Bildungsbedingungen von Al-Fe(III)-Epidoten

Ohne Zusammenfassung     

Bildungsbedingungen von Al-Fe (III)-Epidoten

Relations between the composition of Al-Fe(III)-epidotes and the Fe content and oxidation ratio of a series of metamorphic rocks from the Hohen Tauern area, Tyrol (Austria), were investigated. The Fe(III) content of the epidotes depends on the oxidation ratio Fe(III)×100/(Fe(III)+ Fe(II)) of the rocks. The Fe(III) content of the epidotes as well as the oxidation ratio decreases within the series from greenschist to almandin-amphibolite facies. The relation between epidote composition and oxidation ratio can be explained by the following redox reactions: 6 Fe(III) Al₂ Ep+6 Mu+6 Qz+6 Hä+n Ab ? (1a) (12 An+n Ab) Plag+6 Bio+3 H₂O+4 1/2O₂. 6 Fe(III) Al₂ Ep+6 Mu+6 Qz+n Ab ? (1b) (12 An+n Ab) Plag+2 Bio+4 Kf+7 H₂O+1 1/2O₂. These reactions are in good agreement with the observed mineral assemblages and may explain the increase of the An content of coexisting plagioclase with increasing metamorphic grade.     

The Al-Fe(III)epidote miscibility gap in a metamorphic profile through the penninic series of the Tauern window,Austria

The compositional variations in epidotes, Ca₂Al₂(Fe³⁺, Al)-Si₃O₁₂(OH), from a prograde Mesozoic rock series in the Eastern Alps, Austria, are systematically related to metamorphic grade and the oxidation state of the rock. With increasing metamorphic grade the average composition of the zoned epidotes shifts to Fe³⁺-poorer compositions reflecting not only the effect of temperature and total pressure but also the concomitant decrease of the oxidation state of the rocks. Oxidized hematite-bearing assemblages are: 90 mole % Al₂FeEp (greenschists) 70 mole % Al₂FeEp (garnet amphibolites) 58 mole % Al₂FeEp (eclogites); reduced sulfidebearing assemblages are: 42 mole % Al₂FeEp (greenschists) 24 mole % Al₂FeEp (garnet amphibolites) 23 mole % Al₂FeEp (eclogites).A similar compositional evolution of the epidotes as in the spatial sequence of the samples can be observed within the single zoned crystals, reflecting the temporal changes of temperature, total pressure and oxygen fugacity during the prograde crystallization. The Fe³⁺-contents of core and rim decrease with increasing metamorphic grade and decreasing oxidation state. Generally the zoned epidotes consist of a Fe³⁺-rich core (90 to 63 mole % Al₂FeEp) and a Fe³⁺-poorer rim (55 to 23 mole % Al₂FeEp). Core and rim of the epidote crystals are separated by a compositional gap the extension of which is independent of the bulk rock composition, the oxidation state, and the mineralogical composition of the assemblages but becomes smaller with increasing metamorphic grade: 7253 mole % Al₂FeEp (low grade greenschists, 400° C) 6355 mole % Al₂FeEp (higher grade greenschists, 500° C), and 6055 mole % Al₂FeEp (garnet amphibolites, 500–550° C). At the temperature conditions of the highest grade garnet amphibolites and eclogites (550° C) the compositional gap closes at a composition of 58 mole % Al₂FeEp.The data presented thus confirm clearly the existence of an asymmetric miscibility gap in the monoclinic Al-Fe(III)-epidote solid solution series, which, for the first time, has been assumed by Strens (1964, 1965).A model is proposed that describes the prograde compositional evolution of the epidotes studied through the competing mechanisms of growth and diffusional Al-Fe³⁺ exchange and their dependence on metamorphic grade and oxidation state.     

Die Bildungsbedingungen von alpinotypem Eklogitamphibolit und Metagabbro,erläutert and Gesteinen der Koralpe,Steiermark

Zusammenfassung Eklogitamphibolite und Metagabbros, die in dem mächtigen Gneis- und Schieferkomplex der Koralpe, westliche Steiermark, auftreten, haben mit großer Wahrscheinlichkeit gemeinsam mit den sie umgebenden Gesteinen unter den Bedingungen 8–10 Kb und 500 bis 600°C ihre Prägung erfahren. Der Übergang von Gabbro zu Metagabbro ist im Handstückbereich zu verfolgen.Die einzelnen Mineralphasen wurden im Detail auf ihre chemischen und physikalischen Eigenschaften untersucht, so daß ein ausgebreiteter Vergleich mit dem reichlichen statistischen Material der Literatur möglich ist. Hier machen es die Verteilungsquotienten einzelner Elemente sehr wahrscheinlich, daß zumindest im Eklogitamphibolit das Gleichgewicht erreicht ist. Eine ebenfalls detaillierte Untersuchung der Gesteinschemismen macht eine Aussage über die Vorgänge bei der Umwandlung von Gabbro zu Metagabbro möglich, die schrittweise im Dünnschliff beobachtet werden kann. Diese Umwandlung verläuft wesentlich isochemisch und ist durch den Zutritt von Wasser bei den angeführten Drucken und Temperaturen bestimmt.Dadruch erscheint es sinnvoll, das bekannte ACF-Diagramm der wasserfreien Eklogite durch Einführung wasserhältiger Phasen um den Parameter H₂O zu erweitern. Die sich so ergebenden Teiltetraeder erklären die beobachteten Gesteinsparagenesen der Eklogitamphibolite und der Metagabbros. Ferner ist es damit auch möglich, die alpine Eklogitfazies oder Hornblendeklogitfazies zu deuten.

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Conditions of formation of alpinotype eclogiteamphibolite and metagabbro, illustrated by rocks from the Koralpe, Styria

Summary Amphibole-bearing eclogites and metagabbros appearing in the widespread highly metamorphic complex of gneisses and micaschists very probably have been formed, together with the surrounding rocks, at pressures from 8–10 Kb and temperatures of 500–600°C. The transition from gabbro to metagabbro can occasionally be observed within a range of a few centimeters.Chemical and physical properties of the individual mineral phases were investigated in detail and the results presented so that a comparison with ample statistical data already published can be made. The distribution quotients of some elements make it probable for the components of amphibole-bearing eclogite at least to have reached equilbrium. A detailed study of the chemical composition of the rocks makes the changes from gabbro to metagabbro understandable. The stages of this transformation can be studied in thin sections. The transformation is isochemical and governed by water entering under the above mentioned conditions of pressure and temperature.Therefore, with the addition of water-containing mineral phases it is logical to extend the generally known ACF-diagramm of waterfree eclogite by the parameter H₂O. Partial tetrahedrons in the system A–C–F–H₂O then explain the observed combinations of minerals in amphibole-bearing ecologites and in metagabbros. Thus an interpretation of the so called alpine eclogite—facies or hornblendeeclogite facies becomes possible.

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Mit 15 Abbildungen     

A spectrophotometric study of Nd(III), Sm(III) and Er(III) complexation in sulfate-bearing solutions at elevated temperatures

The speciation of Nd(III), Sm(III), and Er(III) in sulfate-bearing solutions has been determined spectrophotometrically at temperatures from 25 to 250 °C and a pressure of 100 bars. The data obtained earlier on the speciation of Nd in sulfate-bearing solutions (Migdisov et al., 2006) have been re-evaluated and corrected using a more appropriate activity model and are compared with the corresponding data for Sm(III) and Er(III) and new data for Nd(III). Based on this comparison, the dominant species in the solution are interpreted to be and , with the latter complex increasing in importance at higher temperature. Equilibrium constants were calculated for the following reactions:

     

Effect of hydrolysed aluminum(III) and chromium(III) cations on the lipophilicity of talc

Liquid-liquid extraction and electrokinetic studies show that both the talc particles and the isooctane droplets are affected by the presence of hydrolysable metal species of Al(III) and Cr(III). The inherent lipophilicity of talc is unchanged by the hydroxo complexes of these metal species, while positive shifts in zeta potentials of talc and isooctane take place due partly to the strong adsorption of these hydroxo complexes. In the pH range where the hydroxide precipitates, the talc particles are rendered hydrophillic between the precipitation pH and the point-of-zero charge of the metal hydroxide. This hydrophile-lipophile transition of talc in the isooctane-water system relates to heterocoagulation among talc particles, isooctane droplets and hydroxide precipitates.     

Role of Iron(III) and Aluminum Hydroxides in Concentration/reduction of Au(III) Complexes

Abstract: The adsorption of gold on iron(III) and aluminum hydroxides from solutions containing Au(III) complexes has been studied as a function of pH and chloride concentration at 30C. Iron(III) hydroxide was more effective in adsorbing gold from solution than aluminum hydroxide. However, both hydroxides controlled the behavior of Au(III) complex with very similar manner. The most effective gold adsorption occurred in aqueous solution with near neutral pH and low Cl concentration. In this solution condition, Au(III) complexes were mainly dissolved as AuCl₂(OH)₂^- and AuCl(OH)₃^-, and the surface charge for both hydroxides was positive. In addition, the adsorbed Au(III) complexes were spontaneously reduced to elemental gold in spite of the absence of a specific reducing agent.
The results of this study suggest that adsorption and spontaneous reduction of gold complexes on the surface of hydrous metal oxides with positive charge play an important role in gold precipitation in subsurface environment.     

Die Strahlenblende von Accesa (SW-Toskana)

Zusammenfassung Innerhalb der Blei-Kupfer-Zink-Vererzung der Grube Accesa tritt Strahlenblende auf. Sie besteht zum größten Teil aus Sphalerit und geringen Mengen Wurtzit. Die Chalkopyriteinschlüsse dieses Zinksulfids lassen sich den die Altersstellung der Blende kennzeichnenden Strukturtypen zuordnen. Die Strahlenblende wird als eine frühe Ausscheidung angesehen, die sich im Verlauf der Vererzung in spätige Zinkblende umwandelt. Ihre Eigenschaften und ihre Veränderungen während der Mineralisation werden im folgenden dargestellt.

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Fibrous sphalerite from accesa, Southwest Tuscany, Italy

Summary Within the lead-copper-zinc-mineralization at Accesa Mina a Strahlenblende (fibrous sphalerite) has been found. The main component is sphalerite with very small amounts of wurtzite. The chalcopyrite inclusions in this zinc sulfide may be attributed to certain types of texture according with their age of formation. The Strahlenblende is believed to have formed early in the succession, grading into younger sparlike sphalerite. Its properties and later alteration during ore mineralization will be described.

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Mit 3 Abbildungen     

Die Kaolinlagerstatte von Geisenheim (Rheingau)

Zusammenfassung Das Kaolinvorkommen von Geisenheim besteht aus einem in Phyllite des Gedinne eingeschalteten wechselnd stark kaolinisierten Quarzkeratophyrkörper von mehrfach verzweigter zungenförmiger Gestalt. Als Ursache der Kaolinisierung wurden im bisherigen Schrifttum einerseits tertiäre Oberflächenverwitterung (F. Michels), von anderer Seite hydrothermale Lösungszufuhr (W. Wagner) angenommen. Die von uns durchgeführten Untersuchungen erbrachten weitere Hinweise auf eine Kaolinisierung durch hydrothermale bis thermale Lösungszufuhr. Der Kaolinisierung geht voraus eine durch die tektonische Einschlichtung und mechanische Durchbewegung unter seicht-epizonalen Bedingungen verursachteSericitisierung eines Teiles der Feldspatkomponente. Durch chemische, röntgenographische and mikroskopische Mineralbestandsbestimmungen an Proben von verschiedenem Kaolinisierungsgrad konnte der zunehmende Abbau des Feldspatanteiles zu Kaolinit verfolgt werden. Da mit sinkendem Na₂O-Gehalt and Feldspatanteil eine Zunahme von Kaolinit feststellbar ist, muß angenommen werden, daß der Kaolinit in erster Linie auf Kosten von Albit gebildet wurde. Weitere kaolinitische Minerale treten nicht auf.Der im Schrifttum häufig erwahnte Bentonit von Geisenheim (Rheingau) stammtnicht von der hier behandelten Lagerstätte.     

Reductive biotransformation of Fe in shale-limestone saprolite containing Fe(III) oxides and Fe(II)/Fe(III) phyllosilicates

A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: (i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and (ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10-15% of the Fe(III)_TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)_TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe²⁺, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)₂, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite, and/or as a Fe(II)-Al coprecipitate. Sediment aggregation and mineral physical and/or chemical factors were demonstrated to play a major role on the nature and location of the biotransformation reaction and its products.     

Der untersilurische Brandschiefer von Kuckers (Estland)

Ohne Zusammenfassung     

Untersuchungen am Tholeyit von Tholey (Saar)

Zusammenfassung Das Originalvorkommen des Tholeyits am Schaumberg bei Tholey (Saar) wurde auf seinen Mineralbestand und seine chemische Zusammensetzung hin untersucht. Dabei wurde festgestellt, daß nach der Intrusion in dem lagergang-förmigen Vorkommen eine gravitative Kristallisationsdifferentiation stattgefunden hat, deren Umfang von doleritischen Olivinbasalten über Tholeyite bis zu Latiten und Plagiapliten reicht. Die einzelnen Differentiationsprodukte wurden gegeneinander abgegrenzt und, gemäß ihrer Lage im System der magmatischen Gesteine, benannt. Dabei wurde der Original-Tholeyit definiert als ein hypabyssischer, leukokrater Vertreter der Mangeritfamilie. In seiner Nähe vorkommende Pigeonit-Tholeyite und intrusive doleritische Olivinbasalte wurden kurz mineralogisch und chemisch beschrieben. Die Unterschiede zu räumlich und systematisch benachbarten Gesteinen des Saar-Nahe-Pfalz-Gebietes, den Palatiniten und Naviten, wurden herausgestellt. Ein Vergleich mit anderen Tholeyiten und Abkömmlingen des tholeyitbasaltischen MagmasKennedys ergab, daß die Bezeichnung tholeyitbasaltisch irreführend ist, und daß in vielen Fällen auch Vertreter der Diorit- und Gabbrofamilie Tholeyit benannt wurden.     

Microbial reduction of iron(III)-rich nontronite and uranium(VI)

To assess the dynamics of microbially mediated U-clay redox reactions, we examined the reduction of iron(III)-rich nontronite NAu-2 and uranium(VI) by Shewanella oneidensis MR-1. Bioreduction experiments were conducted with combinations and varied concentrations of MR-1, nontronite, U(VI) and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify U(VI) sorption to NAu-2, the reduction of U(VI) by chemically-reduced nontronite-Fe(II), and the oxidation of uraninite, U^(IV)O_2(s), by nontronite-Fe(III). When we incubated S. oneidensis MR-1 at lower concentration (0.5 × 10⁸ cell mL⁻¹) with nontronite (5.0 g L⁻¹) and U(VI) (1.0 mM), little U(VI) reduction occurred compared to nontronite-free incubations, despite the production of abundant Fe(II). The addition of AQDS to U(VI)- and nontronite-containing incubations enhanced both U(VI) and nontronite-Fe(III) reduction. While U(VI) was completely reduced by S. oneidensis MR-1 at higher concentration (1.0 × 10⁸ cell mL⁻¹) in the presence of nontronite, increasing concentrations of nontronite led to progressively slower rates of U(VI) reduction. U(VI) enhanced nontronite-Fe(III) reduction and uraninite was oxidized by nontronite-Fe(III), demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to nontronite-Fe(III). The electron-shuttling activity of U can explain the lack or delay of U(VI) reduction observed in the bulk solution. Little U(VI) reduction was observed in incubations that contained chemically-reduced nontronite-Fe(II), suggesting that biologic U(VI) reduction drove U valence cycling in these systems. Under the conditions used in these experiments, we demonstrate that iron-rich smectite may inhibit or delay U(VI) bioreduction.     

Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation

Published experimental data for Al(III) and Fe(III) binding by fulvic and humic acids can be explained approximately by the Humic Ion-Binding Model VI. The model is based on conventional equilibrium reactions involving protons, metal aquo ions and their first hydrolysis products, and binding sites ranging from abundant ones of low affinity, to rare ones of high affinity, common to all metals. The model can also account for laboratory competition data involving Al(III), Fe(III) and trace elements, supporting the assumption of common binding sites. Field speciation data (116 examples) for Al in acid-to-neutral waters can be accounted for, assuming that 60-70 % (depending upon competition by iron, and the chosen fulvic acid : humic acid ratio) of the dissolved organic carbon (DOC) is due to humic substances, the rest being considered inert with respect to ion binding. After adjustment of the model parameter characterizing binding affinity within acceptable limits, and with the assumption of equilibrium with a relatively soluble form of Fe(OH)₃, the model can simulate the results of studies of two freshwater samples, in which concentrations of organically complexed Fe were estimated by kinetic analysis.The model was used to examine the pH dependence of Al and Fe binding by dissolved organic matter (DOM) in freshwaters, by simulating the titration with Ca(OH)₂ of an initially acid solution, in equilibrium with solid-phase Al(OH)₃ and Fe(OH)₃. For the conditions considered, Al, which is present at higher free concentrations than Fe(III), competes significantly for the binding of Fe(III), whereas Fe(III) has little effect on Al binding. The principal form of Al simulated to be bound at low pH is Al³⁺, AlOH²⁺ being dominant at pH >6; the principal bound form of Fe(III) is FeOH²⁺ at all pH values in the range 4-9. Simulations suggest that, in freshwaters, both Al and Fe(III) compete significantly with trace metals (Cu, Zn) for binding by natural organic matter over a wide pH range (4-9). The competition effects are especially strong for a high-affinity trace metal such as Cu, present at low total concentrations (∼1 nM). As a result of these competition effects, high-affinity sites in humic matter may be less important for trace metal binding in the field than they are in laboratory systems involving humic matter that has been treated to remove associated metals.     

Densification of iron(III) sludge in neutralization

Acid mine drainage (AMD), of which iron is a substantial component, is a potential by-product in the mining industry. Conventional neutralization is a common approach to treat AMD, although it creates a major disposal problem due to the generation of voluminous sludge. Sludge recirculation improves solid density by slowing down the rate of neutralization and allowing the growth of precipitates, while existing solids act as seed particles by providing necessary surface area for precipitation. The mechanisms of iron sludge densification are not fully understood, mainly because of the complex nature of iron chemistry, and the variety of amorphous, polymeric oxides that could be formed. In this work, the effects of alkaline reagents, flocculant addition, and dosing sequence, on the precipitation of iron (III) hydroxide and densification of the recycled sludge were investigated. Slowly dissolving lime (Ca(OH)₂) was found to be more effective than caustic (NaOH) in producing sludge with higher solid contents. Polymers addition created stronger aggregates that could withstand shearing without significant size reduction, but the overall sludge density was lower than those produced without flocculant. Conditioning the sludge at pH between 3.5 and 4.5 by adding fresh lime in a specific dosing manner appeared to be conducive to the growth of large agglomerates. The final sludge solid content of ∼15 wt.% was considerably higher than others produced under different conditions. The plate-like structures of precipitates generated with more recycles in this instance, possibly helped ease the release of entrapped water between solids during shearing, thus producing sludge with higher solid density.     

Control of Fe(III) site occupancy on the rate and extent of microbial reduction of Fe(III) in nontronite

A quantitative study was performed to understand how Fe(III) site occupancy controls Fe(III) bioreduction in nontronite by Shewanella putrefaciens CN32. NAu-1 and NAu-2 were nontronites and contained Fe(III) in different structural sites with 16 and 23% total iron (w/w), respectively, with almost all iron as Fe(III). Mössbauer spectroscopy showed that Fe(III) was present in the octahedral site in NAu-1 (with a small amount of goethite), but in both the tetrahedral and the octahedral sites in NAu-2. Mössbauer data further showed that the octahedral Fe(III) in NAu-2 existed in at least two environments- trans (M1) and cis (M2) sites. The microbial Fe(III) reduction in NAu-1 and NAu-2 was studied in batch cultures at a nontronite concentration of 5 mg/mL in bicarbonate buffer with lactate as the electron donor. The unreduced and bioreduced nontronites were characterized by X-ray diffraction (XRD), Mössbauer spectroscopy, and transmission electron microscopy (TEM). In the presence of an electron shuttle, anthraquinone-2,6-disulfonate (AQDS), the extent of bioreduction was 11%-16% for NAu-1 but 28%-32% for NAu-2. The extent of reduction in the absence of AQDS was only 5%-7% for NAu-1 but 14%-18% for NAu-2. The control experiments with heat killed cells and without cells did not show any appreciable reduction (<2%). The extent of reduction in experiments performed with a dialysis membrane to separate cells from clays (without AQDS) was 2%-3% for NAu-1 but 5%-7% for NAu-2, suggesting that cells probably released an electron shuttling compound and/or Fe(III) chelator. The reduction rate was also faster in NAu-2 than that in NAu-1. Mössbauer data of the bioreduced nontronite materials indicated that the Fe(III) reduction in NAu-1 was mostly from the presence of goethite, whereas the reduction in NAu-2 was due to the presence of the tetrahedral and trans-octahedral Fe(III) in the structure. The measured aqueous Fe(II) was negligible. As a result of bioreduction, the average nontronite particle thickness remained nearly the same (from 2.1 to 2.5 nm) for NAu-1, but decreased significantly from 6 to 3.5 nm for NAu-2 with a concomitant change in crystal size distribution. The decrease in crystal size suggests reductive dissolution of nontronite NAu-2, which was supported by aqueous solution chemistry (i.e., aqueous Si). These data suggest that the more extensive Fe(III) bioreduction in NAu-2 was due to the presence of the tetrahedral and the trans-octahedral Fe(III), which was presumed to be more reducible. The biogenic Fe(II) was not associated with biogenic solids or in the aqueous solution. We infer that it may be either adsorbed onto surfaces of nontronite particles/bacteria or in the structure of nontronite. Furthermore, we have demonstrated that natural nontronite clays were capable of supporting cell growth even in medium without added nutrients, possibly due to presence of naturally existing nutrients in the nontronite clays. These results suggest that crystal chemical environment of Fe(III) is an important determinant in controlling the rate and extent of microbial reduction of Fe(III) in nontronite.     

Selenium isotope fractionation during reduction by Fe(II)-Fe(III) hydroxide-sulfate (green rust)

We have determined the extent of Se isotope fractionation induced by reduction of selenate by sulfate interlayered green rust (GR_SO4), a Fe(II)-Fe(III) hydroxide-sulfate. This compound is known to reduce selenate to Se(0), and it is the only naturally relevant abiotic selenate reduction pathway documented to date. Se reduction reactions, when they occur in nature, greatly reduce Se mobility and bioavailability. Se stable isotope analysis shows promise as an indicator of Se reduction, and Se isotope fractionation by various Se reactions must be known in order to refine this tool. We measured the increase in the ⁸⁰Se/⁷⁶Se ratio of dissolved selenate as lighter isotopes were preferentially consumed during reduction by GR_SO4. Six different experiments that used GR_SO4 made by two methods, with varying solution compositions and pH, yielded identical isotopic fractionations. Regression of all the data yielded an instantaneous isotope fractionation of 7.36 ± 0.24‰. Selenate reduction by GR_SO4 induces much greater isotopic fractionation than does bacterial selenate reduction. If selenate reduction by GR_SO4 occurs in nature, it may be identifiable on the basis of its relatively large isotopic fractionation.     

Das Vorkommen von Sapphirin im Peridotitkörper von Finero (Zone von Ivrea,Italienische Westalpen)

Zusammenfassung Im Peridotitkörper von Finero wurde zum ersten Mal in den Alpen Sapphirin im anstellenden Gestein gefunden. Das Mineral tritt gesteinsbildend auf in einer schmalen Übergangszone zwischen Hornblendeperidotit und Hornblende-Pyroxenfels im Innern des Peridotitkörpers. Der Pauschalchemismus dieser Zone zeichnet sich durch niedrigen Kieselsäuregehalt bei gleichzeitig hohen Magnesium und Aluminiumgehalten aus (ariégitischer Chemismus). Begleiter des Sapphirins sind Enstatit und Spinell oder Enstatit und Pyrop, dazu treten paragasitische Hornblende, eisenarmer Diallag und Bytownit. Aus der Untersuchung der Peridotite der Ivreazone folgt, daß der Peridotitkörper von Finero einer intensiven Umkristallisation in hornblendegranulitischer Fazies unter Einfluß einer fluiden, alkalihaltigen Phase unterworfen war. Das Ausgangsmaterial dürften Granatperidotite gewesen sein, der heutige Mineralbestand entspricht der Fazies der Spinell-Hornblendeperidotite. Die Sapphirinparagenese wird in diesem Zusammenhang als Ungleichgewichtsparagenese in einer Zone unvollkommener Umkristallisation gesehen, der Sapphirin selbst wird als Zwischenphase in einem bestimmten Stadium beim Übergang aus dem Mineralbestand der Granatperidotit-Fazies in den Mineralbestand der Spinellperidotit-Fazies gedeutet.

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The occurence of sapphirine in the ultramafic complex of Finero (Zone of Ivrea, Western Italian Alps)

Sapphirine is found as a rock-forming mineral in a small layer between peridotitic and pyroxenitic rocks in the interior of the ultramafic complex of Finero. Chemically, this layer is characterized by low contents of silica combined with very high contents of both, magnesia and alumina. Sapphirine occurs together with enstatite and spinel or enstatite and pyrope, further constituents of the paragenesis are pargasite, aluminous diopside and bytownite. The rocks of the ultramafic complex are considered being the result of a recrystallisation in the hornblendegranulitic facies. In this context, the sapphirine-bearing layer represents a paragenesis of non-equilibrium in a zone of incomplete recrystallisation. Sapphirine is interpreted as an intermediate phase, appearing during the transition from the garnet-peridotite facies into the spinel-peridotite facies.

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Die Untersuchung des Sapphirinvorkommens von Finero ist ein Teil einer größeren Forschungsarbeit des Verfassers über die Ultramafitite der Zone von Ivrea, welche als Teil des Unternehmen Erdmantel durchgeführt worden ist. Der Verfasser dankt der Deutschen Forschungsgemeinschaft für die Förderung seiner Arbeiten im Rahmen dieses Schwerpunktprogrammes.