered oceanic crust, and high δ¹⁸O calcite is interpreted to have crystallized from a high δ¹⁸O carbonatitic melt derived from subducted ophicarbonate. Similar isotopic signatures of metasomatism are seen throughout the Rio Puerco xenolith suite and at Kilbourne Hole in the southern Rio Grande rift. The discrete metasomatic components likely originated from the subducted Farallon slab but were not mobilized until heating associated with Rio Grande rifting occurred. Oxygen diffusion modeling requires that metasomatism leading to the isotopic disequilibrium between calcite and pyroxene in the pyroxenites occurred immediately prior to entrainment. Melt infiltration into spinel-facies mantle (xenoliths) prior to eruption was thus likely connected to garnet-facies melting that resulted in eruption of the host alkali basalt.