Hydrothermal alteration and oxygen and hydrogen isotope geochemistry of the D-68 zone Cu-Zn Massive Sulfide Deposit,Noranda District,Quebec, Canada

Summary Pervasive hydrothermal alteration zones in quartz-feldspar porphyry domes underly all massive sulfide lenses in the D-68 Zone Cu-Zn deposit, Noranda. Alteration pipes are mineralogically zoned and contain chloritic cores consisting of stringer sulfides, enveloped by sericitic haloes. Silicified rocks are found locally.Alteration took place at nearly constant volume. Na depletion, and K enrichment relative to the least altered rocks, are found in all alteration zones. Fe and Mg have been added to the chloritic zone and subtracted in the sericitic and silicic zones. Ca and Si are enriched mainly in the silicic zone. Al, Ti and Zr were the least mobile of the elements studied.Whole-rock ¹⁸O values vary from +5.6 to +6.2 per mil in chloritized rocks, +5.8 to + 7.3 per mil in sericitized rocks and + 7.2 to + 8.3 per mil in silicified rocks. D values for two chloritized samples are – 63 and – 70 per mil whereas in two sericitized samples they are close to –62 per mil. Quartz from the chlorite alteration zone is isotopically heavier (¹⁸O = 8.6 per mil) than that from the sericite alteration zone (¹⁸O = 6.4 per mil), suggesting equilibration with different hydrothermal fluid or different temperature of alteration. Assuming an alteration temperature of 300° + 50°C the fluid in equilibrium with quartz and chlorite had ¹⁸O and D values of about 1.5 ± 2.0 per mil and –23 ± 5 per mil, respectively. The fluid in equilibrium with quartz and sericite had ¹⁸O and D values of about –0.5 ± 2 per mil and –30 ± 5 per mil, respectively. On the basis of isotopic data, seawater was probably the major constituent of the hydrothermal fluids.

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Hydrothermale Umwandlung und Sauerstoff-Wasserstoff-Isotopengeochemie der Zone D-68 Cu-Zn Derberz Sulfidlagerstätte, Noranda District, Quebec, Canada

Zusammenfassung Hydrothermale Umwandlungszonen in porphyrischen Quarz-Feldspat Gesteinskörpern liegen unterhalb von Derberz Sulfidlinsen in der D-68 Zone Cu-Zn Lagerstätte, Noranda. Umgewandelte pipes sind mineralogisch zoniert; sie enthalten aus Sulfiden bestehende chloritische Kerne, die von sericitischen Höfen umhüllt werden. Lokal treten silicifizierte Gesteine auf.Die Umwandlung ging bei annähernd konstantem Volumen vor sich. Na-Verarmung und K-Anreicherung, bezogen auf die am wenigsten umgewandelten Gesteine, liegen in allen Umwandlungszonen vor. Fe und Mg wurden der Chloritzone zugeführt, in den Sericit- und Si-Zonen abgeführt. Ca und Si sind vor allem in der Si-Zone angereichert. Al, Ti und Zr waren von den untersuchten Elementen am wenigsten mobil.Gesamtgesteins-¹⁸O Werte variieren von +5,6 bis +6,2 in den chloritisierten Gesteinen, von +5,8 bis 7,3 in sericitisierten Gesteinen und von +7,2 bis +8,3 in den silicifizierten Gesteinen. Die D Werte für zwei chloritisierte Proben betragen –63 und –70, in zwei sericitisierten Proben liegen sie hingegen nahe bei –62. Quarz von der Chlorit-Umwandlungszone ist isotopisch schwerer (¹⁸O = 8,6) als von der Sericit-Umwandlungszone (¹⁸O = 6.4), was eine Gleichgewichtseinstellung mit verschiedenen hydrothermalen Lösungen oder eine verschiedene Umwandlungstemperatur nahelegt. Bei einer angenommenen Umwandlungstemperatur von 300 ± 50°C, hatte die im Gleichgewicht mit Quarz und Chlorit stehende Lösung ¹⁸O und D Werte von etwa 1,5 ± 2 bzw. –23 + 5. Die im Gleichgewicht mit Quarz und Sericit befindliche Lösung hatte ¹⁸O und D Werte von etwa –0,5 ± 2%o bzw. –30 ± 5. Aufgrund der Isotopendaten war wahrscheinlich Meerwasser der Hauptbestandteil der hydrothermalen Lösungen.

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With 7 Figures     

Possible non-equilibrium oxygen isotope effects in mantle nodules,an alternative to the Kyser-O'Neil-Carmichael18O/16O geothermometer

Kyser, O'Neil, and Carmichael (1981, 1982) measured the ¹⁸O values of coexisting minerals from peridotite nodules in alkali basalts and kimberlites, interpreting the nodules as equilibrium assemblages. Using Ca-Mg-Fe element-partition geothermometric data, they proposed an empirical¹⁸O/¹⁶O geothermometer: T(°C)=1,151–173–68 ², where is the per mil pyroxene-olivine fractionation. However, this geothermometer has an unusual crossover at 1,150 °C, and in contrast to what might be expected during closed-system equilibrium exchange, the most abundant mineral in the nodules (olivine) shows a much greater range in ¹⁸O (+4.4 to +7.5) than the much less abundant pyroxene (all 50 pyroxene analyses from spinel peridotites lie within the interval +5.3 to +6.5). On ¹⁸O-olivinevs. ¹⁸O-pyroxene diagrams, the mantle nodules exhibit data arrays that cut across the ¹⁸O=zero line. These arrays strongly resemble the non-equilibrium quartzfeldspar and feldspar-pyroxene ¹⁸O arrays that we now know are diagnostic of hydrothermally altered plutonic igneous rocks. Thus, we have re-interpreted the Kyser et al. data as non-equilibrium phenomena, casting doubt on their empirical geothermometer. The peridotite nodules appear to have been open systems that underwent metasomatic exchange with an external, oxygen-bearing fluid (CO₂, magma, H₂O, etc.); during this event, the relatively inert pyroxenes exchanged at a much slower rate than did the coexisting olivines and spinels, in agreement with available exchange-rate and diffusion measurements on these minerals. This accounts for the correlation between ¹⁸O pyroxene-olivine and the whole-rock ¹⁸O of the peridotites, which is a major difficulty with the equilibrium interpretation.Contribution No. 3978, Publications of the Division of Geological and Planetary Sciences, California Institute of Technology     

18O/16O ratios in ash-flow tuffs and lavas erupted from the central Nevada caldera complex and the central San Juan caldera complex,Colorado

Oxygen isotope compositions were measured on 129 quartz, feldspar, and biotite phenocrysts from ash-flow tuffs and lava domes erupted from the Oligocene central Nevada and central San Juan caldera complexes. Most of the ash-flow tuffs are compositionally zoned with low-phenocryst rhyolite bases and high-phenocryst quartz-latite tops, but both within individual units and throughout each of the eruptive sequences at each locality, the ¹⁸O values are remarkably constant. ¹⁸O values of the central Nevada magmas range from +9.1 to +9.8 per mil: These values are high and indicate the involvement of high-¹⁸O geosynclinal sediments in the melting process. Magmatic ¹⁸O values decrease by only about 0.4 per mil from the initial eruption sequence to the middle eruptive, the giant Monotony Tuff (3000 km³). The initial higher ¹⁸O values are reestablished in the late eruptive sequence, but decrease again by about 0.4 per mil in the latest ring-fracture eruptions. ¹⁸O values in the central San Juan magmas range from +6.8 to +7.5: These values are relatively low and indicate involvement of lower cratonal crust and upper mantle in the melting process. Magmatic ¹⁸O values decrease by about 0.4 per mil from the early sequence (Fish Canyon, Carpenter Ridge, and Mammoth Mountain Tuffs) to the late sequence (Wason Park, Nelson Mountain, and Snowshoe Mountain Tuffs). ¹⁸O/¹⁶O fractionations among phenocrysts in both Nevada and Colorado are much smaller than among corresponding minerals in plutonic granitic rocks. These fractionations also decrease from stratigraphically lower to higher samples in each cooling unit, so the ¹⁸O/¹⁶O data agree with other evidence that these represent quenched equilibrium at magmatic temperatures, and that prior to eruption the tops of the magma chambers were cooler than the deeper portions. In striking contrast to what is observed in Iceland and in the late-Tertiary to Quaternary southwest Nevada and Yellowstone caldera complexes, we have found no evidence for any low-¹⁸O rhyolitic magmas. Thus, low-¹⁸O rhyolitic magmas must be less common than heretofor believed, and their origin must be a result of special circumstances involving the timing, depth, and intensity of meteoric-hydrothermal activity. We tentatively suggest that extensional tectonics and regional rifting may be one of the prerequisites for their development.Contribution No. 4106, Publications of the Division of Geological and Planetary Sciences, California Institute of Technology     

A sulfur isotope study of volcanogenic massive sulfide deposits of the Eastern Black Sea province,Turkey

Kuroko-type massive sulfide deposits of the Eastern Black Sea province of Turkey are related to the Upper Cretaceous felsic lavas and pyroclastic rocks, and associated with clay and carbonate alteration zones in the footwall and hangingwall lithologies. A complete upward-vertical section of a typical orebody consists of a stringer-disseminated sulfide zone composed mainly of pyrite and chalcopyrite; a massive pyrite zone; a massive yellow ore consisting mainly of chalcopyrite and pyrite; a black ore made up mainly of galena and sphalerite with minor amounts of chalcopyrite, bornite, pyrite and various sulfosalts; and a barite zone. Most of the deposits in the province are associated with gypsum in the footwall or hangingwall. The paragenetic sequence in the massive ore is pyrite, sphalerite, chalcopyrite, bornite, galena and various sulfosalts, with some overlap between the mineral phases. Massive, stringer and disseminated sulfides from eight kuroko-type VMS deposits of the Eastern Black Sea province have a ³⁴S range of 0–7 per mil, consistent with the ³⁴S range of felsic igneous rocks. Sulfides in the massive ore at Madenköy (4.3–6.1 per mil) differ isotopically from sulfides in the stringer zone (6.3–7.2 per mil) suggesting a slightly increased input of H₂S derived from marine sulfate with time. Barite and coarse-grained gypsum have a ³⁴S range of 17.7–21.5 per mil, a few per mil higher than the ³⁴S value of contemporaneous seawater sulfate. The deposits may, therefore, have formed in restricted basins in which bacterial reduction of sulfate was taking place. Fine-grained, disseminated gypsum at Kutlular and Tunca has ³⁴S values (2.6–6.1 per mil) overlapping those of ore sulfides, indicating sulfide oxidation during waning stages of hydrothermal activity.     

Oxygen and hydrogen isotope compositions as indicators of granite genesis in the New England Batholith,Australia

Oxygen and hydrogen isotope studies of a number of granite suites and mineral separates from the New England Batholith indicate that O¹⁸ can be used to discriminate the major granite protoliths. The granite suites previously subdivided on the basis of mineralogical and geochemical criteria into S-type (sedimentary) and I-type (igneous) have O¹⁸ values consistently higher in the S-type granites (10.4–12.5) than in the spatially related I-type plutons (7.7–9.9). There appears to be a systematic variation in O¹⁸ from the most S-type to the most I-type granites, the dividing point between the two occuring at O¹⁸ equal to 10. A group of leucocratic granites that form about half of the batholith and difficult to classify mineralogically and geochemically is found to have low O¹⁸ values (6.4–8.1), suggesting an affinity to the most I-type granites. A single leucogranite pluton with minor muscovite has a O¹⁸ of 9.6 which is significantly higher than other leucogranites indicating a different origin perhaps involving amphibole fractionation.The behavior of D in the plutonic rocks is much less systematic than O¹⁸. Excluding samples collected adjacent to major faults, the D values show a rough positive correlation with water content similar to, but less pronounced than, the trend previously observed in the Berridale Batholith, southeastern Australia. This relation is considered to reflect an interaction between meteoric water and the granites, the largest effect being observed in samples with the least amount of water. Of note is the generally lower D values of the upper Paleozoic New England Batholith compared with the Silurian Berridale Batholith. This difference may be related to a near equatorial paleolatitude of 22 °S in the Silurian and near polar paleolatitudes in the late Carboniferous that have been inferred for these regions. Granite samples collected from near major faults, and one ignimbrite sample of rhyodacite composition, have very low D values (less than –120) suggesting a much greater degree of interaction with meteoric water.     

Stable isotope and fluid inclusion studies of carbonate deposits from the Tolfa Mountains mining district (Latium,central Italy)

Carbon and oxygen isotope analyses were made of representative samples of calcite and quartz from the carbonate deposits in the Tolfa Mountains mining district. Measurements were also made of hydrogen isotope compositions, filling temperatures and salinities of fluid inclusions in these minerals. There are three stages of mineralization at Tolfa. In stage I, characterized by calc-silicate hornfels, the carbonates have relatively high ¹⁸O values of 14.5 to 21.6 suggesting a rather low water/rock ratio. ¹³C values of –0.3 to 2.1 indicate that appreciable decarbonation or introduction of deep-seated carbon did not occur. Stage II is marked by phanerocrystalline carbonates; ¹⁸O values of 13.1 to 20.0 and ¹³C values of 0.7 to 5.0 identify them as hydrothermal veins rather than marbles. D values of –56 to –50 for inclusion fluids suggest a possible magmatic component to the hydrothermal fluid. Filling temperatures of coarse-grained samples of Calcite II are 309° to 362° C with a salinity range of 5.3 to 7.1 weight percent NaCl. Calculated ¹⁸O values of 11–12 for these fluids are again indicative of low water/rock ratios. The sparry calcites of stage III have ¹⁸O and ¹³C values of 8.1 to 12.9 and –1.7 to 3.2, respectively. D values of inclusion fluids are –40 to –33, clearly heavier than in earlier stages and similar to values of modern local ground waters. A salinity measurement of <0.1 weight percent NaCl in a sample of Calcite III is compatible with a relatively unaltered ground water origin for this fluid. Precipitation of the sparry calcite took place at much lower temperatures, around 160° C. For quartz, ¹⁸O values of 9.3 to 12.4 and D values for inclusions of –53 to –28 are consistent with its late occurrence and paragenetic link with associated carbonates.     

Characteristics and chronology of fracture — fluid infiltration in the Archean,Eye Dashwa Lakes pluton,Superior Province: evidence from H,C, O-isotopes and fluid inclusions

The Archean Eye Dashwa Lakes pluton (2672±24 Ma) has domains of mineralogically fresh isotropic granite, domains that have undergone bulk hydrothermal alteration, and at least eleven sets of sequential fracture arrays, each with distinctive mineral assemblages. Fresh granite is characterized by whole rock ¹⁸O=8.1 to 8.6 and primary magmatic quartz-feldspar (+1.3), quartz-biotite (5.2 to 5.4) and quartz-magnetite (+9.8) fractionations. Magmatic fluids had a calculated isotopic composition of ¹⁸O=7.9±0.5, and D=–80±5. These isotropic volumes of the granite have not experienced significant incursion of external thermal waters. Pegmatites, quartz-molybdenite veins, and phlogopite-muscovite coated fractures are sporadically distributed in the granite, and were precipitated from high-temperature magmatic fluids where ¹⁸O=8.0 to 10.3 and D=–80±5.The most abundant variety of fracture filling assemblage is epidote-quartz-chlorite±muscovite: fractures are bounded by domains of mineralogically similar bulk hydrothermal alteration of the granite. These minerals formed at 160 to 280° C, in the presence of NaCl, and NaCl-MgCl₂ brines (up to 25 wt% NaCl equivalent) of probable evolved marine water origin ( ¹⁸O=+0.4 to +3.8, D=–10 to –35) undergoing transient boiling. Upper plateau ⁴⁰Ar/³⁹Ar ages for the muscovite are 2650±15 Ma. Sequentially in the chronology of fracture-infiltration events, calcite-fluorite veins were deposited from boiling fluids at 340 to 390° C, isotopically characterized by ¹⁸O=4.7 and ¹³C=–5; and rare prehnite-chlorite lined fractures formed at 250 to 290° C. A generation of adularia-bearing veins precipitated at 140 to 230° C, from CaCl₂-NaCl brines, where ¹⁸O=0 to –6.5 and D=–10 to –30. Incremental ⁴⁰Ar/³⁹Ar age spectra on the K-feldspar yield an upper plateau of 1100 Ma. Subsequently, hematite developed during reactivation of earlier fractures, at 140 to 210° C in the presence of fluids characterized by ¹⁸O=–0.4 to –5.4 and D=–15 to –25. Arrays of open fractures partially occupied by gypsum and goethite reflect a fluid infiltration event at temperatures <50° C. Many of the earlier generations of fracture minerals have transgranular fracture infillings which record the presence of low temperature (88–190° C), hypersaline CaCl₂-NaCl brines. Narrow fractures lined with clays±calcite are sites for seepage of modern ground-waters. The isotopic signature of clay ( ¹⁸O=12 to 20, D=–80±5) plots near the line for modern kaolinites, confirming its formation in the presence of recent surface waters. Calcites coexisting with the clay minerals, and in fractured pegmatite show a common isotopic signature ( ¹⁸O=23±0.5, ¹³C=–13.6), indicating precipitation from modern groundwaters, where reactivated fractures have acted as conduits for infiltration of surface waters to depths of 200 m. Intermittent fracture-infiltration has occurred over 2.7 Ga. The early sequences of fracture-related fluid flow are interpreted in terms of devolatilization of the granite, followed by thermal contraction fracturing, incursion of marine water and convective cooling in the Archean. Hematite and adularia fracture fillings correspond to a stage when meteoric water infiltrated the volcanicplutonic terrain during Proterozoic and later times. Episodic fracture-fluid expulsion events may have been driven by seismic pumping, in response to magmatically and tectonically induced stresses within the Shield, with surface waters penetrating to depths of 15 km in the crust.     

Ion microprobe analysis of oxygen isotope ratios in granulite facies magnetites: diffusive exchange as a guide to cooling history

Ion microprobe analysis of magnetites from the Adirondack Mountains, NY, yields oxygen isotope ratios with spatial resolution of 2–8 m and precision in the range of 1 (1 sigma). These analyses represent 11 orders of magnitude reduction in sample size compared to conventional analyses on this material and they are the first report of routinely reproducible precision in the 1 per mil range for analysis of ¹⁸O at this scale. High precision micro-analyses of this sort will permit wide-ranging new applications in stable isotope geochemistry. The analyzed magnetites form nearly spherical grains in a calcite matrix with diopside and monticellite. Textures are characteristic of granulite facies marbles and show no evidence for retrograde recrystallization of magnetite. Magnetites are near to Fe₃O₄ in composition, and optically and chemically homogeneous. A combination of ion probe plus conventional BrF₅ analysis shows that individual grains are homogeneous with ¹⁸O=8.9±1 SMOW from the core to near the rim of 0.1–1.2 mm diameter grains. Depth profiling into crystal growth faces of magnetites shows that rims are 9 depleted in ¹⁸O. These low ¹⁸O values increase in smooth gradients across the outer 10 m of magnetite rims in contact with calcite. These are the sharpest intracrystalline gradients measured to date in geological materials. This discovery is confirmed by bulk analysis of 150–350 m diameter magnetites which average 1.2 lower in ¹⁸O than coarse magnetites due to low ¹⁸O rims. Conventional analysis of coexisting calcite yields °¹⁸O=18.19, suggesting that bulk ¹⁸O (Cc-Mt)=9.3 and yielding an apparent equilibration temperature of 525° C, over 200° C below the temperature of regional metamorphism. Consideration of experimental diffusion data and grain size distribution for magnetite and calcite suggests two contrasting cooling histories. The data for oxygen in calcite under hydrothermal conditions at high P(H₂O) indicates that diffusion is faster in magnetite and modelling of the low ¹⁸O rims on magnetite would suggest that the Adirondacks experienced slow cooling after Grenville metamorphism, followed by a brief period of rapid cooling, possibly related to uplift. Conversely, the data for calcite at low P(H₂O) show slower oxygen diffusion than in magnetite. Modelling based on these data is consistent with geochronology that shows slow cooling through the blocking temperature of both minerals, suggesting that the low ¹⁸O rims form by exchange with late, low temperature fluids similar to those that infiltrated the rock to serpentinize monticellite and which infiltrated adjacent anorthosite to form late calcite veinlets. In either case, the ion microprobe results indicate that two distinct events are recorded in the post-metamorphic exchange history of these magnetites. Recognition of these events is only possible through microanalysis and has important implications for geothermometry.     

Zoning in the Carboniferous-Lower Permian Cracow epithermal vein system, central Queensland, Australia

Four epithermal vein deposits (i.e. Dawn, Central Extended, Rose's Pride and Klondyke) in the Cracow gold field, central Queensland were investigated in terms of paragenesis, mineralogy, vein textures, fluid inclusions and stable isotopes. The Cracow epithermal field is confined to an area approximately 6 by 5 kilometers. All the deposits are hosted by the massive Camboon Andesite of Upper Carboniferous to Lower Permian age, occur as open-space vein fillings, and have similar paragenesis. However, significant variations in mineralogy, textures of quartz and adularia, and fluid geochemistry were found for a main mineralisation stage (Stage II) of each individual deposits. At Rose's Pride and Klondyke, basemetal sulphides are virtually absent, but significant amounts of calcite and quartz with minor adularia are widely distributed. Replacement textures are distinct, and mineralisation temperature is less than 220 °C and salinity less than 0.2 wt%. The ¹⁸O values of quartz and calcite range from –2.65 to –2.06 and from –6.66 to –6.34%. respectively, and calculated ¹⁸O_H2_O value is about –17%. which represents a nearly unshifted palaeo-meteoric water. Gold mineralisation is best developed at Central Extended among the studied deposits, where patches rich in electrum are often observed in polished thin sections and where gold grades exceeding 10 g/t are frequently indicated by assays. Base-metal sulphides are only present locally and rarely exceed 5 volume percent of the vein samples. Quartz is the dominant gangue mineral, but significant amounts of rhombic adularia and chlorite are widely distributed. Various primary and recrystallisation textures possibly inherited from silica gel are well developed and widespread. At individual sites where crustiform bands developed from both walls of a fissure, temperatures could drop sharply from 275 °C to less than 220 °C. The ore-forming fluid at Central Extended, compared with that at Rose's Pride and Klondyke, was isotopically shifted from meteoric water with ¹⁸O_H2_O value of –13.5 calculated in equilibrium with quartz ( ¹⁸O values of –3.09 to –1.44%.). The orebodies at Dawn are rich in base-metal sulphides which are commonly coarse-grained and form up to 20 volume percent of the vein materials. Quartz is the predominant gangue mineral, and commonly shows a coarse comb texture. The ore-forming fluid was 275 ± 10 °C and low salinity (0.4 to 0.7 wt%). The ¹⁸O values of quartz range from –3.97 to –3.22%., and calculated ¹⁸O_H2_O value is about –12, indicating large isotopic shifts from palaeo-meteoric water. A depth zoning in typical boiling epithermal systems, corresponding to different fluid compositions, wall rock permeability and boiling behaviors, was invoked to explain different characteristics of these selected epithermal veins.     

Fluid inclusion and stable isotope studies of Pb-Zn-fluorite-barite mineralization in the lower and middle Benue Trough,Nigeria

Lead-zinc-fluorite-barite veins in the lower and middle Benue Trough (Nigeria) are located within the Lower Cretaceous (Albian) carbonaceous shales, limestones, and arkosic sandstones of this intracontinental rift structure. The veins in the lower Benue Through consist of sphalerite + galena+marcasite ± chalcopyrite ± barite in a gangue of siderite and quartz hosted by carbonaceous shales, whereas in the middle Benue Trough, fluorite, barite, quartz, and similar sulfide minerals are hosted by limestone and sandstone. Fluid inclusion temperatures in vein minerals range from 95°C to 200°C (without pressure corrections) and salinities range from 14 to 24 equiv. wt% NaCl. Oxygen isotope compositions of limestone wall rocks (middle Benue) have been lowered from premineralization ¹⁸O values of about 25 per mil to approximately 16 per mil. Fluid in equilibrium with vein calcite has a calculated ¹⁸O of +2.6 per mil at 130°C. The ⁸⁷Sr/⁸⁶Sr ratio of this calcite (0.71497) suggests that strontium and calcium had a considerably more radiogenic source than the Cretaceous limestone or evaporite did (⁸⁷Sr/⁸⁶Sr=0.7073–0.7078). Observed strontium data, lead isotope compositions of galena, and REE patterns in fluorite suggest that the Lower Paleozoic basement rocks in the trough or their weathered equivalents are likely sources for the Benue Trough ore components. Sulfur isotope data suggest that the sulfur was probably contributed from the Cretaceous evaporites in the trough.Our data favor a basinal brine source for the ore-forming fluid. Fluid criculation probably resulted from high geothermal gradients accompanying continental rifting. Brine interaction with the clastic, carbonate, and evaporite rocks led to metal and sulfur leaching and later deposition in fractures accompanying the Cenomanian deformation and uplift in the Benue Trough.     

Ultra-high temperatures from oxygen isotope thermometry of a coesite-sanidine grospydite

The oxygen isotope compositions of coesite, sanidine, kyanite, clinopyroxene and garnet were measured in an ultra-high pressure-temperature grospydite from the Roberts Victor kimberlite, South Africa. The ¹⁸O values (per mil v. SMOW) of each phase and (1 ) are as follows: coesite, 8.62 (0.31); sanidine, 8.31 (0.02); kyanite, 7.98 (0.08); pyroxene, 7.63 (0.11); garnet, 7.53 (0.03). In situ analyses of the coesite with the laser extraction system are ¹⁸O=9.35 (0.08), n=4, demonstrating that the coesite is homogeneous. The coesite has partially inverted to polycrystalline quartz and the pyroxene is extensively altered during uplift. The larger scatter for the mineral separate coesite and pyroxene data may be due to partial reequilibration between the decompression-related breakdown products of these two phases. The anomalously high ¹⁸O value of the grospydite (¹⁸O_wholerock=7.7) is consistent with altered oceanic crust as a source rock. Temperature estimates from a linear regression of all the data to three different published calibrations correspond to an equilibrium temperature of 1310±80°C. The calculated isotopic pressure effect is to lower these estimates by about 40°C at 40 kb. The estimated temperature based on Al–Si disorder in sanidine is 1200±100°C and that from Fe–Mg exchange thermometry between garnet and clinopyroxene is 1100±50°C. Given the large errors associated with thermometry at such high temperatures, it is concluded that the xenolith equilibrated that 1200±100°C. Pressure estimates are 45±5 kb, based on dilution of the univariant equilibria albite = jadeite + coesite and 2 kyanite + 3 diopside = grossular + pyrope + 2coesite. Zoning in the outer 20 m of the feldspar from Ab_0.8 to Ab₁₆ indicates rapid decompression to 25 kb or less. The isotopic temperature estimates are the highest ever obtained and combined with the high degree of Al–Si disorder in sanidine require rapid cooling from ultra-high temperatures. It is inferred that the xenolith was sampled at the time of equilibration, providing a point on the upper Cretaceous geotherm in the mantle below South Africa.     

Geological,fluid inclusion and stable isotope studies of Mo mineralization,Galway Granite,Ireland

Mo mineralization within the Galway Granite at Mace Head and Murvey, Connemara, western Ireland, has many features of classic porphyry Mo deposits including a chemically evolved I-type granite host, associated K- and Si-rich alteration, quartz vein(Mace Head) and granite-hosted (Murvey) molybdenite, chalcopyrite, pyrite and magnetite mineralization and a gangue assemblage which includes quartz, muscovite and K-feldspar. Most fluid inclusions in quartz veins homogenize in the range 100–350°C and have a salinity of 1–13 eq. wt.% NaCl. They display Th-salinity covariation consistent with a hypothesis of dilution of magmatic water by influx of meteoric water. CO₂-bearing inclusions in an intensely mineralized vein at Mace Head provide an estimated minimum trapping temperature and pressure for the mineralizing fluid of 355°C and 1.2 kb and are interpreted to represent a H₂O-CO₂ fluid, weakly enriched in Mo, produced in a magma chamber by decompression-activated unmixing from a dense Mo-bearing NaCl-H₂O-CO₂ fluid. ³⁴S values of most sulphides range from c. 0 at Murvey to 3–4 at Mace Head and are consistent with a magmatic origin. Most quartz vein samples have ¹⁸O of 9–10.3 and were precipitated from a hydrothermal fluid with ¹⁸O of 4.6–6.7. Some have ¹⁸O of 6–7 and reflect introduction of meteoric water along vein margins. Quartz-muscovite oxygen isotope geothermometry combined with fluid inclusion data indicate precipitation of mineralized veins in the temperature range 360–450°C and between 1 and 2 kb. Whole rock granite samples display a clear ¹⁸O-D trend towards the composition of Connemara meteoric waters. The mineralization is interpreted as having been produced by highlyfractionated granite magma; meteoric water interaction postdates the main mineralizing event. The differences between the Mace Head and Murvey mineralizations reflect trapping of migrating mineralizing fluid in structural traps at Mace Head and precipitation of mineralization in the granite itself at Murvey.     

Carbon isotopic study on coexisting calcite and graphite in the Ryoke metamorphic rocks,northern Kiso district,central Japan

Carbon isotope fractionation between coexisting calcite and grpahite ( ¹³C_cc-gr) has been determined in metamorphosed limestones and calc-silicate rocks from the Ryoke metamorphic belt in the northern Kiso district. In this district, the Ryoke metamorphic rocks, ranging from the lower greenschist facies to the upper amphibolite facies, are widely distributed. The fractionation of ¹³C/¹²C between calcite and graphite decreases regularly with increasing metamorphic grade and is independent of absolute ¹³C values of calcite. This evidence suggests that carbon isotopic exchange equilibrium has been attained during metamorphism even in the greenschist facies and isotopic modification, possibly caused by retrogressive metamorphism, is not distinguished. For T=270–650° C, the fractionation is expressed by the following equation: ¹³C_cc-gr=8.9×10⁶T^–2–7.1 (T in °K).This equation has a slope steeper than the current results on the ¹³C_cc-gr versus 10⁶T^–2 diagram. It can be used as a potential geothermometer for almost the entire temperature range of metamorphism. ¹³C values of carbonaceous matter in unmetamorphosed limestones in this district are approximately –22, due to its biogenic origin. Graphite from metamorphosed limestones is also considered to be of biogenic origin but shows enrichment of ¹³C due to isotopic exchange with calcite. ¹³C values of graphite as well as ¹³C_cc-gr confirm that zone II represents the lowest grade zone of Ryoke metamorphism. The maximum equilibrium fractionation of ¹³C between calcite and graphite is considered to be approximately 23%, which corresponds to 270° C. Below this temperature, it seems that carbon isotopic exchange between the minerals does not occur.Calcite in marble from the higher grade zones has relatively lower ¹³C and ¹⁸O values. The depletion of heavy isotopes is considered to be caused by the loss of ¹³C and ¹⁸O enriched carbon dioxide during decarbonation reactions. For oxygen, it is considered that isotopic exchange with metamorphic fluids plays an important role in lowering the ¹⁸O value of calcite in some higher grade marbles.     

Oxygen isotope geochemistry of hydrothermally-altered synmetamorphic granitic rocks from South-Central Maine,USA

Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock ¹⁸O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have ¹⁸O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of _Q–F ( ¹⁸O_quartz– ¹⁸O_feldspar)=2.4 and _Q–M ( ¹⁸O_quartz– ¹⁸O_muscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured _Q–F and _Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic ¹⁸O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock ¹⁸O>12.1 and contain quartz and feldspar with ¹⁸O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock ¹⁸O<11.4 and contain quartz and feldspar with ¹⁸O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO₂-H₂O fluids of and ¹⁸O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and ¹⁸O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO₂ were also enriched in ¹⁸O. Because CO₂ was added to the granites during hydrothermal alteration and because fluids enriched in CO₂ were enriched in ¹⁸O, some or all of the variation in ¹⁸O of altered granites may have been caused by addition of ¹⁸O to the rocks during the hydrothermal event. The source of both the CO₂ and ¹⁸O could have been high-¹⁸O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in ¹⁸O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.     

Oxygen and hydrogen isotope evidence for meteoric water infiltration during mylonitization and uplift in the Ruby Mountains-East Humboldt Range core complex,Nevada

Stable isotope analyses of rocks and minerals associated with the detachment fault and underlying mylonite zone exposed at Secret Creek gorge and other localities in the Ruby-East Humboldt Range metamorphic core complex in northeastern Nevada provide convincing evidence for meteoric water infiltration during mylonitization. Whole-rock ¹⁸O values of the lower plate quartzite mylonites (95% modal quartz) have been lowered by up to 10 per mil compared with structurally lower, compositionally similar, unmylonitized material. Biotite from these rocks has D values ranging from -125 to -175, compared to values of -55 to-70 in biotite from unmylonitized rocks. Mylonitized leucogranites have large disequilibrium oxygen isotope fractionations ( ^{quartz-feldspar} up to 8 per mil) relative to magmatic values ( ^{quartz-feldspar}1 to 2 per mil)). Meteoric water is the only major oxygen and hydrogen reservoir with an isotopic composition capable of generating the observed values. Fluid inclusion water from unstrained quartz in silicified breccia has a D value of-119 which provides a plausible estimate of the D of the infiltrating fluid, and is similar to the isotopic composition of present-day and Tertiary local meteoric water. The quartzite mylonite biotites would have been in equilibrium with such a fluid at temperatures of 480–620° C, similar to independent estimates of the temperature of mylonitization. The relatively high temperatures required for isotopic exchange between quartz and water, the occurrence of fluid inclusion trails and deformed veins in quartzite mylonites, and the spatial association of the low-¹⁸O, low-D rocks with the shear zone all constrain isotopic exchange to the mylonitic (plastic) deformation event. These observations suggest thata significant amount of meteoric water infiltrated the shear zone during mylonitization to depths of at least 5 to 10 km below the surface. The depth of penetration of meteoric fluids into the lower plate mylonites was at least 70 meters below the detachment fault. In contrast, the upper-plate unmylonitized fault slices are dominated by brittle fracture and are often intensely veined (carbonates) or silicified (volcanic rocks and breccias). The fluids associated with the veining and silicification were also meteoric as evidenced by low ¹⁸O values of the veins, which are often 10 per mil lower than the adjacent carbonate matrix, and the exceptionally low ¹⁸O values (down to-4.4) of the breccias. Several previous studies have documented the infiltration of meteoric fluids into the brittley deformed upper plate rocks of core complexes, but this study provides convincing evidence that surface fluids have penetrated lower plate rocks undergoing plastic deformation. It is proposed that infiltration took place as the shear zone began the transition from plastic flow to brittle fracture while the lower plate rocks were being uplifted. During this period, plastic flow and brittle fracture were operating simultaneously, perhaps allowing upper plate meteoric fluids to be seismically pumped down into the lower plate mylonites.     

Using environmental isotopes in the study of the recharge-discharge mechanisms of the Yarmouk catchment area in Jordan

The recharge sources, the flow mechanisms and discharge areas of the different groundwater bodies underlying the Yarmouk River catchment area in Jordan, have, until now, not been adequately explained, although a wide range of hydrological, hydrogeological, and hydrochemical studies have been done. Along the Jordanian part of the catchment area of the Yarmouk River, groundwater issues from different aquifers with a variety of chemistries and types within the same aquifer and in between the different aquifers. Conventional recharge/discharge mechanisms, water balances and chemical analyses did not adequately explain the chemical variations and the different water types found in the area. Applying environmental isotopic tools combined with their altitude effects due to topographic variations (250–1,300 m a.s.l. within a distance of 20 km), and taking into consideration re-evaporation effects on the isotopic depletion and enrichment of rainwater, has greatly helped in understanding the recharge discharge mechanisms of the different aquifers. Precipitation along the highlands of an average of 600 mm/year is found to be depleted in its isotopic content of O¹⁸ = –7.0 to –7.26 and D = –32.2 to –33.28, whereas that of the Jordan Valley of 350 mm/year is highly enriched in isotopes with O¹⁸ = –4.06 and D = –14.5. The groundwater recharged along the highlands is depleted in isotopes (O¹⁸ = ~ –6, D = ~ –30), groundwater at the intermediate elevations is enriched (O¹⁸ = ~ –5, D = ~ –23) and that of the Jordan Valley aquifers containing meteoric water is highly enriched (O¹⁸ ~ –3.8, D = ~ –18). The deep aquifers in the Jordan Valley foothills are depleted in isotopes (O¹⁸ –18 = –6, D = –30) and resemble those of the highland aquifers. Only through using isotopes as a tool, were the sources of the different groundwater bodies and recharge and discharge mechanisms unambiguously explained. It was found that recharge takes place all over the study area and produces groundwater, which, from the highlands towards the Jordan Valley, shows increasing enrichment in isotopes. The highlands aquifer, with its groundwater depleted in isotopes, becomes confined towards the Jordan Valley; and, due to its confining pressure, leaks water upwards into the overlying aquifers causing their water to become less enriched in isotopes. Water depleted in its isotopic composition also seeps upward to the ground surface at the mountain foothills through faults and fissures.

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Resumen Las fuentes de recarga, los mecanismos de flujo y las áreas de descarga de los diferentes cuerpos de agua subterránea que subyacen el área de la cuenca del Río Yarmouk en Jordania, se han explicado de manera no ambigua únicamente mediante la aplicación de los isótopos como herramienta. A lo largo de la parte Jordana del área de la cuenca del Río Yarmouk el agua subterránea emerge de diferentes acuíferos con una variedad de tipos y composiciones, ya sea que provengan del mismo acuífero o de diferentes acuíferos. Los mecanismos convencionales de recarga/descarga, balances hídricos y variaciones químicas no han podido explicar las variaciones químicas y los diferentes tipos de aguas. La aplicación de herramientas de isótopos ambientales combinadas con los efectos de altitud derivados de variaciones topográficas (250 hasta 1,300 m s.n.m. en una distancia de 20 km) y tomando en consideración los efectos de re-evaporación en el empobrecimiento de isótopos y enriquecimiento del agua de lluvia han ayudado fuertemente en el entendimiento de los mecanismos de recarga/descarga de los diferentes acuíferos. La precipitación en el área varía de 600 mm/año, a lo largo de las tierras altas, a 350 mm/año en el área del Valle Jordán. El flujo de agua subterránea ocurre de las tierras altas hacia el Valle Jordán. El agua subterránea de las tierras altas está empobrecida en isótopos (O¹⁸ =~ –6, D =~ –30), el agua subterránea de elevaciones intermedias está enriquecida (O¹⁸ =~ –5, D =~ –23), y el agua de los acuíferos del Valle Jordan contiene agua meteórica que se encuentra altamente enriquecida (O¹⁸ =~ –3.8, D =~ –18). Los acuíferos profundos que se localizan al pie de las tierras altas del Valle Jordán están empobrecidos en isótopos (O¹⁸ =~ –6, D =~ –30) y son similares a los acuíferos de las tierras altas. Solo al aplicar los isótopos ambientales como herramienta pudo explicarse de manera inequívoca las fuentes de los diferentes cuerpos de agua subterránea y los mecanismos de recarga y descarga.

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Résumé Les zones de recharge, les mécanismes découlement et les zones de décharges des différentes masses deau souterraine sous le bassin versant de la rivière Yarmouk en Jordanie, étaient expliquées de manière ambiguë par les seuls outils isotopiques. Le long de la parti Jordanienne du bassin versant de la rivière Yarmouk leau souterraine provient de différents aquifères et se distinguent par leur type et leur composition chimique, selon que leau provient du même ou des différents aquifères. Les mécanismes conventionnels de recharge et de décharge, bilan hydrologique ne donnaient pas dexplications satisfaisantes concernant les variations chimiques et les différents types deau. En appliquant les isotopes environnementaux combinés aux effets de laltitude sur les variations des teneurs isotopiques (laltitude varie de 250 à 1,300 m sur une distance de 20 km.) et en prenant en considération les effets de ré-évaporation sur lappauvrissement et lenrichissement isotopique des eaux pluviales ont fortement contribués à une meilleure compréhension des mécanismes de recharge des différents aquifères. Les précipitations annuelles sont comprises entre 600 mm dans les zones en altitude et 350 mm dans la vallée de la Jordanie. Les écoulements de leau souterraine sont dirigés des zones en altitude vers la vallée de la Jordanie. Les eaux souterraines des zones en altitude sont isotopiquement appauvries (O¹⁸ = ~ –6, D = ~ –30), les eaux souterraines des zones de moyenne altitude sont enrichies (O¹⁸ = ~ –5, D = ~ –23) et les eaux de la vallée très enrichies (O¹⁸ ~ –3.8, D = ~ –18). Les aquifers profonds dans la vallée de la Jordanie sont appauvris (O¹⁸ –18 = –6, D = –30) et se confondent avec les eaux des zones situées en altitude. En appliquant uniquement les isotopes environnementaux comme des outils de compréhension des phénomènes hydrogéologiques, la source des différentes masses deau souterraines, les mécanismes de la recharge et de la décharge pourraient être expliqués de manière ambiguë.

     

Probing the relationship between surface waters and aquifers by <Superscript>18</Superscript>O measurements on the top of the Araripe Plateau/NE Brazil

The Araripe Plateau in northeastern Brazil has an area of about 8,000 km², confined by 39°05E and 40°55E, and 7°10S and 7°50S. Due to high permeability of soils, a surface drainage system is practically inexistent. Water is stored in excavations with clayey soil, the barreiros. Monthly samples were taken for ¹⁸O measurements, from September 1999 to August 2000, from four barreiros, three dug wells and five drilled wells. Results show that (1) groundwaters in the eastern part of the plateau are derived from present-day rainfall (¹⁸O–3.2), whereas groundwaters in the western portion are isotopically different (¹⁸O–5.0); (2) barreiros are strongly marked seasonally by elevated ¹⁸O during the dry period due to elevated evaporation; (3) a dug well at a distance of 30 m from a barreiro exhibits ¹⁸O similar to that of the reservoir, indicating a strong interaction between groundwater and surface water; and (4) a tubular well of 242-m depth, located in a fault, exhibits strong seasonal changes in ¹⁸O and electrical conductivity, revealing downward leakage between aquifers.     

Stable isotope and fluid inclusion studies of gem-bearing granitic pegmatite-aplite dikes,San Diego Co., California

Late Cretaceous, granitic pegmatite-aplite dikes in southern California have been known for gem-quality minerals and as a commercial source of lithium. Minerals, whole-rock samples, and inclusion fluids from nine of these dikes and from associated wall rocks have been analyzed for their oxygen, hydrogen, and carbon isotope compositions to ascertain the origins and thermal histories of the dikes. Oxygen isotope geothermometry used in combination with thermometric data from primary fluid inclusions enabled the determination of the pressure regime during crystallization.Two groups of dikes are evident from their oxygen isotope compositions (¹⁸O_qtz+10.5 in Group A, and +8.5 in Group B). Prior to the end of crystallization, Group A pegmatites had already extensively exchanged oxygen with their wall rocks, while Group B dikes may represent a closer approximation to the original isotopic composition of the pegmatite melts. Oxygen isotope fractionations between minerals are similar in all dikes and indicate that the pegmatites were emplaced at temperatures of about 730 ° to 700 ° C. Supersolidus crystallization began with the basal aplite zone and ended with formation of quench aplite in the pocket zone, nearly to 565 ° C. Subsolidus formation of gem-bearing pockets took place over a relatively narrow temperature range of about 40 ° C (approximately 565–525 ° C). Nearly closed-system crystallization is indicated.Hornblende in gabbroic and noritic wall rocks (D_w.r. = –90 to –130) in the Mesa Grande district crystallized in the presence of, or exchanged hydrogen with, meteoric water (D –90) prior to the emplacement of the pegmatite dikes. Magmatic water was subsequently added to the wall rocks adjacent to the pegmatites.Groups A and B pegmatites cannot be distinguished on the basis of their hydrogen isotope compositions. A decrease in D of muscovite inward from the walls of the dikes reflects a decrease in temperature. D values of H₂O from fluid inclusions are: –50 to –73 (aplite and pegmatite zones); –62 to –75 (pocket quartz: Tourmaline Queen and Stewart dikes); and –50 ± 4 (pocket quartz from many dikes). The average ¹³C of juvenile CO₂ in fluid inclusions in Group B pegmatites is –7.9. In Group A pegmatities, ¹³C of CO₂ is more negative (–10 to –15.6), due to exchange of C with wall rocks and/or loss of ¹³C-enriched CO₂ to an exsolving vapor phase.Pressures during crystallization of the pockets were on the order of 2,100 bars, and may have increased slightly during pocket growth. A depth of formation of at least 6.8 km (sp. gr. of over burden = 3.0, and P _fiuid=P _load) is indicated, and a rate of uplift of 0.07 cm/yr. follows from available geochronologic data.     

Contrasting serpentinization processes in the eastern Central Alps

Stable isotope compositions have been determined for serpentinites from between Davos (Arosa-Platta nappe, Switzerland) and the Valmalenco (Italy). D and ¹⁸O values (–120 to –60 and 6–10, respectively) in the Arosa-Platta nappe indicate that serpentinization took place on the continent at relatively low temperatures in the presence of limited amounts of metamorphic fluids that contained a component of meteoric water. One sample of chrysotile has a ¹⁸O value of 13 providing evidence of high W/R ratios and low formation temperature of lizardite-chrysotile in this area. In contrast, relatively high D values (–42 to –34) and low ¹⁸O values (4.4–7.4) for serpentine in the eastern part of the Valmalenco suggest a serpentinization process that took place at moderate temperatures in fluids that were dominated by ocean water. The antigorite in the Valmalenco is the first reported example of continental antigorite with an ocean water signature. An amphibole sample from a metasomatically overprinted contact zone to metasediments (D=-36) indicates that the metasomatic event also took place in the presence of ocean water. Lower D values (–93 to –60) of serpentines in the western part of the Valmalenco suggest a different alteration history possibly influenced by fluids associated with contact metamorphism. Low water/rock ratios during regional metamorphism (and metasomatism) have to be assumed for both regions.