The origin of clay minerals in active and relict hydrothermal deposits

Samples of Fe-oxide-rich hydrothermal sediments were collected from active and inactive portions of the TransAtlantic Geotraverse (TAG) hydrothermal field on the Mid-Atlantic Ridge. Clays separated from TAG metalliferous sediments in this study all consist of Al-poor nontronite. Oxygen isotope thermometry of the clays yields formation temperatures of 54-67°C for samples from the inactive Alvin mound compared with 81-96°C for samples from the active TAG site. The latter are the highest recorded temperatures for authigenic hydrothermal clays. Sr isotope analysis of the clays from the active mound suggests that they precipitated from seawater-dominated fluids, containing less than 15% hydrothermal end-member fluid. In contrast, nontronite from the inactive Alvin mound has ⁸⁷Sr/⁸⁶Sr values that closely resemble that of detrital North Atlantic clays, suggesting a dominantly continental source for the Sr. Rare earth element data are consistent with a significant detrital input to the inactive site but also demonstrate the extent of hydrothermal input to the low temperature fluid. Crystallographic fractionation of the trivalent REE is apparent in the heavy REE enrichments for all nontronite samples. The inferred formation-mechanism for nontronite-rich Fe-oxyhydroxide deposits at the surface of the active mound is by direct precipitation from low temperature fluids. At the inactive Alvin site, in contrast, the deposits form during alteration of pelagic sediments by diffuse fluids and replacement of biogenic carbonate with nontronite and Fe-oxyhydroxide. These two modes of formation are both important in seafloor hydrothermal settings where clay minerals are a significant component of the hydrothermal deposit.     

Composition,oxygen isotope geochemistry and origin of smectite in the metalliferous sediments of the Bauer Deep,southeast Pacific

The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite.Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite.Infra-red and Mossbauer spectroscopy and wet chemical analysis (LiBO₂ fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3°C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth.Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed.Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO₃ accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions).     

Authigenic transition elements in Pacific pelagic clays

The concentrations of Sc, Ti, Fe, Mn, Co, Ni, Cu, La, Th and U have been measured in several Pacific pelagic clays having widely different accumulation rates, 0.4–9.0 mm/10³ yr. The authigenic fractions and deposition rates of these elements have been estimated from the measured concentrations using various models. The results show that in Pacific clays about 90% Mn, 80% Co and Ni and 50% Cu are authigenic whereas the major fraction (?90%) of Sc, Ti, Fe, La, Th and U are of detrital origin.Anticorrelation between the clay accumulation rates and the concentrations of Mn, Co, Ni and Cu is observed. This suggests a uniform authigenic deposition of these elements superimposed on varying amounts of detrital materials. The concentrations of Sc, Ti and Th are almost independent of sedimentation rates, indicating that their authigenic deposition is small compared to their detrital contribution.Comparison of the authigenic deposition and river input rates shows that Mn, Co and Ni are accumulating in excess of their supply by factors of 2–10, whereas the converse is true for Cu and U. Additional sources to account for the budgetary discrepancies of Mn, Co and Ni are discussed, with particular reference to in situ leaching of detrital phases transported to the oceans via rivers.     

Detrital,metamorphic and metasomatic tourmaline in high-pressure metasediments from Syros (Greece): intra-grain boron isotope patterns determined by secondary-ion mass spectrometry

The boron isotopic composition of zoned tourmaline in two metasediments from the island of Syros, determined by secondary-ion mass spectrometry (SIMS), reflects the sedimentary and metamorphic record of the rocks. Tourmaline from a silicate-bearing marble contains small (≤20 μm) detrital cores with highly variable δ ¹¹B values (−10.7 to +3.6‰), pointing to a heterogeneous protolith derived from multiple sources. The sedimentary B isotopic record survived the entire metamorphic cycle with peak temperatures of ∼500°C. Prograde to peak metamorphic rims are homogeneous and similar among all analysed grains (δ ¹¹B ≈ +0.9‰). The varying δ ¹¹B values of detrital cores in the siliceous marble demonstrate that in situ B isotope analysis of tourmaline by SIMS is a potentially powerful tool for provenance studies not only in sediments but also in metasediments. A meta-tuffitic blueschist bears abundant tourmaline with dravitic cores of detrital or authigenic origin (δ ¹¹B ≈ −3.3‰), and prograde to peak metamorphic overgrowth zones (−1.6‰). Fe-rich rims, formed during influx of B-bearing fluids under retrograde conditions, show strongly increasing δ ¹¹B values (up to +7.7‰) towards the margins of the grains. The δ ¹¹B values of metamorphic tourmaline from Syros, formed in mixed terrigenous–marine sediments, reflect the B signal blended from these two different sources, and was probably not altered by dehydration during subduction.     

Argillization processes at the El Berrocal analogue granitic system (Spain): mineralogy,isotopic study and implications for the performance assessment of radwaste geological disposal

The El Berrocal granite/U-bearing quartz vein (UQV) system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective was to understand the geochemical behaviour of natural nuclides under different physicochemical conditions. Within this framework, the argillization processes related to fracturing and formation of the uranium–quartz vein were studied from a mineralogical and isotopic standpoint in order to establish their temperatures of formation and thus complete the geothermal history of the system. For this purpose, δ¹⁸O values were determined for pure mineral from the unaltered granite and quartz from the uranium–quartz vein, as well as for mixture samples from the hydrothermally altered granite (sericitised granite) and clayey samples from fracture fillings, including the clayey walls of the uranium–quartz vein. The isotopic signature of quartz from the uranium–quartz vein and the monophasic nature of its fluid inclusions led us to conclude that the isotopic signature of water in equilibrium with quartz was approximately in the range from −8.3‰ to −5.7‰ V-SMOV, its temperature of formation being around 85–120 °C. The δ¹⁸O values of pure sericite from the hydrothermally altered granite, calculated by means of the oxygen fraction molar method, indicate that its temperature of formation, in equilibrium with the aforementioned waters, is also in the range from 70 °C to approximately 120 °C. Clays from fracture fillings and clayey walls of the uranium–quartz vein are usually mixtures, in different proportions, of illite, approximately formed between 70 and 125 °C; two generations of kaolinite formed at approximately 90–130 °C and at around 25 °C, respectively; smectite, formed at ≤25 °C; and occasionally palygorskite, formed either between 30 and 45 °C or 19 and 32 °C, depending on the fractionation equation used. These data suggest that sericite from the hydrothermally altered granite, quartz from the uranium–quartz vein, illite and the first generation of kaolinite from the fracture fillings resulted from the same hydrothermal process affecting the El Berrocal granite in relation to fracturing. Under certain physicochemical conditions (T≈100 °C, pH≈8 and log [H₄SiO₄] between −4 and −3), illite and kaolinite can be paragenetic. As a result of weathering processes, smectite was formed from hydrothermal illite and inherited albite under alkaline weathering, while the second generation of kaolinite was formed from smectite, under acid conditions and close to the sulphide-rich uranium–quartz vein. Palygorskite is an occasional mineral formed probably either during the thermal tail of the above-described hydrothermal process or during weathering processes. In both cases, palygorskite must have formed from alkaline Si–Mg-rich solutions. Finally, these data and processes are discussed in terms of natural analogue processes, drawing some implications for the performance assessment of a deep geological radwaste repository (DGRR).     

Further evidence for a Jurassic mineralizing event in central Europe: K–Ar dating of hydrothermal alteration and fluid inclusion systematics in wall rocks of the Käfersteige fluorite vein deposit in the northern Black Forest, Germany

The hydrothermal fluorite vein deposit of `Käfersteige' ranks among the biggest in central Europe. It is located along the suture zone that separates the Moldanubian and Saxothuringian units in the northern Black Forest, and is hosted in Bunter sandstone and underlying granitic basement. K–Ar ages of authigenic illite from the wall rocks give a Jurassic formation age of around 145?Ma for the deposit. Age data scatter down to 80?Ma in illite from the clay gouge and indicate a younger Cretaceous-Tertiary hydrothermal overprint. The pyrophyllite component in authigenic illite from wall rocks and the re-equilibration of illite suggest a formation temperature around 200?°C. Secondary fluid inclusions in quartz from the wall rocks define a syn-mineralization fluid episode involving Ca–Mg–K–Na–Cl-rich brines (about 27 wt% NaCl_eq) with a T _h of about 125?°C, and a post-mineralization Na–Cl-rich fluid overprint with a T _h of about 100?°C. Both generations of fluid inclusions relate to the final event of each cycle, while authigenic illite composition and re-equilibration of illite in the clay gouge may document initial temperatures of formation. The Upper Jurassic fluid system can be traced all over western Europe. It is probably an expression of continent-wide rifting and concomitant regional fluid circulation in connection with major tectonic disturbances, magmatism and abnormal heat flow during the opening of the North Atlantic ocean. The younger barren fluid overprint could be related to the onset of the Alpine orogeny.     

Mineralogy and Isotope Geochemistry of Active Submarine Hydrothermal Field at Suiyo Seamount, Izu–Bonin Arc, West Pacific Ocean

This report presents mineralogical, geochemical and isotopic data on samples obtained using the Benthic Multi‐coring System (BMS) to drill a submarine hydrothermal deposit developed in a caldera on the summit of the Suiyo Seamount in the Izu–Bonin Island Arc, south of Japan. This deposit is regarded as the first example of Kuroko‐type sulfide mineralization on a volcano at the volcanic front of an island arc. The mineralization and hydrothermal alteration below the 300 × 150‐m area of active venting was investigated to depths of 2–9 m below the sea floor. Drilling beneath the area of active venting recovered a sequence of altered volcanic rocks (dacite lavas, pyroclastic rocks of dacite–rhyolite compositions and pumice) associated with sulfide veining and patches/veins of anhydrite. No massive sulfide was found, however, and the subsea‐floor mineralization to 10 m depth is dominated by anhydrite and clay minerals with some sulfides. Sulfide‐bearing samples contained high Au (up to 42 ppm), Ag (up to 263 ppm), As (up to 1550 ppm), Hg (up to 55 ppm), Sb (up to 772 ppm), and Se (up to 24 ppm). Electron probe microanalyzer indicated that realgar, orpiment, and mimetite were major As‐bearing minerals. The sulfides were also characterized by high Zn (>10%) compared to Cu (<6.3%) and Pb (<0.6%). The δ²⁰²Hg/¹⁹⁸Hg, δ²⁰²Hg/¹⁹⁹Hg and δ²⁰²Hg/²⁰⁰Hg of the sulfide‐bearing dacite samples and a sulfide chimney decreased with increasing Hg/Zn concentration ratio. The variation of the δ²⁰²Hg/¹⁹⁸Hg ranged from ?2.8 to +0.5‰ to relative to S‐HG02027. The large range of these δ²⁰²Hg/¹⁹⁸Hg was greater than might be expected for such a heavy element and may be due to a predominance of kinetic effects. The variation of δ²⁰²Hg/¹⁹⁸Hg of sulfide‐bearing dacite samples suggested that light Hg isotope in the vapor mixed with oxygenated seawater near sea floor during mineralization. Lead isotope ratios of the sulfide were very similar to those of the dacite lava, suggesting that lead is of magmatic origin. The ⁸⁷Sr/⁸⁶Sr ratio (0.70872) of anhydrite was different from that of the dacite lava, and suggests an Sr derivation predominantly from seawater. Hydrothermal alteration of the dacite in the Suiyo hydrothermal field was characterized by Fe‐sulfides, anhydrite, barite, montmorillonite, chlorite/montmorillonite mixed‐layer minerals, mica, and chlorite with little or no feldspar or cristobalite. Hydrothermal clay minerals changed with depth from montmorillonite to chlorite/montmorillonite mixed‐layer minerals to chlorite and mica. Hydrogen isotope ratios of chlorite/montmorillonite and mixed‐layer, mica‐chlorite composites obtained below the active venting sites ranged from ?49 to ?24‰, suggesting seawater as the dominant fluid causing alteration. Oxygen isotope ratios of anhydrite ranged from 9.2 to 10.4‰ and anhydrite formation temperatures were calculated to be 188–207°C. Oxygen isotope ratios ranged from +5.2 to +9.2‰ for montmorillonite, +3.2 to +4.5‰ for chlorite/montmorillonite mixed‐layer minerals, and +2.8 to +3.8‰ in mixtures of chlorite and mica. The formation temperatures of montmorillonite and of the chlorite–mica mixture were 160–250°C and 230–270°C, respectively. The isotope temperatures for clay minerals (220–270°C) and anhydrite (188°C) were significantly lower than the borehole temperature (308.3°C) measured just after the drilling, suggesting that temperature at this site is now higher than when clay minerals and anhydrite were formed.     

Isotopic geochemistry of burial-metamorphosed volcanogenic sediments,Great Valley sequence,northern California

Isotopic and mineralogic data from an 8500-m thick section of the Great Valley sequence, northern California, indicate that changes in the δ¹⁸O values of authigenic minerals resulted from the conversion of smectite to a 10 Å clay-mineral as temperature increased with burial in the Jurassic- Cretaceous outer-arc basin. The clay-mineral assemblage in mudstone is characterized by a proportional increase of the 10 Å clay-mineral with increasing stratigraphic depth, and by a depletion in the δ¹⁸O value of the mixed-layer smectite/10 Å clay-mineral with descending stratigraphic position from +21.9 to + 15.5%. SMOW. Modeling of the oxygen isotopic data from authigenic phases, based on equilibrium fractionation during clay-mineral diagenesis, indicates that δ¹⁸O values of calcite in mudstones and of calcite cements in sandstone precipitated along a temperature gradient of about 25°C/km during maximum burial to about 6–7 km. δD values of the mixed-layer smectite/10 Å clay-mineral range between ?69 to ?44%. SMOW. Using temperatures calculated from the oxygen isotopic data, the deuterium and oxygen isotopic data indicate that the smectite underwent late-stage dehydration and probably buffered the composition of formation waters from sea water values to isotopic compositions of δ¹⁸O ≈ +8%. SMOW and δD ≈ ?25%. SMOW. The δ¹³C values of calcite from mudstone and sandstone imply that crystallization of authigenic calcite was linked to organic diagenesis during which dissolved HCO^t-₃ was continuously enriched in ¹³C as temperature increased with burial. At the base of the sequence and immediately overlying the ophiolitic basement rocks, several hundred meters of strata were altered by more oxygen-depleted (δ¹⁸O ? +4 to +5%.) hydrothermal fluids emanating from the ophiolitic rocks, probably at maximum burial depth.     

Sulfide-impregnated and pure silica precipitates of hydrothermal origin from the Central Indian Ocean

This is the first report about silica-rich hydrothermal precipitates which were sampled together with hydrothermal sulfides (chimney fragments) in an extinct vent field in the Central Indian Ocean. There are two kinds of silica-rich rocks: a jasper which is impregnated and replaced to various degrees mainly by sphalerite, and to a lesser extent by barite, pyrite and traces of chalcopyrite, and an opalite which is an almost pure silica-phase without any sulfide or sulfate impregnations, but which is sometimes covered by manganese crusts.No internal concentric zoning indicating typical chimney structures can be recognized in the jasper and/or opalite samples, the textures rather suggest a sedimentary silica and/or iron deposition from diffuse, low-temperature (±60 °C) vent fluids, partly with still visible indications of former bacterial mats and synsedimentary deformation structures; the sphalerite- and barite-impregnations within the jasper, however, are considered to have precipitated from white-smoker-type fluids since they were deposited under intermediate temperatures between 155 and 265 °C, according to fluid inclusion studies.The sulfur isotopic composition (δ³⁴S) of our sulfide samples has mean values of 6.1% for sphalerite and 5.7% for pyrite indicating a mixture of predominantly basaltic sulfur with subordinate amounts of reduced seawater sulfur. The oxygen isotope signals of some pure jasper concentrate samples indicate that the mean formation temperature calculated from these values lies at 63.2 °C.The relationship between the massive pyrite- and chalcopyrite-ores from the extinct chimney structures and the silica-rich precipitates can be explained by different cycles of hydrothermal activity: one high-temperature (above 300 °C) cycle dominated by pyrite and chalcopyrite formation and one later epithermal (below 300 °C) cycle which resulted in sphalerite- and silica-dominated precipitates. Furthermore, zonation and zone-refining processes are part of the evolution of the mineralized field.     

In situ LA-(MC)-ICP-MS trace element and Nd isotopic compositions and genesis of polygenetic titanite from the Baogutu reduced porphyry Cu deposit,Western Junggar,NW China

Titanite (sphene, CaTiSiO₅) is sensitive to changes in temperature, oxygen and water fugacity, and fluid composition. In order to understand formation processes and the nature of hydrothermal fluids, various types of titanite from Cu ores at the Baogutu reduced porphyry Cu deposit were chosen for detailed study. Magmatic titanite is associated with biotite, plagioclase and K-feldspar, whereas hydrothermal titanite occurs with K-feldspar, chlorite, actinolite and calcite. The formation of hydrothermal titanite was related to hydration of igneous minerals under high fH₂O, whereas the widespread replacement of ilmenite by titanite (without magnetite) indicates a relatively low oxygen fugacity. Magmatic titanite has low Al, high Fe, Y, Sn, Zr, Nb and REE contents, relative to hydrothermal titanite. On the basis of the Zr-in-titanite and Al-in-chlorite geothermometers, formation temperatures for magmatic and hydrothermal titanite are estimated to be 687–739 °C and 250–670 °C, respectively. The gradual decrease in REE, Y and Sn contents from magmatic to late hydrothermal titanite was probably caused by precipitation of REE-bearing minerals. Magmatic and hydrothermal titanites have similar chondrite-normalized REE patterns with negative Eu anomalies and relatively flat HREE. Randomly selected titanites have Nd isotopic compositions similar to the host rocks. Thus, both magmatic and hydrothermal titanite are believed to have been predominantly derived from a mantle source.     

Evidence for Late-Paleozoic brine migration in Cambrian carbonate rocks of the central and southern Appalachians: Implications for Mississippi Valley-type sulfide mineralization

Many Lower Paleozoic limestones and dolostones in the Valley and Ridge province of the central and southern Appalachians contain 10 to 25 weight percent authigenic potassium feldspar. This was considered to be a product of early diagenesis, however, ${}^{40}\text{Ar}{}^{39}\text{Ar}$ analyses of overgrowths on detrital K-feldspar in Cambrian carbonate rocks from Pennsylvania, Maryland, Virginia, and Tennessee yield Late Carboniferous-Early Permian ages (278–322 Ma). Simple mass balance calculations suggest that the feldspar could not have formed isochemically, but required the flux of multiple pore volumes of fluid through the rocks, reflecting regional fluid migration events during the Late-Paleozoic Alleghanian orogeny.Microthermometric measurements of fluid inclusions in overgrowths on detrital K-feldspar and quartz grains from unmineralized rocks throughout the study area indicate homogenization temperatures from 100° to 200°C and freezing point depressions of −14° to −18.5°C (18–21 wt.% NaCl equiv). The apparent similarity of these fluids to fluid inclusions in ore and gangue minerals of nearby Mississippi Valley-type (MVT) deposits suggests that the regional occurrences of authigenic K-feldspar and MVT mineralization may be genetically related. This hypothesis is supported by the discovery of authigenic K-feldspar intergrown with sphalerite in several mines of the Mascot-Jefferson City District, E. Tennessee. Regional potassic alteration in unmineralized carbonate rocks and localized occurrences of MVT mineralization are both explainable by a gravity-driven flow model, in which deep brines migrate towards the basin margin under a hydraulic gradient established during the Alleghanian orogeny. The authigenic K-feldspar may reflect the loss of K during disequilibrium cooling of the ascending brines. MVT deposits are probably localized manifestations of the same migrating fluids, occurring where the necessary physical and chemical traps are present.     

Mineralogical characterization of acid weathered phyllosilicates with implications for secondary martian deposits

The detection of phyllosilicates and sulfates on Mars has revealed a complex aqueous history which suggests distinct geochemical environments separated temporally and spatially. Recent observations by MRO CRISM in Mawrth Vallis have shown that phyllosilicate deposits exhibit a specific stratigraphy, which remains incompletely understood. Moreover, MER Spirit has evidenced association between phyllosilicates, amorphous silica and sulfates. We investigated the hypothesis that these parageneses resulted from the acidic weathering of older phyllosilicate deposits. We exposed nontronite (Fe-rich smectite), montmorillonite (Al-rich smectite) and kaolinite to H₂SO₄ solutions at pH 0, 2 and 4, and at a temperature of 60 °C. After the acid treatment, a combination of mineralogical techniques was used to assess the degree of alteration of the three phyllosilicate minerals. XRF, XRD and ESEM measurements show that nontronite was the most unstable when acid leached, followed by montmorillonite and then kaolinite. Progressive acidic leaching of nontronite leads to alteration of the phyllosilicate to amorphous silica, along with Fe-sulfate and anatase, and the formation of an acidic Al,Fe-rich solution. Alteration of montmorillonite resulted in the formation of Fe-, Al-, Ca- and Mg-sulfates, and a Al-rich leaching solution. Comparatively, leaching of kaolinite resulted in the formation of Al-sulfates and a Al-rich solution as well, with only slight alteration of the primary mineralogical features. The effects of acid leaching of the phyllosilicates were also observed in NIR reflectance spectra, allowing a comparison with CRISM spectra from Mawrth Vallis. Based on our results, we propose a new model where acid leaching of mixed phyllosilicate deposits leads to kaolinite overlaying montmorillonite, which in turn caps Fe,Mg-smectites. Leaching of cations and subsequent evaporation leads to sulfate deposits, as supported by geochemical modeling, while amorphous silica remains as a residue. Depending on the intensity (pH) and length of exposure of acidic leaching, our model can explain the stratigraphic distribution of phyllosilicates, and the association of sulfates, silica and smectites.     

The effect of iron on montmorillonite stability. (II) Experimental investigation

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, P_sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl₂ which were reacted at temperatures of 80, 150, and 250 °C, P_sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.     

Diagenesis in tertiary sandstones from Kettleman North Dome. California—II. Interstitial solutions: Distribution of aqueous species at 100°C and chemical relation to the diagenetic mineralogy

Interstitial brines from the Temblor and the McAdams sandstones at Kettleman are essentially NaCaCl solutions with subsidiary SO₄ and the total salinities are roughly 30,000 and 10,000 ppm, respectively. Activities of H⁺ and all other aqueous species have been calculated for 100°C (the in situ temperatures of the brines) from chemical analyses of the brines and 100-degree dissociation constants alone. The brine alkalinities measured at surface temperature appear to be too low when comparing them against alkalinities calculated from the measured pHs of the brines. Consequently, alkalinities calculated for 25°C were substituted for the measured ones in the calculation of the distribution of aqueous species at 100°C.Although the brines are nearly neutral (pH 6·3–d7·9) at surface temperature, their pHs calculated for 100°C range from 8·1 to 8·7 (± 0·35). These pHs and the 100-degree activities of the other aqueous species permit graphic representation of the brines on activity diagrams. Most brines fall at or near the boundaries between the stability fields of quartz, albite, microcline, mica, montmorillonite and anhydrite. Because these minerals are present as authigenic phases in the sandstones, the calculations suggest that the minerals are in stable equilibrium with the brines. By contrast, the calculations suggest that the brines are supersaturated by about three orders of magnitude with respect to calcite, also present in the sandstones. One possible explanation for this is kinetic inhibition of calcite crystallization by Mg²⁺ and SO₄^2? ions in the brines. Phosphatic pellets, glauconite and probably dolomite, pyrite and some kaolinite are early authigenic minerals preserved in the sandstones and they are not now in equilibrium with the brines, which are supersaturated with respect to dolomite and pyrite. The chemical relationship between the brines and the diagenetic minerals laumontite and sphene, also present in the Temblor Formation, cannot be assessed reliably until the thermodynamic properties of laumontite and of aqueous titanium complexes are well known.     

Microfabric analyses applied to the Witwatersrand gold- and uranium-bearing conglomerates: constraints on the provenance and post-depositional modification of rock and ore components

Microfabrics of detrital quartz grains and quartz cement of four gold- and uranium-bearing conglomerates of various goldfields of the Witwatersrand Basin, South Africa, were investigated by optical and cathodoluminescence microscopy. The study revealed that the vast majority of quartz grains (<5 mm) originate from felsic magmatic source rocks. Cherts and polymineralic mineral grains, pointing to greenschist to amphibolite facies metasedimentary rocks, follow in abundance, whereas diagenetic to weakly metamorphosed quartzites are subordinate. Material from hydrothermal vein quartz is almost completely lacking, both in the sand and in the pebble fraction. No obvious relationships are discernible between the varying proportions of detrital siliciclastic components of the different reefs and their ore grades. Assuming a sedimentological control of gold distribution, this finding supports multiple sources for the detrital components, which were thoroughly mixed during transport. The post-depositional history of the sediments is characterized by a complex polyphase succession of deformation, cementation and hydrothermal alteration events. Both fragmentation and pressure solution features within detrital quartz, quartz cement and round grains of pyrite, zircon, chromite and uraninite demonstrate that these materials were present in the conglomerates during diagenesis, and, thus, are true detrital grains with abraded, rounded grain morphologies. By analogy, it is assumed that gold is also a detrital component, although most of the gold grains display characteristics of hydrothermal overprinting. During subsequent metamorphism, micro-shear zones are developed, and brittle-ductile crystal-plastic deformation and limited quartz recrystallization occur. Maximum temperatures of about 350 °C were reached on the prograde metamorphic path. Recrystallization and redistribution of detrital siliciclastic and ore minerals took place, and various hydrothermal/metamorphic minerals including chlorite, sericite, pyrophyllite and chloritoid were formed. These redistribution processes involved existing detrital minerals only and were generally isochemical because little evidence exists for the development of a secondary porosity and permeability that would allow major external inputs into the Witwatersrand conglomerates. Most of the gold grains have hydrothermal characteristics, as evidenced by their authigenic, crystalline shapes and their chemical compositions. However, these features are regarded to result from overprinting. Most likely, the gold grains experienced more drastic modifications relative to other ore components because of the ductile and mobile nature of gold. The retrograde metamorphic path is characterized by percolating radioactive fluids at T<300 °C, recorded by radiation damage indicated by cathodoluminescence alteration rims along quartz grain boundaries and microcracks. The degrees of radiation damage observed are proportional to the uranium contents of the conglomerate ores. The collective evidence of our study supports the modified placer model for the genesis of the Witwatersrand ores. This model explains most of the observations on the detrital mineral assemblage and its post-depositional modification elegantly and in a satisfactory manner.     

Oxygen isotope study of quartz-Al2SiO5 pairs from the Mica Creek area, British Columbia: implications for the recovery of peak metamorphic temperatures

Oxygen isotope analyses of quartz-Al₂SiO₅ pairs have been made for samples from the Mica Creek area, British Columbia. We have analysed quartz–kyanite nodules and quartz–kyanite and quartz–sillimanite in multiphase pelitic rocks from the staurolite–kyanite, kyanite, and sillimanite zones. Apparent temperatures calculated from oxygen isotopic fractionation range from 555 °C (staurolite–kyanite zone) to 695 °C (sillimanite zone). Temperatures from the quartz–kyanite nodules range from 630 to 675 °C. Some of the nodules show isotopic disequilibrium. Most of the results confirm predictions that bimineralic rocks will yield an estimate of peak metamorphic temperatures, when the less abundant mineral (an aluminium silicate) is the slower oxygen diffuser. Using cooling rates of 10–100 °C Ma^?1 for the multiphase rocks, measured crystal sizes and modes, the Fast Grain Boundary diffusion model with ‘wet’ diffusion data (P_H2O?1.0 kbar) yields predicted apparent temperatures which are generally lower than the measured apparent temperatures. The agreement is improved if slower diffusion coefficients are used. This suggests that f (H₂O) during cooling was lower than that of the hydrothermal experiments and thus that there was little interaction with aqueous fluids of internal or external origin to modify the isotopic compositions. The measured apparent isotopic temperatures and apparent garnet–biotite Fe–Mg exchange temperatures show very poor agreement for the sillimanite zone samples, with the garnet–biotite Fe–Mg exchange temperatures generally higher than the oxygen isotope temperatures. Compared with the other calibrations that we tested the measured apparent temperatures using the Sharp calibration show the best agreeement with recently published P–T grids, although some variability in agreement is expected due to variable f (H₂O) during cooling.     

An Overview of Dissolved and Suspended Matter Fluxes in the Loire River Basin: Natural and Anthropogenic Inputs

The spatial and temporal distributions of major elements were investigated in the surface waters and in associated suspended matter at two sites of the upper Loire basin (Orleans and Brehemont) between 1995 and 1998.According to geochemical and isotopic patterns, the dissolved load appears to result from a process of mixing rainwater inputs, weathering processes of carbonate and silicate bedrock, and agricultural and urban inputs. Natural inputs influence 60% of water chemical composition at both sites. Annual dissolved fluxes were estimated to be 1300 10³ t/y at Orleans and 1620 10³ t/y at Brehemont. Major elements are transported mainly in the dissolved fraction. After correcting for atmospheric and anthropogenic inputs, the silicate specific export rate was calculated to be 11 t/y/km² throughout the basin and the carbonate specific export rate to be from 47 t/y/km² at Orleans to 23 t/y/km² at Brehemont.The suspended load appears to result from at least two particle reservoirs: a silicate reservoir and a carbonate reservoir. The silicate reservoir has a detrital origin, mainly during periods of high flow, while the carbonate reservoir has a detrital origin during periods of high flow and an authigenic origin during periods of low flow. Of the total annual flow of suspended matter, this authigenic material represents 16% at Orleans, 25% at Brehemont and 37% in the fluvial part of the estuary. After correcting authigenic inputs, the specific export rate due to mechanical weathering was estimated to be 8 t/y/km² throughout the Loire basin.     

18O/16O ratios of anorthosites and related rocks from the Rogaland Complex (SW Norway)

The South Rogaland Complex (South Western Norway) consists of several anorthositic intrusions emplaced in granulite facies metamorphic rocks. The anorthosites and related norites and jotunites have δ ¹⁸O values of 5.2 to 7‰ suggesting a mantle origin for these rocks, in agreement with the strontium isotopic evidence. The acidic rocks, mostly charnockitic, associated with the anorthosites have similar δ ¹⁸O values and thus a comagmatic relation between these two rock types is inferred. Small departures from mantle values are explained in terms of crustal contamination by surrounding gneisses that have δ ¹⁸O values between 4.3 and 10‰ Locally, this corresponds to important anatexis as has been suggested for the Farsund charnockite on the basis of strontium isotope and REE geochemistry. The isotopic temperatures calculated from the isotopic fractionations are in the range 500°–700° C, lower than the orthomagmatic temperatures and probably due to subsolidus isotopic exchange during the slow cooling of these plutonic rocks, either during a late magmatic deuteric stage or during a slow, postorogenic ascent under wet conditions.     

The Rožná uranium deposit (Bohemian Massif, Czech Republic): shear zone-hosted, late Variscan and post-Variscan hydrothermal mineralization

Three major mineralization events are recorded at the Rožná uranium deposit (total mine production of 23,000 t U, average grade of 0.24% U): (1) pre-uranium quartz-sulfide and carbonate-sulfide mineralization, (2) uranium, and (3) post-uranium quartz-carbonate-sulfide mineralization. (1) K–Ar ages for white mica from wall rock alteration of the pre-uranium mineralization style range from 304.5 ± 5.8 to 307.6 ± 6.0 Ma coinciding with the post-orogenic exhumation of the Moldanubian orogenic root and retrograde-metamorphic equilibration of the high-grade metamorphic host rocks. The fluid inclusion record consists of low-salinity aqueous inclusions, together with H₂O-CO₂-CH₄, CO₂-CH₄, and pure CH₄ inclusions. The fluid inclusion, paragenetic, and isotope data suggest that the pre-uranium mineralization formed from a reduced low-salinity aqueous fluid at temperatures close to 300°C. (2) The uraniferous hydrothermal event is subdivided into the pre-ore, ore, and post-ore substages. K–Ar ages of pre-ore authigenic K-feldspar range from 296.3 ± 7.5 to 281.0 ± 5.4 Ma and coincide with the transcurrent reorganization of crustal blocks of the Bohemian Massif and with Late Stephanian to Early Permian rifting. Massive hematitization, albitization, and desilicification of the pre-ore altered rocks indicate an influx of oxidized basinal fluids to the crystalline rocks of the Moldanubian domain. The wide range of salinities of fluid inclusions is interpreted as a result of the large-scale mixing of basinal brines with meteoric water. The cationic composition of these fluids indicates extensive interaction with crystalline rocks. Chlorite thermometry yielded temperatures of 260°C to 310°C. During this substage, uranium was probably leached from the Moldanubian crystalline rocks. The hydrothermal alteration of the ore substage followed, or partly overlapped in time, the pre-ore substage alteration. K–Ar ages of illite from ore substage alteration range from 277.2 ± 5.5 to 264.0 ± 4.3 Ma and roughly correspond with the results of chemical U–Pb dating of authigenic monazite (268 ± 50 Ma). The uranium ore deposition was accompanied by large-scale decomposition of biotite and pre-ore chlorite to Fe-rich illite and iron hydrooxides. Therefore, it is proposed that the deposition of uranium ore was mostly in response to the reduction of the ore-bearing fluid by interaction with ferrous iron-bearing silicates (biotite and pre-ore chlorite). The Th data on primary, mostly aqueous, inclusions trapped in carbonates of the ore substage range between 152°C and 174°C and total salinity ranges over a relatively wide interval of 3.1 to 23.1 wt% NaCl eq. Gradual reduction of the fluid system during the post-ore substage is manifested by the appearance of a new generation of authigenic chlorite and pyrite. Chlorite thermometry yielded temperatures of 150°C to 170°C. Solid bitumens that post-date uranium mineralization indicate radiolytic polymerization of gaseous and liquid hydrocarbons and their derivatives. The origin of the organic compounds can be related to the diagenetic and catagenetic transformation of organic matter in Upper Stephanian and Permian sediments. (3) K–Ar ages on illite from post-uranium quartz-carbonate-sulfide mineralization range from 233.7 ± 4.7 to 227.5 ± 4.6 Ma and are consistent with the early Tethys-Central Atlantic rifting and tectonic reactivation of the Variscan structures of the Bohemian Massif. A minor part of the late Variscan uranium mineralization was remobilized during this hydrothermal event.     

The sedimentary cycle of the boron isotopes

Marine sediments contain two isotopically distinct components: a non-desorbable fraction with δ¹¹B between −4.3 and +2.8 per mil (n = 10) and a desorbable component with δ¹¹B between 13.9 and 15.8 per mil (n = 6). The adsorption coefficient, K, for the uptake of B from seawater by fluvial suspended material (Mississippi) has an experimentally determined value of 1.54 ± 0.05. The associated isotope fractionation factor, α, is 0.974 ± 0.003. Empirical values for K, determined from the analysis of marine sediments (n = 6), were between 3 and 4. The amount of B adsorbed onto fluvial suspended material during estuarine mixing is about 9 × 10⁹ moles/yr. Based on pore water data, adsorption experiments and comparative size fraction analyses (suspended sediments from the Mississippi River vs. bottom deposits from the Delta) there is no evidence for the incorporation of B into detrital sediments at low temperature. However, the high B content of Bauer Deep metalliferous sediments must be due to incorporation of seawater B during formation of authigenic silicates. The δ¹¹B of these minerals is 2 ± 3 per mil.Hydrothermally altered sediments from DSDP Hole 477, Guaymas Basin, Gulf of California have variable B contents, from 33 ppm, similar to the unaltered detritus, to 1.2 ppm in the recrystallized material. The latter has δ¹¹B as low as −9.0 per mil, substantially lower than the unaltered material. Hydrothermal solutions collected from vents adjacent to the hole have boron contents elevated by about a factor of 4 relative to seawater and δ¹¹B between 16.5 and 23.2 per mil. The B mobilized from the sediments is isotopically fractionated with the fluids being preferentially enriched in the heavy isotope.Analysis of an oxisol profile developed over granite in the Guyana Shield showed that boron is partially mobilized during weathering with an isotopic offset of 2.5 per mil between bedrock and soil.The observed enrichment of B in shales relative to igneous rocks does not occur during weathering or during exposure to seawater at low temperature. Incorporation occurs only during burial diagenesis at temperatures greater than about 60°C. However, the enrichments cannot be attained during a single cycle of primary weathering and burial but must be cumulative over many cycles.