Nd-Sr isotopic and trace element study of rocks and fluids from the continental deep drilling Project (KTB), Germany

Geochemical analyses were interpreted on the dominant lithological units and on a deep crustal fluid from the Continental Deep Drilling Project (KTB) Pilot Hole, situated at the western margin of the Variscan Bohemian Massif. The biotite gneiss (from 384 m depth) shows a rare earth element pattern very similar to the European shale composite with Nd model ages of 940 Ma (CHUR) and 1.4 Ga (DM). The lamprophyre dike in the upper profile (1549 m), a nepheline and olivine normative basalt, is geochemically and isotopically similar to rocks from the Tertiary Central European Volcanic Province. The lower metabasite sequence (3575–4000 m), with an intrusion age of approximately 500 Ma, is made up primarily of highly metamorphosed subalkalic olivine basalts. The geochemical characteristics of the metabasites are a (La/Yb)_N of 5–10, an La concentration of 20–50 times chondrite as well as (⁸⁷Sr/⁸⁶Sr)_i of 0.7035–0.7038 and _Nd(T) of 4–6. These values suggest a depleted mantle source for the igneous precursors, evolving by assimilation-fractional crystallization processes with up to 25% of upper crust into the ultramafic, basaltic, and intermediate rock types of the metabasite sequence. The strong geochemical and chronological similarities between the KTB metabasites and rocks from the Münchberg Massif suggest that these units belong to the same lithological complex. The high salinity as well as the radiogenic ⁸⁷Sr/⁸⁶Sr ratio of 0.709413 in the KTB fluid from 4000 m depth might be the result of migrating fluids reacting with the regional Permo-Mesozoic evaporite deposits, followed by extensive Sr isotopic exchange with the upper crust.     

Origin of convex tetrads in rare earth element patterns of hydrothermally altered siliceous igneous rocks from the Zinnwald Sn-W deposit, Germany

The chondrite-normalized rare earth element (REE) patterns of whole rock samples from evolved granitic systems hosting rare metal deposits sometimes show a split into four consecutive curved segments, referred to as tetrads. In the present contribution, a rigorous statistical method is proposed that can be used to test whether geological significance should be attributed to tetrads that are only of limited size. The method involves a detailed evaluation of element and sample specific random and systematic errors that are constrained on the basis of independent repeated preparations and analyses of sample and reference materials. Application of the proposed method to samples from the granite-hosted Zinnwald Sn-W deposit, Germany, revealed that at least two tetrads in normalized whole rock REE patterns have to be analytically significant to rule out that fractional crystallization led to the unusual behavior of the REEs. Based on the analysis of altered albite granite and greisen samples from the endocontact of the Zinnwald granite massif, it is demonstrated that the lanthanide tetrad effect is responsible for the formation of the convex tetrads. Geological and petrological evidence suggests that the tetrads in the samples developed prior to greisenization and related cassiterite precipitation. In contrast to the endocontact samples, the rhyolitic wall rocks are typified by normalized REE patterns having tetrads that are variable in size and frequently close to the limit of analytical significance. The sizes of the tetrads apparently correlate with the intensity of albitization, but show no relation to subsequent alteration processes including greisenization and low-temperature argillization. This observation proves that curved segments in normalized whole rock REE patterns can be introduced during hydrothermal fluid-rock interaction.     

胶东新立构造蚀变岩型金矿床元素地球化学行为

新立金矿位于华北克拉通东部胶东金矿省内,是一个典型的蚀变岩型(焦家型)金矿床,矿床受区域三山岛-仓上断裂带控制,产出于蚀变的玲珑花岗岩中。在主断裂带下盘蚀变矿化发育,可以划分为五个阶段:钾长石化阶段、绢英岩化阶段、黄铁绢英岩矿化阶段、多金属硫化物矿化阶段和碳酸盐化阶段。不同的蚀变矿化过程导致各阶段样品具有不同的矿物组合和地球化学特征。钾长石化花岗岩以高钾钠含量为特征,因为样品中含有新生成的二次钾长石及残留的钠长石;绢英岩的钙钠含量明显低于钾长石化花岗岩,是绢英岩化阶段斜长石蚀变分解所致;黄铁绢英岩FeT2O3含量普遍较高且SiO 2含量波动明显,与该阶段样品中大量黄铁矿的产出及部分样品中包含石英团块或石英脉相一致;多金属硫化物矿化样品的元素含量与黄铁绢英岩基本类似;碳酸盐化蚀变样品以高CaO含量为特征,与该阶段大量沉淀析出的方解石相符。在原始地幔标准化微量元素配分图上,不同阶段矿化蚀变样品,大离子亲石元素Rb、Ba、K、Sr差异性明显,而高场强元素Zr、Hf、Nb、Ta、P差异性较小,表明热液蚀变过程中大离子亲石元素活动性较强,高场强元素相对稳定。在稀土元素球粒陨石标准化图中,不同阶段样品均呈明显的右倾性,蚀变早期(钾长石化阶段)样品铕异常不明显,蚀变矿化主期(绢英岩化阶段至多金属硫化物矿化阶段)样品普遍具有负铕异常,而蚀变晚期(碳酸盐化阶段)样品普遍具有正铕异常。元素相关性分析表明,金与银、砷、铋和硫具明显正相关,与铜、铅具有一定的相关性。成矿元素因子分析也显示出金与砷、硫、铁、钴在矿化过程中具有类似的地球化学行为。实测剖面上不同位置样品元素地球化学特征的差异性主要受构造及蚀变矿化类型、强度控制,成矿元素在主断裂附近达到峰值,在远离主断裂方向上,其含量整体呈下降趋势,但在次级矿化断裂发育地段,含量又明显回升;另外在断裂附近由于微裂隙及节理相对发育,有利于热液的渗透,蚀变较强,对成矿元素的空间分布亦具有控制作用。     

Magma–carbonate interaction: An experimental study on ultrapotassic rocks from Alban Hills (Central Italy)

The Alban Hills ultrapotassic volcanic district is one of the main districts emplaced during Quaternary time along the Tyrrhenian margin of Italy. Alban Hills lava flows and scoria clasts are made up essentially of clinopyroxenes and leucites and their chemical composition is mostly K-foiditic. Differentiated products (MgO < 3 wt.%) are characterised by low SiO₂ concentration (< 50 wt.%) and geochemical features indicate that this unique differentiation trend is driven by crystal fractionation plus carbonate crust interaction. Notably, the Alban Hills Volcanic District was emplaced into thick limestone units. With the aim of constraining the magmatic differentiation, we performed experiments on the Alban Hills parental composition (plagioclase-free phono-tephrite) under anhydrous, hydrous, and hydrous-carbonated conditions. Experiments were carried out at 1 atm, 0.5 GPa and 1 GPa, temperatures ranging from 1050 to 1300 °C, and H₂O and CaCO₃ in the starting material up to 2 and 7 wt.%, respectively. The experiments performed at 0.5 GPa are the most representative of the Alban Hills plumbing system. Clinopyroxene and leucite are the main phases occurring under all the investigated conditions and the liquidus phases. Nevertheless, our experimental results demonstrate that the occurrence of CaCO₃ in the starting material strongly affects phase relations. Experiments performed under hydrous conditions crystallize magnetite and phlogopite at relatively high temperature. This early crystallization drives the glass composition towards a silica enrichment, resulting in a differentiation trend moving from phono-tephritic (Alban Hills parental composition) to phonolitic compositions. This is in contrast with micro-textural evidence showing late crystallization of magnetite and phlogopite in the natural products and with the composition of the juvenile products. On the contrary, in the CaCO₃-bearing experiments (i.e., simulating magma–carbonate interaction) the magnetite and phlogopite stability fields are strongly reduced. As a consequence, the melt differentiation is mainly controlled by the cotectic crystallization of clinopyroxene and leucite, resulting in a differentiation trend moving towards K-foiditic compositions. These experimental results are in agreement with micro-textural features and chemical compositions of Alban Hills natural products and with the magmatic differentiation model inferred by geochemical data. Magma–carbonate interaction is not a rare process and its occurrence has been demonstrated for different plumbing systems. However, the uniqueness of the Alban Hills liquid line of descent suggests that the efficacy of the carbonate contamination process is controlled by different factors, the dynamics of the plumbing system being one of the most important.     

An evaluation of the Rb vs. (Y + Nb) discrimination diagram to infer tectonic setting of silicic igneous rocks

The most commonly used tectonic discrimination diagrams for granites were introduced by Pearce et al. [Pearce, J.A., Harris, N.B.W., Tindle, A.G., 1984. Trace element discrimination diagrams for the tectonic interpretation of granitic rocks. J. Petrol. 25, 956–983.]. Since then, many studies have shown that some granites defy classification or their geochemical assignment does not fit with the geodynamic environment in which they are thought to have formed. In this paper we evaluate the performance of the Pearce et al. tectonic discrimination method, specifically, the most widely-used Rb-(Y + Nb) diagram, using a new data base of over 250 occurrences worldwide, the tectonic settings of which are fairly well known. We conclude that a correlation of geochemistry and tectonic position exists, but that ambiguities and misclassifications arise from one or both of the following factors. First, complex or polyphase orogeny can mix source rocks of different tectonic provenance. This is common in continental arcs and collisional settings, which can be closely associated in space and time with extensional regimes. Second, differentiation can produce compositional trends which cross field boundaries, especially the VAG to WPG boundary. One can minimize this problem by using less felsic, noncumulate members of cogenetic series.

We demonstrate the inherent weaknesses of trace element tectonic discrimination diagrams. Such diagrams are of little use if applied alone, but they can be valuable in combination with other methods such as dating and geologic assessment.     

Finite element study of the Nevis Bluff (New Zealand) rock slope failure

SummaryFinite Element Study of the Nevis Bluff (New Zealand) Rock Slope Failure In June 1975, part of the Nevis Bluff rock slope failed along State Highway 6 in the South Island of New Zealand. The slope is near the bottom of the Kawarau River valley, which has been deeply entrenched in chlorite schist rocks. The detailed geology of the slope, and the mechanical properties of the rocks comprising the slope are described. For the purposes of finite element modelling, the schist was assumed to be a transversely isotropic material with four independent deformability parameters. A two dimensional finite element program was used to establish the regional state of stress, the results from which were then used in a larger scale model of the rock slope. The results of finite element analyses suggested that slope failure occurred by flexural toppling, where continuous columns broke in flexure as they slid along schistosity surfaces. Flexural cracking was then responsible for propagating the plane along which sliding occurred. When the shear strength available along this plane was exceeded by shear stresses, the slope failed.

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ZusammenfassungUntersuchung des Bruches eines Felshanges des Nevis Bluff (Neuseeland) mit Hilfe der Methode der Finiten Elemente Im Juni 1975 brach ein Teil des Felshanges von Nevis Bluff entlang der Autobahn 6 auf der Südinsel von Neuseeland. Die Rutschung ereignete sich nahe des Talbodens des Flusses Kawarau, welcher sehr tief in Chloritschiefer eingeschnitten ist. Die detaillierte Geologie dieser Rutschung und die mechanischen Eigenschaften der dabei wirksamen Felspartien werden beschrieben. Im Hinblick auf eine Untersuchung des Rutschvorganges mit Hilfe der Methode der Finiten Elemente wurde das schiefrige Medium als transversal isotropes Medium mit vier voneinander unabhängigen Verformungsparametern angenommen. Für die Ermittlung des primären Spannungszustandes wurde ein zweidimensionales Finite-Elemente-Programm benützt. Die Ergebnisse dieser Untersuchung wurden dann in einem erweiterten Rechenmodell für die Hangrutschung verwendet. Die Ergebnisse der Untersuchung zeigten, daß die Rutschung auf einen Mechanismus ähnlich dem Hakenwerfen zurückzuführen sein dürfte, wobei bei diesem Vorgang durchgehende Platten durch Biegung zum Bruch kamen, als sie auf den Schieferungsflächen abglitten. Biegerisse waren die Ursache für die Ausbildung einer durchgehenden Gleitfläche. Sobald die Scherfestigkeit in dieser Gleitfläche überschritten wurde, kam der Hang zu Bruch.

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RésuméÉtude de la rupture de pente rocheuse de Nevis Bluff par la méthode d'éléments finis En juin 1975, une partie de la paroi rocheuse de Nevis Bluff, le long de la route nationale 6 en Nouvelle Zélande s'est éffondrée. La pente est près du fond de la vallée de la rivière Kawarau qui s'est profondément encaissée dans des schistes chloritiques. La géologie détaillée de la paroi et les propriétés mécaniques des roches constitutives sont décrites. Pour la modélisation par éléments finis, le schiste a été supposé se comporter comme un matériau orthotrope avec quatre paramètres de déformation. L'utilisation d'un programme d'éléments finis bidimensionnels a permis d'établir l'état de contrainte régional qui fut transféré à un modèle de la paroi rocheuse de plus grande échelle. Les résultats de l'analyse par éléments finis suggèrent que la rupture a en lieu par fauchage des couches dans lequel des colonnes continues se fissurent en flexion à mesure qu'elles glissent le long de surfaces de schistosité vers l'ouverture. Les fissures de flexion se sont approfondies jusqu'à former un plan sur lequel le glissement a eu lieu. Quand la résistance au cisaillement le long de ce plan a été dépassée par les contraintes de cisaillement, la paroi s'est éffondrée.

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With 16 Figures     

Paleoproterozoic subduction-related metasomatic signatures in the lithospheric mantle beneath NE Brazil: inferences from trace element and Sr–Nd–Pb isotopic compositions of Neoproterozoic high-K igneous rocks

Late Neoproterozoic (ca. 580 Ma), high-K, mafic-intermediate rocks represent voluminous bimodal magmatism in the Borborema Province, northeast Brazil. These rocks show the following chemical signatures that reflect derivation from a subduction-modified lithospheric mantle source: (1) enrichment in large ion lithophile elements (Rb, Ba, K, Th) and light rare-earth elements (REE) (La/Yb_CN=11–70), (2) pronounced negative Nb anomalies, and (3) radiogenic Sr (0.71202–0.7059) and unradiogenic Nd (_Nd from −9.3–−20.1) isotopic compositions. T_DM model ages suggest that modification of the lithospheric mantle source (metasomatised garnet lherzolite) may have occurred in the Paleoproterozoic during the Transamazonian/Eburnean tectonics that affected the region. Interaction with asthenospheric fluids is believed to have partially melted this enriched source in the Neoproterozoic, probably as a result of asthenosphere-derived fluid percolation in the Brasiliano/Pan-African shear zones that controlled the emplacement of these mafic-intermediate magmas. The involvement of this asthenospheric component is supported by the nonradiogenic Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb=16–17.3, ²⁰⁷Pb/²⁰⁴Pb=15.1–15.6, ²⁰⁸Pb/²⁰⁴Pb=36–37.5), which contrast with the enriched Sr and Nd compositions and thereby suggest the decoupling of Rb–Sr, Sm–Nd, and U–Pb systems at the time of intrusion of the mafic-intermediate magmas in the crust.     

Tectonic analysis and paleo-stress determination of the upper lava section at ODP/IODP site 1256 (East Pacific Ocean)

Research on the deep sea is of great importance for a better understanding of the mechanism of magma emplacement and the tectonic evolution of oceanic crust. However, details of the internal structure in the upper levels of the oceanic crust are much less complete than that of the more fully studied sub-aerial areas. For the first time, this study proposes a dynamic analysis using the inversion method on core data derived from the drilled basement of the present-day intact oceanic crust at ODP/IODP Site 1256 in the Cocos plate. The research is based on an innovative core reorientation process and combines different stress hypothesis approaches for the analysis of heterogeneous failure-slip data via exploitation of two distinct techniques. From the analysis of the failure-slip data, both techniques produce 5 distinct subsystem datasets. All calculated subsystems are mechanically and geometrically admissible. Interpretation of the results allows the researchers to note a complex local and regional tectonic evolution deriving from the interplay of (1) the ridge push and rotation of both the East Pacific Rise and the Cocos-Nazca Spreading Center, (2) the effect of the slab pull of the Middle America Trench, (3) the influence of lava emplacement mechanisms, and (4) intra-plate deformation.     

Application of light hydrocarbons (C4–C13) to oil/source rock correlations:: a study of the light hydrocarbon compositions of source rocks and test fluids from offshore Mid-Norway

Relatively little work has been published on the correlation between the light hydrocarbon distributions in reservoir fluids and their proposed source rocks [Philippi, G. T. (1981)]. The aim of our work was to study this relationship in detail for samples from Mid-Norway. The main source rocks offshore Mid-Norway are the marine shales of the Late Jurassic Spekk Formation and the coals and paralic shales of the Early Jurassic Åre Formation. Reliable light hydrocarbon (C₄–C₁₃) data for source rock samples were acquired by thermal extraction-GC of the source rocks. Of these, notably the hydrocarbons in the C₆–C₈ range (routinely measured in test fluids) were used to discriminate between the Spekk and Åre Formation samples. A total of twenty-six samples from the Spekk Formation and twenty-four samples from the Åre Formation at different maturity levels and facies were analyzed. In general, the two source rock types differ in their light hydrocarbon composition by the presence of relatively more aromatics and cyclohexanes in the Åre samples, while the Spekk samples are richer in cyclopentanes and acyclic hydrocarbons. We show that source rock facies is a more important indicator of light hydrocarbon composition than maturity variation. Differences in the chemical composition, which can be used to discriminate between the two source rocks, were supported by differences in the carbon isotope composition of individual components of the same fraction, as determined by GHM-IR-MS analysis of eleven samples. Further, the light hydrocarbon compositions of reservoir fluids (oils and condensates) were compared with those for the source rock(s). Sixty-six gas chromatograms of oils and condensates, representing most of the known petroleum accumulations in Mid-Norway, were collected. Of these, five oil samples were selected for detailed isotopic analysis of individual components (GC-IR-MS). When using a classification scheme based on data from sediment samples, data for the light hydrocarbon fraction of oils and condensates indicate that the Spekk Formation is the dominant source for most of the fields from Mid-Norway, with a significant contribution from the Åre Formation being detected principally in one field. Differences in the chemical composition of the C₆–C₈ fractions were supported by differences in the carbon isotope composition of individual components, which also discriminate between the oils. Although the classification diagrams used in this study are based on source rock data from Mid-Norway, the method can be applied to other areas, providing that the diagrams are calibrated with source rock data from the area of interest.     

Chemistry of fluids from a natural analogue for a geological CO2 storage site (Montmiral, France): Lessons for CO2–water–rock interaction assessment and monitoring

Chemical and isotope studies of natural CO₂ accumulations aid in assessing the chemical effects of CO₂ on rock and thus provide a potential for understanding the long-term geochemical processes involved in CO₂ geological storage. Several natural CO₂ accumulations were discovered during gas and oil exploration in France’s carbogaseous peri-Alpine province (south-eastern France) in the 1960s. One of these, the Montmiral accumulation at a depth of more than 2400 m, is currently being exploited. The chemical composition of the water collected at the wellhead has changed in time and the final salinity exceeds 75 g/L. These changes in time can be explained by assuming that the fraction of the reservoir brine in the recovered brine–CO₂–H₂O mixture varies, resulting in variable proportions of H₂O and brine in the sampled water. The proportions can be estimated in selected samples due to the availability of gas and water flowrate data. These data enabled the reconstruction of the chemical and isotope composition of the brine. The proportions of H₂O and brine can also be estimated from isotope (δ²H, δ¹⁸O) composition of collected water and δ¹⁸O of the sulfates or CO₂. The reconstituted brine has a salinity of more than 85 g/L and, according to its Br⁻ content and isotope (δ²H, δ¹⁸O, δ³⁴S) composition, originates from an evaporated Triassic seawater that underwent dilution by meteoric water. The reconstitution of the brine’s chemical composition enabled an evaluation of the CO₂–water–rock interactions based on: (1) mineral saturation indices; and (2) comparison with initial evaporated Triassic seawater. Dissolution of K- and SO₄-containing minerals such as K-feldspar and anhydrite, and precipitation of Ca and Mg containing minerals that are able to trap CO₂ (carbonates) are highlighted. The changes in concentration of these elements in the brine, which are attributed to CO₂ interactions, illustrate the relevance of monitoring the water quality at future industrial CO₂ storage sites.     

An experimental study of rare earth element partitioning between a shergottite melt and pigeonite: implications for the oxygen fugacity of the mart ian interior

A series of experiments on a synthetic, pigeonite-saturated, basaltic shergottite were carried out to constrain the variation of D(Eu/Gd)_{pigeonite/melt} and D(Eu/Sm)_{pigeonite/melt} with oxygen fugacity (f_O2). The experiments have been run under both dry and hydrous conditions. The shergottite was doped with 0.1, 0.5, and 1.0 wt.% Eu, Gd, and Sm oxides in different experiments and was equilibrated at liquidus conditions for 24 hours. D(Eu/Gd)_{pigeonite/melt} in dry melts ranges from 0.156 ± 0.014 (f_O2 = IW − 1) to 0.630 ± 0.102 (IW + 3.5). D(Eu/Sm)_{pigeonite/melt} in dry melts ranges from 0.279 ± 0.021 (IW − 1) to 1.114 ± 0.072 (IW + 3.5). Due to difficulties with low-f_O2 experiments, hydrous distribution coefficients were measured, but were not used in the calibration of the Eu-oxybarometers. These two Eu-oxybarometers provide an accurate way to measure f_O2 recorded during pigeonite crystallization, thereby yielding a record of f_O2 during the earliest period of Martian meteorite parent magma crystallization history.Using this new calibration, Martian meteorite pigeonite cores record f_O2 values of IW − 0.6 (±0.3) (QUE94201) to IW + 1.9 (±0.6) (Shergotty). These new values differ in magnitude, but not trend, from previously published data. The pigeonite Eu-oxybarometer yields an f_O2 range in the basaltic shergottites of 2 to 3 orders of magnitude. Several processes have been proposed to explain the origin of this f_O2 range, the majority of which rely on assimilation of an oxidized source. A potential correlation between this new pigeonite data and recent Fe-Ti oxide data, however, is consistent with intrinsic f_O2 differences in the magma source region being responsible for the measured f_O2 variations. This implies that the Martian meteorite source region, the mantle or lithosphere, may be heterogeneous in nature. However, the process of assimilation cannot be completely ruled out in that an assimilation event that took place before crystallization commenced would result in the overprinting of the source region f_O2 signature.     

Influence of natural fulvic acids on the solubility of sulfide ores (experimental study)

Model experiments were performed on the solubility of sulfide ores from the Kyzyl-Tashtyg deposit in distilled water and fulvic-acid (FA) solutions of different concentrations. It has been established that the oxidation of sulfide minerals in ores under atmospheric conditions might produce acid drainage waters with toxic heavy metals (Cu, Zn, Cd). The influence of natural organic acids depends on the capability of ore and host rock to neutralize the acidity of solutions. If carbonate content is enough at the first stage, a considerable increase in the pH value of FA-free solutions ensures Fe and Cu removal into the solid phase, whereas the formation of metal fulvate complexes hinders this process. However, when the rocks exhaust their neutralizing potential, all the solutions remain acidic for > 100 days of leaching. In this case, FAs, on the contrary, inhibit the oxidation of the surface of sulfide minerals and reduce the removal of heavy metals into the solution.     

Physical properties of ultrahigh-pressure metamorphic rocks from the Sulu terrain, eastern central China: implications for the seismic structure at the Donghai (CCSD) drilling site

About 30 samples representing major lithologies of Sulu ultrahigh-pressure (UHP) metamorphic rocks were collected from surface exposures and exploration wells, and compressional (Vp) and shear wave (Vs) velocities and their directional dependence (anisotropy) were determined over a range of constant confining pressures up to 600 MPa and temperatures ranging from 20 to 600 °C. Samples range in composition from acidic to ultramafic. P- and S-wave velocities measured at 600 MPa vary from 5.08 to 8.64 km/s and 2.34 to 4.93 km/s, respectively. Densities are in the range from 2.60 to 3.68 g/cm³. To make a direct tie between seismic measurements (refraction and reflection) and subsurface lithologies, the experimental velocity data (corresponding to shallow depths) were used to calculate velocity profiles for the different lithologies and profiles of reflection coefficients at possible lithologic interfaces across the projected 5000-m Chinese Continental Scientific Drilling Program (CCSD) crustal segment. Comparison of calculated in situ velocities with respective intrinsic velocities suggests that the in situ velocities at shallow depths are lowered by an increased abundance of open microcracks. The strongly reflective zone beneath the Donghai drill site can be explained by the impedance contrasts between the different lithologies. Contacts between eclogite/peridotite and felsic rocks (gt-gneiss, granitic gneiss), in particular, may give rise to strong seismic reflections. In addition, shear-induced (lattice preferred orientation (LPO)-related) seismic anisotropy can increase reflectivity. For the explanation of the high velocity bodies (>6.4 km/s) around 1000 m and below 3200-m depth, large proportions of eclogite/peridotite (about 40 and 30 vol.%, respectively) are needed.     

Enrichment of SiO2 in rhyolites by fractional crystallization: An experimental study of peraluminous granitic rocks from the St. Francois Mountains, Missouri, USA

Experiments were conducted to test the hypothesis that higher silica rhyolites of the St. Francois Mountains, Missouri, USA are products of fractional crystallization of lower silica granitic magmas. Experiments were carried out at pressures of 0.5 and 1.0 kb under water-saturated conditions, temperatures ranged from 800° to 925°C and the oxygen fugacity for all experiments were maintained at, or near, the nickel-nickel oxide (NNO) buffer level.

Results of experiments with Butler Hill granite indicate that fractionation of near liquidus silicate phases, orthopyroxene and plagioclase, causes an enrichment of SiO₂ in the residual melts. Mineralogical and chemical compositions of the experimental charges are similar to that of higher silica Grassy Mountain rhyolites of the St. Francois Mountains. Experiments also show that at pressures of 1.0 Kb or higher orthopyroxene reacts with the hydrous melt to produce biotite which is a common phase in the plutonic rocks of the St. Francois Mountains.     

The genesis of Variscan (Hercynian) plutonic rocks: Inferences from Sr,Pb, and O studies on the Maladeta igneous complex,central Pyrenees (Spain)

The Maladeta plutonic complex formed during the latest stages of the Variscan orogeny. It was emplaced into the Paleozoic sedimentary sequence of the Pyrenees. The eastern part, investigated in the present study, consists of an early intrusion of cumulate gabbronorites followed in order of emplacement by the main biotite-hornblende granodiorite, which was itself intruded by two small stocks of two-mica cordierite granite. An ⁸⁷Rb-⁸⁷Sr isochron dates the granodiorite at 277±7 m.y. with an initial (⁸⁷Sr/⁸⁶Sr)_o ratio of 0.7117±3. Gabbroic rocks have lower strontium initial ratios, down to 0.7092, while those of granite range from that of the granodiorite up to about 0.715. The three rock types have distinctive ¹⁸O values: 8.7 to 9.6 for the gabbronorites, 9.4 to 10.4 for the granodiorites and 10.3 to 11.8 for the granites. Lead isotopic compositions of rocks and feldspars are all radiogenic. Feldspars give consistent Pb model ages around 280 m.y., with and values of about 9.7 and 4.05, respectively. No pristine, mantle-derived magma was found among the investigated samples and the rocks cannot be related to one another by any simple mechanism of fractional crystallization. Some type of mixing process involving two end members seems to be required: a high-¹⁸O, high-⁸⁷Sr material that is clearly of crustal origin, and a lower-¹⁸O, lower-⁸⁷Sr end member derived from the mantle. Examination of various mixing models does not support magma mixing nor assimilation of crustal rocks by a mafic magma. The most acceptable model involves melting at different levels of a vertically-zoned source in the continental crust; this source was formed by mixing between mantle-derived magmas and crustal metasediments. This material was apparently thickened, tectonically downwarped and partially melted. None of the Maladeta magma-types appear to have been derived at a consuming plate boundary.Contribution Number 3280, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA     

Crystallographic procedures in the study of experimental rocks: x-ray single-crystal structure refinement of C2/c clinopyroxene from lunar 74275 high-pressure experimental basalt

Summary The possibility of applying X-ray single crystal techniques to minerals pertaining to rocks experimentally crystallized in laboratory has been investigated as a new approach to precisely relate crystal-chemistry to pressure, temperature, fO₂, and composition of the magma from which the crystal formed.A clinopyroxene from the experimental lunar basalt (74275 composition) ofGreen et al. (1975) crystallized at 12 Kb and 1320 °C, was successfully refined to an R factor of 0.041. Its structure configuration turned out to be exceptional, expecially in relation to the record low Ca(M2) occupancy (0.57 atoms per formula unit henceforth a.f.u.), but comparable with the other lunar C2/c clinopyroxene previously studied with X-ray single crystal methodology: augite 12052 (Takeda 1972 a). Comparative analysis of the two lunar clinopyroxene structures revealed their common high temperature origin and the high-pressure imprint of the experimental specimen relative to the natural one.Both lunar samples differ radically from the studied terrestrial clinopyroxenes of C2/c diopside-like structure: the main difference of lunar clinopyroxenes with respect to terrestrial analogues is the high Ally (T) (Al^IV > 0.20 a.f.u.) in spite of low Ca(M2). Relative to the ideal diopside structure, Si⁴⁺ Al^IV and Ca Mg + Fe²⁺ substitutions in T and M2 sites, respectively, turned out to be not compatible with terrestrial clinopyroxenes.

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Kristallographische methoden zur untersuchung experimenteller gesteine: struktur verfeinerung von C₂/c klinopyroxen aus dem experimentellen hochdruck mond-basalt 74275

Zusammenfassung Die Anwendung von Einkristallverfahren auf Minerale aus experimentell hergestellten Gesteinen wurde untersucht; sie wird als ein neuer Weg zur quantitativen Korrelation der Kristallchemie mit Druck, Temperatur, fO₂ und der Zusammensetzung des Magmas, aus dem der Kristall gebildet wurde, gesehen.Die Struktur eines Klinopyroxens aus dem experimentellen Mond-Basalt (Zusammensetzung 74275) vonGreen et al. (1975), der bei 1320 °C kristallisierte, wurde mit Erfolg bis auf einen R-Faktor von 0.041 verfeinert. Es zeigte sich, daß seine Struktur-Konfiguration außergewöhnlich war, besonders im Hinblick auf die besonders niedrige Ca(M2) Besetzungsdichte (0.57 Atome pro Formeleinheit). Sie ist jedoch vergleichbar mit dem anderen lunaren C2/c Klinopyroxen der bisher mit Röntgen-Einkristallverfahren untersucht wurde, nämlich Augit 12052) (Takeda, 1972a). Vergleichsanalysen der beiden lunaren Klinopyroxen-Strukturen lassen ihre gemeinsame Hochtemperatur-Entstehung erkennen, sowie den — im Gegensatz zu der natürlichen Probe — deutlichen Einfluß hoher Drucke auf die experimentell hergestellte Probe.Beide lunare Proben unterscheiden sich deutlich von den untersuchten terrestrischen Klinopyroxenen mit Diopsid-artiger C2/c Struktur: der Hauptunterschied zwischen lunaren Klinopyroxenen und ihren terrestrischen Analogen ist der hohe Al^IV (T) (Al^IV > 0.20 a.f.u.) trotz niedrigem Ca(M2). Im Vergleich mit der idealen Diopsidstruktur zeigte sich daß, Si⁴⁺ Al^IV und Ca Mg + Fe²⁺ Substitutionen an T resp. M2 Plätzen nicht kompatibel mit terrestrischen Klinopyroxenen sind.

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With 4 Figures     

The solubility of nantokite (CuCl(s)) and Cu speciation in low-density fluids near the critical isochore: An in-situ XAS study

The solubility of nantokite (CuCl_(s)) and the structure of the predominant copper species in supercritical water (290-400 bar at 420 °C; 350-450 °C at 290 bar; 500 °C at 350 bar; density = 0.14-0.65 g/cm³) were investigated concurrently using synchrotron X-ray absorption spectroscopy (XAS) techniques. These conditions were chosen as they represent single phase solutions near the critical isochore, where the fluid density is intermediate of typical values for vapour and brine and is highly sensitive to even small changes in pressure. X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption spectroscopy (EXAFS) analyses show that aqueous copper occurs in a slightly distorted linear coordination in the solutions studied, with an average of 1.35(±0.3) Cl and 0.65(±0.3) O neighbours. The solubility of CuCl_(s) decreases exponentially with decreasing water density (i.e., decreasing pressure at constant temperature), in a manner similar to the solubility behaviour of salts such as NaCl in water vapour. Based on this similarity, an apparent equilibrium constant for the dissolution reaction of 0.5 ± 0.4 was calculated from a regression of the data at 420 °C, and it was determined that each Cu atom is solvated by approximately three water molecules. This indicates that under these conditions, copper solubility is controlled mainly by the structure of the second-shell hydration, which is essentially invisible to the XAS techniques used in this study.These results demonstrate that for a supercritical fluid near the critical isochore, decreasing pressure may initiate precipitation of copper even before boiling or phase separation. Such a process could be responsible for near-surface ore deposition in seafloor hydrothermal systems, where supercritical fluids experience rapid pressure changes during the transition between lithostatic and hydrostatic domains.     

Sr isotopes and K,Rb, Sr balance in sediments and igneous rocks from the subducted plate of the Vanuatu (New Hebrides) active margin

To evaluate the possible contribution of ocean floor sediments during the genesis of the volcanism of Vanuatu (New Hebrides) active margin, we have determined the balance of Sr isotopes and K, Rb and Sr contents for the stratigraphic column of site 286 (leg 30, DSDP). This site is located on the oceanic plate that will be subducted. Analyses have been performed on sedimentary and igneous rocks, before and after acid leaching. The Sr isotopic data do not support the occurrence of some continental component in arc magmas of this active margin which is really intraoceanic. It is demonstrated that the d'Entrecasteaux fracture zone results from the intense fracturing of typical oceanic crust. The analyses of the volcanogenic components of the sediments show a change in the source of volcanoclastic detritus from the Loyalty islands in the Eocene to the volcanic arc of Vanuatu (New Hebrides) during Pliocene and Quaternary times. The determined balance of Sr isotopes and of K, Rb, Sr contents, may be used for calculation of multicomponent melting mixing models for the origin of Vanuatu arc magmas, but we emphasize that in these models the Sr isotopes cannot be considered as an appropriated tracer of sediment contribution.     

An experimental study of the solubility of baddeleyite (ZrO2) in fluoride-bearing solutions at elevated temperature

The solubility of baddeleyite (ZrO₂) and the speciation of zirconium have been investigated in HF-bearing aqueous solutions at temperatures up to 400 °C and pressures up to 700 bar. The data obtained suggest that in HF-bearing solutions zirconium is transported mainly in the form of the hydroxyfluoride species ZrF(OH)₃° and ZrF₂(OH)₂°. Formation constants determined for these species (Zr⁴⁺ + nF⁻ + mOH⁻ = ZrF_n(OH)_m°) range from 43.7 at 100 °C to 46.41 at 400 °C for ZrF(OH)₃°, and from 37.25 at 100 °C to 43.88 at 400 °C for ZrF₂(OH)₂°.Although the solubility of ZrO₂ is retrograde with respect to temperature, the measured concentrations of Zr are orders of magnitude higher than those predicted from theoretical extrapolations based on simple fluoride species (ZrF³⁺-ZrF₆²⁻). Model calculations performed for zircon show that zirconium can be transported by aqueous fluids in concentrations sufficient to account for the concentration of this metal at conditions commonly encountered in fluoride-rich natural hydrothermal systems.