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

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

Na-rich carbonate inclusions in perovskite and calzirtite from the Guli intrusive Ca-carbonatite,polar Siberia

Carbonate phases, some rich in Na₂O and comparatively rich in SrO and BaO, occur as inclusions in perovskite and calzirtite (Ca₂Zr₅Ti₂O₁₆) in the carbonatite of the Guli complex, Siberia. This is the first record of alkali carbonates, akin to nyerereite [Na₂Ca(CO₃)₂], in plutonic igneous rocks. The inclusion populations suggest that the parental magma of the complex was Ca-rich but developed Na-rich differentiates during the latest stages. This points to the dominant calcic carbonatites of the complex not being derivatives of alkali-rich parental carbonatites. These alkali-rich carbonate inclusions (and rare inclusions of djerfisherite) have been preserved due to the resistance of perovskite and calzirtite to processes of leaching, hydrothermal alteration and weathering.     

An Example of Island-Arc Petrogenesis: Geochemistry and Petrology of the Southern Luzon Arc, Philippines

Volcanism throughout the Luzon arc is associated with eastwardsubduction of the South China Sea floor along the Manila Trench.The southern section of the arc, the focus of this study, extendsfrom the Lingayen-Dingalan fault to the small islands just southof Luzon. Two segments appear to exist along this section ofthe arc the northern Bataan and southern Mindoro segments whichare separated by the Macolod Corridor. The volcanic rocks have typical arc phenocryst mineralogies:olivine, clinopyroxene, plagioclase, and titanomagnetite inthe most mafic rocks and clinopyroxene, plagioclase, orthopyroxene,titanomagnetite, ? amphibole in the more felsic samples. Complexzoning, sieve textures, and decoupling of incompatible traceelements suggest that processes such as assimilation have takenplace. The rocks from the study area range from basalts to rhyolitesand show typical calc-alkaline features. The rocks of the MacolodCorridor and Mindoro segment are particularly enriched in largeion lithophile elements (LILE), light rare earth elements (LREE),and radiogenic Sr compared with the Bataan segment. The datafall within the mantle array on Sr-Nd isotopic diagrams andgrade toward higher Sr and lower Nd isotopic values from northto south. A likely source for the volcanics of this study is either amid-ocean ridge basalt (MORB)-type mantle that undergoes higherdegrees of partial melting than regions involved in MORB generationor a previously depleted source. We suggest that the high fieldstrength element (HFSE) anomalies have been derived throughdifferential element partitioning during fluid transport fromthe subducted lithosphere to the mantle wedge. Continental crustal material seems to play a significant roleparticularly in the Macolod Corridor and the Mindoro segment,based on the high LILE, La/Sm ratios, radiogenic Sr isotopes,and ¹⁸O values. The Macolod Corridor and the Mindoro segmenthave undergone source contamination by crustal material fromthe North Palawan-Mindoro crustal block either during the collisionof this block with the Manila Trench or by subduction of sedimentsrich in this crustal material. A similar component has alsobeen detected in the Bataan segment but in minor amounts. Thetrace element and isotopic differences between the northernand southern sections of the arc are interpreted in terms ofvariable composition (i. e., variable amounts of a crustal componentintroduced from the Palawan-Mindoro crustal terrain) of themetasomatic fluids released into the source.     

Geochemical specialization of the tin-bearing granitoid massifs of NW Bohemia

The geochemistry of Hercynian tin-bearing granitoid massifs of the Krune hory Mts. (Erzgebirge), Slavkovský les Forest (Kaiserwald) and Smriny (eastern Fichtelgebirge) is compared by statistical processing of 270 analyses including a wide spectrum of major and trace elements. Seven different types of granites are distinguished. Out of these, five types represent the successive differentiation of the largest massif of NW Bohemia: the Karlovy Vary (Karlsbad) massif. This comprises strongly differentiated peraluminous granites evolving towards extreme Li-Rb-Cs-F-and Sn-enrichment in the youngest members, which are albite-topaz-zinwaldite lithium granites. The sixth and seventh types are different from the former by their location in the eastern Krune hory and tectonic setting, and they display geochemical features of anorogenic granites: they are metaluminous albite-zinwaldite granites with marked enrichment of Nb, Y, and HREE in addition to Li, Rb, Cs, F and Sn, indicating contamination by sub-crustal material. Sn-W mineralizations, including flat peri-contact greisen bodies, steep greisen veins and tourmalinized phyllites, are all intimately associated with the most strongly differentiated granites — the Li-granite and the Cinovec-granite respectively.     

The effect of bulk rock composition on the stability of amphibole in the upper mantle: Implications for solidus positions and mantle metasomatism

Summary The stability of pargasitic amphibole in the upper mantle is a function of water content and bulk rock composition, and under water-undersaturated conditions, the stability of amphibole controls the solidus position. Experiments in the system Tinaquillo peridotite +0.2% H₂O, a refractory peridotite under water-undersaturated conditions, show that amphibole is stable to 1030°C and 26 kb. In contrast, pargasitic amphibole is stable to 1150°C and 30 kb in Hawaiian pyrolite, a more fertile peridotite composition. This indicates that under water-undersaturated conditions, the most fertile part of a crystallizing mantle diapir with an inhomogeneous composition will solidify first while a more refractory component will contain an alkali-rich melt which will have the ability to metasomatize adjacent regions. The relative stabilities of amphibole in refractory and fertile bulk compositions may result in increasing rather than diminishing chemical contrasts in high temperature lherzolite, i.e. a process of metamorphic differentiation. Ti, Fe, Al and Na metasomatism can therefore be considered a normal occurrence associated with the upward migration and solidification of an H₂O-bearing mantle diapir.

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Der Einfluß der Gesamtgesteins-Zusammensetzung auf die Stabilität von Amphibol im oberen Mantel: Bedeutung für Solidus-Positionen und Mantel-Metasomatose

Zusammenfassung Die Stabilität pargasitischer Amphibole im oberen Mantel ist eine Funktion von Wassergehalt und Gesamtgesteins-Zusammensetzung. Unter wasser-untersättigten Bedingungen, kontrolliert die Stabilität von Amphibol die Solidus-Position. Experimente in dem System Tinaquillo Peridotit +0,2% H₂O, einem refraktären Peridotit unter wasser-untersättigten Bedingungen, zeigen daß Amphibol bis 1030°C und 26 Kb stabil ist. Im Gegensatz dazu ist pargasitische Hornblende in einem Hawaii-Pyrolit, von mehr fertiler Peridotit-Zuammensetzung, bis 1150°C und 30 Kb stabil. Das zeigt, daß bei wasser-untersättigten Bedingungen der am meisten produktive Teil eines kristallisierenden Mantel-Diapirs mit inhomogener Zusammensetzung sich zuerst verfestigen wird, während eine mehr refraktäre Komponente eine alkali-reiche Schmelze enthalten wird, die wiederum die Fähigkeit hat, umliegende Bereiche metasomatisch zu beeinflussen. Die relativen Stabilitäten von Amphibol in refraktären und fertilen Gesamtzusammensetzungen können dazu führen, daß die chemischen Gegensätze in Hochtemperaturlherzoliten eher zunehmen als abnehmen, d. h. ein Prozeß metamorpher Differentiation. Ti, Fe, Al und Na Metasomatose können deshalb als ein verbreiteter Vorgang, der mit der Aufwärtsbewegung und Verfestigung eines H₂O-führenden Mantel-Diapirs assoziiert ist, betrachtet werden.

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An internal variable model for the creep of rocksalt

Summary The creep strain rate of rocksalt, like that of other ductile crystalline materials, can be described by a power law equation of the type ( ) ⁿ , where the active stress is the difference between the total deviatoric applied stress and an internal stress _i . In this paper, the origin and the nature of this internal stress, which develops during inelastic deformation of the material, are discussed. It is shown that this internal stress can serve as an internal (or state) variable in the constitutive model of rocksalt, which reflects the microstructure evolution of the material under the competitive action of hardening and recovery mechanisms.An analysis of experimental data, both our own and those taken from the literature, demonstrates that such a law is able to correctly reproduce rocksalt creep test results in the steady-state domain. The proposed model is in accordance with the macroscopic and microscopic behavior of salt, and with direct measurements of the internal stresses made by others on this material.     

Evolution of nappes in the eastern margin of the Bohemian Massif: a kinematic interpretation

The entire pile of nappes in the eastern margin of the Bohemian massif is characterized by two stages of Variscan nappe emplacement each exhibiting a different kinematic and metamorphic evolution.The older emplacement (D1) probably occurred around 350-340 Ma ago and was synmetamorphic. The nappes show a typical systematic superposition of higher grade metamorphic units over lower grade ones. Thus, the crystalline complexes showing a HT-MP Barrovian imprint (Svratka allochthonous unit and Moldanubicum) were thrust over an intermediate unit affected by MTMP recrystallization (Bíte orthogneiss and its country rock), and at the base of the D1 nappe pile the Inner Phyllite Nappe (Biý Potok Unit) is characterized by LT/LP metamorphism.The second stage of tectonic evolution (D2) is characterized by a thin-skinned northward-oriented nappe emplacement that occurred under LT-LP conditions dated at 320-310 Ma. The whole nappe sequence formed during the first tectonometamorphic period (D1) was transported northward over the autochthonous »Deblín polymetamorphic and granitic complex« of Upper Proterozoic age and its Devonian sedimentary cover with very low metamorphism. During this second tectonic event the Brno granite massif (580 Ma) was only marginally incorporated in the Variscan nappe tectonics which resulted in kilometer-scale cover and basement duplexes. The tectonic evolution of the nappe pile ended with stage D3, represented by large- to medium-scale east-vergent folds with limited displacement.

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Zusammenfassung Der Deckenbau am Ostrand der Böhmischen Masse erfolgte in zwei aufeinanderfolgenden Stadien, die sich sowohl in ihrer Kinematik als auch in ihrer Metamorphoseentwicklung deutlich voneinander unterschieden.Die ältere Phase (D1 ca. 350-340 Ma) ist durch synmetamorphe Überschiebungen charakterisiert. Sie führt zu einer metamorphen Inversion der überschobenen Deckeneinheiten, so daß generell hohe metamorphe Einheiten schwach metamorphe tektonisch überlagern. Der Svratka Komplex und das Moldanubikum als hangendste Decken sind durch MP/HT Paragenesen vom Barrow-Typ gekennzeichnet. Beide Einheiten sind auf den MP/MT-metamorphen Bite-Gneis und seine Rahmengesteine überschoben. Die Bílý potok Einheit als liegende Decke zeigt nur noch eine LP/ LT Regionalmetamorphose.Das jüngere Stadium (D2 ca. 320-310 Ma) ist durch eine Thin-skinned Tektonik mit nordvergentem Deckentransport unter LP/LT Bedingungen charakterisiert. Der gesamte, invers metamorphe D1-Deckenstapel wird dabei nach N über den autochtonen Deblín Komplex bzw. seine devonische Sedimenthülle überschoben.Das Brno Granit Massiv (580 Ma) wird nur randlich in diesen variszischen Deckenbau einbezogen. Die tektonische Entwicklung endet mit einem mittel bis großräumigen E-vergenten Faltenbau (D3 phase).

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Résumé L'empilement des nappes a la bordure orientale du Massif de Bohème est caractérisé par deux stades de mise en place présentant différentes évolutions cinématiques et métamorphiques.La tectonique majeure de mise en place des nappes crustales intervient lors d'un métamorphisme de type barrowien, calé autour de 350-340 Ma. L'empilement qui en résulte montre une superposition systématique d'unités à fort degré de métamorphisme sur des unités moins métamorphiques. Ainsi les complexes cristallins, montrant des reliques de métamorphisme de haute à moyenne pression-haute température (unités cristallines de Svratka et du Moldanubien), chevauchent une unité intermédiaire affectée par un métamorphisme de moyenne à basse pression-moyenne température (l'orthogneiss de Bíte et son encaissant). A la base de cette pile édifiée durant la tectonique D1, l'unité des phyllites internes (unité de Bílý potok) est caractérisée par un métamorphisme de basse témperature-basse pression.Le second stade D2 de l'évolution tectonique est caractérisé par une tectonique pelliculaire à vergence nord datée à 320-310 Ma. L'empilement résultant de D1 est ainsi transporté vers le nord, au dessus du complexe autochtone d'âge protérozoïque supérieur (groupe de Deblín) et sa couverture sédimentaire dévonienne très faiblement métamorphisée.Le massif granitique de Brno (580 Ma) n'est que marginalement incorporé à cette tectonique de nappe varisque. Ceci se traduit par des duplex socle-couverture d'échelle plurikilométrique. L'évolution tectonique s'achève lors d'une troisième phase, marquée par de grands plis à vergence est. Le déplacement associé est alors d'amplitude limitée.

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Geochemistry of Gneiss-Granulite transformation in the “incipient charnockite” zones of southern India

Summary Upper amphibolite facies gneisses in the southern Indian Shield show local transformation into veins, clots and patches of orthopyroxene-bearing dry granulites (incipient charnockites). Depending upon the protolith composition, these desiccated zones are classified into ortho- and para-charnockites and have developed within rocks of distinct mineralogy and chemistry at different time intervals through the structurally-controlled influx of carbon dioxide-rich fluids. Our geochemical investigations at five critical quarry sections indicate that the incipient charnockites have undepleted chemistry and very low K/Rb values. In the paracharnockite localities, where granulite formation is characterized by consumption of garnet, biotite and quartz to produce orthopyroxene, loss of Rb and Ba and enrichment of Ti are observed. In contrast, the orthocharnockite localities show marked LILE enrichment with gain of K, Rb and Ba and loss of CaO, suggesting extensive replacement of plagioclase in the gneisses by K-feldspar in the charnockite through K-Na-Ca exchange reactions with influxing carbonic fluids. The marked depletion in Fe, Mg, Ti and P in these rocks correlates with progressive dissolution of hornblende, biotite, magnetite and accessory apatite. Our study indicates that gneiss to granulite transformation, even if on a local scale, is not an isochemical phenomenon, but attended by distinct element mobilities, although they are contrastingly different from the geochemical trends in some regional high grade terrains.

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Geochemie von Gneiss-Granulit-Übergängen in den Incipient Charnockite Zonen von Süd-Indien

Zusammenfassung Gneise der oberen Amphibolit-Fazies im Südteil des Indischen Schildes zeigen lokal Umwandlungen in Adern, and unregelmäßigen Bereichen von orthopyroxen-führenden trockenen Granuliten (Incipient Charnockites). In Abhängigkeit von der Zusammensetzung des Ausgangsgesteins werden diese Zonen in Ortho- und Paracharnockite eingeteilt. Sie entwickelten sich in Gesteinen von charakteristischer mineralogischer und chemischer Zusammensetzung zu verschiedenen Zeit-Intervallen durch die tektonisch kontrollierte Zufuhr von kohlendioxid-reichen Fluiden. Unsere geochemischen Untersuchungen an fünf strategisch ausgewählten Steinbruchen zeigen, daß die Incipient Charnockite eine nicht verarmte chemische Zusammensetzung und sehr niedrige K/Rb Werte haben. In den Paracharnockit-Lokalitäten, wo Granulitbildung charakterisiert wird durch das Verschwinden von Granat, Biotit und Quartz, aus denen Orthopyroxene gebildet werden, ist Verlust von Rb und Ba und Anreicherung an Ti zu beobachten. Im Gegensatz dazu zeigen die Orthocharnockite eindeutige LILE Anreicherung mit Zunahme von K, Rb, und Ba und Verlust von Ca0. Dies weist auf extensiven Ersatz von Plagioklas in den Gneisen durch K-Feldspat in den Charnockiten durch K-Na-Ca Austausch-Reaktionen mit zugeführten C0₂-Fluiden hin. Die deutliche Verarmung an Fe, Mg, Ti und P in diesen Gesteinen wird mit zunehmender Auflösung von Hornblende, Biotit, Magnetit und akzessorischem Apatit erKlärt. Unsere Untersuchungen zeigen, daß die Gneis-Granulit Transformation auch im lokalen Maßstab nicht ein isochemisches Phänomen ist, sondern durch charakteristische Elementtransporte charakterisiert wird. Diese unterscheiden sich jedoch deutlich von den geochemischen Trends, die in einigen regional-metamorphen high grade terrains zu beobachten sind.[/p]

     

New compositional and optical data for antimonian and bismuthian varieties of hemusite from Japan

Summary New compositional and optical data are reported for antimonian and antimonianbismuthian varieties of hemusite from epithermal Au-Ag-Cu deposits in Japan. The empirical formula for the antimonian variety, from the Iriki mine is: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00(S_7.85Se_0.15)_8.00, and that of the Sb-Bi variety from the Kawazu mine is: (Cu_5.84Fe_0.14Ag_0.01)_5.99Mo_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07(S_7.80Se_0.12)_7.92. The theoretical formula of hemusite is Cu⁺ ₄Cu²⁺ ₂MO⁴⁺Sn⁴⁺S₈, whilst the most probable formula of the Iriki hemusite is Cu⁺ _4.5CU²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, with Sb⁵⁺ substituting for Sn⁴⁺ and forming (SbS₄)^3– tetrahedra as might be expected, given that the metal to sulphur ratio is 1, and given the sphalerite-like structure of the mineral. However Bi³⁺ cannot be so accommodated, resulting in a deficiency in (S + Se) for Kawazu hemusite. Reflectance spectra for both are compared with those of the tungsten analogue (compositional) of hemusite, kiddcreekite. The relationship between hemusitesensu stricto and these newly reported varieties is discussed in terms of simple and coupled chemical substitutions, and inferences are drawn on the valency of Sb, Bi, Mo and Cu in the hemusite structure.

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Neue chemische und optische Daten für antimon- und bismuthführende Varietäten von Hemusit aus Japan

Zusammenfassung Neue chemische und optische Daten für antimon- und bismuthführende Hemusite auf epithermalen Au-Ag-Cu Lagerstätten in Japan werden vorgelegt. Die empirische Formel für die antimon-führende Varietät aus der Iriki-Mine ist: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00 (S_7.85Se_0.15)_8.00, und die der Sb-Bi Varietät aus der Kawazu Mine ist: (Cu_5.84Fe_0.14Ag_0.01)_5.99M0_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07 (S_7.80Se_0.12)_7.92. Die theoretische Formel von Hemusit ist Cu⁺ ₄Cu²⁺ ₂Mo⁴⁺Sn⁴⁺S₈, während die wahrscheinlichere Formel für den Hemusit von Iriki Cu⁺ ₄Cu²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, mit Sb⁵⁺ an der Stelle von Sn⁴⁺, das(SbS₄)^3– Tetraeder bildet, wie zu erwarten ist, unter der Voraussetzung, da das Metall zu Schwefelverhältnis 1 und die Struktur sphaleritähnlich ist. Bi³⁺ kann jedoch nicht in dieser Weise untergebracht werden, und das führt zu einem Mangel an (S + Se) für den Hemusit von Kawazu. Die Reflektions-Spektren beider Minerale werden mit denen des Wolfram-Equivalents von Hemusit (Kiddcreekit) verglichen. Die Beziehung zwischen Hemusitsensu stricto und diesen jetzt beschriebenen Varietäten wird auf der Basis einfacher und gekoppelter chemischer Substitution diskutiert. Auf dieser Basis werden Schlüsse auf die Valenz von Sb, Bi Mo und Cu in der Hemusit-Struktur gezogen.