Sedimentary provenance of Mid-Devonian clastic sediments in the Teplá-Barrandian Unit (Bohemian Massif): U–Pb and Pb–Pb geochronology of detrital zircons by laser ablation ICP-MS

Summary The provenance of the Mid-Devonian clastic sediments in the Teplá-Barrandian Unit (TBU) of the Bohemian Massif was investigated by laser ablation ICP-MS U–Pb zircon dating, bulk sediment geochemistry and mineralogical study of the heavy mineral fraction. In contrast to the island arc provenance of the TBU Neoproterozoic sediments, the Early Palaeozoic sediments contain significant amounts of differentiated crustal material. The detrital zircon populations in the Barrandian Mid-Devonian siltstones and sandstones show ages ranging from Archaean (3.0Ga) to Early Palaeozoic (0.39Ga). Major age maxima are at 2.6Ga, 2.0–2.25Ga, 0.62 and 0.51Ga. The youngest identified zircons so far correspond to Lower and Mid-Devonian ages. The extensive mechanical abrasion of zircons having Archaean (3.0, 2.8 and 2.6Ga) to Paleoproterozoic ages (2.25–2.0Ga) suggest their provenance from recycled old sedimentary sequences. The relatively large number of zircons with ages between 2.0 and 3.0Ga may indicate the presence of relicts of the Archaean/Paleoproterozoic crust in the source areas of the studied Mid-Devonian sediments. The absence of detrital zircon ages between 0.9 and 1.2Ga and the presence of zircon ages of 2.0–2.25 and 0.5–0.8Ga correspond to the zircon age pattern from the Gondwana-related North African, rather than Gondwana-related South American and Baltic terranes. The material was entering the basin predominantly from the west and consisted primarily of detrital material of Cambrian granitoids and recycled material of Neoproterozoic meta-sedimentary sequences.     

Entwurf einer Mikrogefüge-Einteilung von Marschböden

Zusammenfassung Die üblichen Bodengefügeeinteilungen nach dem Grad der Aggregatbildung waren für die Anwendung an Marschböden unzureichend. Es wird ein Entwurf einer Mikrogefüge-Einteilung besprochen, die auf dem Gehalt an Matrix (Kornanteil < 6. geschätzt) wie auf ihrem Ausrichtungsgrad basiert. Der visuell beurteilte Ausrichtungsgrad der Matrix wird als sehr schwach, schwach, mäßig, stark und sehr stark eingestuft, der geschätzte Matrixgehalt in hoch ( > 40%), mittel (23–40%), gering (5–23%), und sehr gering (0–5%) unterteilt.     

Evaluation of biotite-garnet geothermometers: application to the English River subprovince,Ontario

In recent years, there have been numerous calibrations of the biotite-garnet Fe-Mg exchange geothermometer. The Eastern Lac Seul region of the English River subprovince, Ontario, provides an excellent field area in which to compare these calibrations.Trend surface analysis using the temperatures obtained from garnet cores and matrix biotites-showed almost identical trends in the eastern Lac Seul region regardless of the calibration used. The absolute temperatures and the precision of each calibration do, however, show large variation. Geothermometers based solely on lnK_D were found to give more precise results than the calibrations that attempt to incorporate non-Fe-Mg components. The Perchuk and Lavrent'eva (1983) thermometer yields the most precise and accurate results. If a sufficient number of samples are collected over a region, it can be used to estimate metamorphic temperature trends to ±30° C. Metamorphism and migmatization of the English River subprovince occurred during the Kenoran orogeny, 2.68 b.y. ago. Our results show that a thermal anticline has been preserved, with temperatures of 600° C at the north and south contacts with Uchi and Wabigoon Greenstone belts, increasing to 725 °C at the center of the subprovince. A garnet-cordierite in isograd occurs at 650° C and an orthopyroxene in isogradat 700° C.     

Petrology of ultramafic nodules from West Kettle River,near Kelowna,Southern British Columbia

A basanitoid flow of Miocene age, exposed near the West Kettle River, 25 km southeast of Kelowna, British Columbia, contains abundant ultramafic and mafic nodules. The subangular nodules are 1–20 cm across and typically show granular textures. A study of 250 nodules indicates that spinel lherzolite (60%) is the dominant type with subordinate olivine websterite (10%), websterite (7%), clinopyroxenite (4%), wehrlite (4%), pyroxene gabbro (4%), dunite (2%), harzburgite (1%) and granitic rocks (8%). Ultramafic nodules are of two types. Most of the wehrlites and clinopyroxenites belong to the black pyroxene (aluminous clinopyroxene) series, whereas the other clinopyroxene-bearing nodules belong to the green pyroxene (chromian diopside) series. Some spinel lherzolite nodules have distinctive pyroxene- and olivine-rich bands. Microprobe analyses of the constituent minerals of more than thirty nodules from the green pyroxene series indicate that grain to grain variations within individual nodules are small even when banding is present. Olivine, orthopyroxene, clinopyroxene and spinel in spinel lherzolite have average compositions of Fo₉₀, En₉₀, Wo₄₇Fs₅En₄₈, Cr/(Cr+ Al+Fe³)=0.1 and Mg/(Mg+Fe²⁺)=0.8. Equilibration temperatures, which were calculated using the two pyroxene geothermometer of Wells (1977), range between 920–980° C. Based on published phase stability experiments, pressures of equilibration are between 10–18 kbar. In summary, the upper mantle beneath southern British Columbia is dominated by spinel lherzolite but contains some banding on a scale of cm to meters. The temperature in the upper mantle is 950° C at a depth of 30–60 km.On leave from the Geological Institute, University of Tokyo, Japan     

Origin and differentiation of picritic arc magmas,Ambae (Aoba), Vanuatu

Key aspects of magma generation and magma evolution in subduction zones are addressed in a study of Ambae (Aoba) volcano, Vanuatu. Two major lava suites (a low-Ti suite and high-Ti suite) are recognised on the basis of phenocryst mineralogy, geochemistry, and stratigraphy. Phenocryst assemblages in the more primitive low-Ti suite are dominated by magnesian olivine (mg 80 to 93.4) and clinopyroxene (mg 80 to 92), and include accessory Cr-rich spinel (cr 50 to 84). Calcic plagioclase and titanomagnetite are important additional phenocryst phases in the high-Ti suite lavas and the most evolved low-Ti suite lavas. The low-Ti suite lavas span a continuous compositional range, from picritic (up to 20 wt% MgO) to high-alumina basalts (<5 wt% MgO), and are consistent with differentiation involving observed phenocrysts. Melt compositions (aphyric lavas and groundmasses) in the low-Ti suite form a liquid-line of descent which corresponds with the petrographically-determined order of crystallisation: olivine + Cr-spinel, followed by clinopyroxene + olivine + titanomagnetite, and then plagioclase + clinopyroxene + olivine + titanomagnetite. A primary melt for the low-Ti suite has been estimated by correcting the most magnesian melt composition (an aphyric lava with 10.5 wt% MgO) for crystal fractionation, at the oxidising conditions determined from olivine-spinel pairs (fo₂ FMQ + 2.5 log units), until in equilibrium with the most magnesian olivine phenocrysts. The resultant composition has 15 wt% MgO and an mg ^Fe2 value of 81. It requires deep (3 GPa) melting of the peridotitic mantle wedge at a potential temperature consistent with current estimates for the convecting upper mantle (T _p 1300°C). At least three geochemically-distinct source components are necessary to account for geochemical differences between, and geochemical heterogeneity within, the major lava suites. Two components, one LILE-rich and the other LILE- and LREE-rich, may both derive from the subducting ocean crust, possibly as an aqueous fluid and a silicate melt respeetively. A third component is attributed to either differnt degrees of melting, or extents of incompatible-element depletion, of the peridotitic mantle wedge.     

Some thoughts on the pre-Alpine metamorphic history of the austridic basement of the Eastern Alps

Summary In several places of the old crystalline basement of the Eastern Alps a classification of the pre-Alpine metamorphic effects into an older, high-to intermediate-pressure metamorphism (eclogites, kyanite) and a younger, lower-pressure one (and±ky±cord) is recognizable. Some local geological situations allow a sharp chronological distinction to be made between these two events; and the available radiometric age values demonstrate the Caledonian age (500 m.y.) of the older metamorphism and the Hercynian age (320 m.y.) of the younger one. Elements exist showing that the Caledonian metamorphism, belongs to a complex cycle of geological processes which took place substantially during the Ordivician age (?) and has all the ingredients of the orogenic cycles. This evolutional picture represents a possible model for the whole of the Eastern Alps.

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Überlegungen zur Entwicklung der voralpidischen Metamorphose im Ostalpin

Zusammenfassung An mehreren Stellen im altkristallinen Grundebirge der Ostalpen ist eine Gliederung der voralpidischen metamorphen Ereignisse in eine ältere Metamorphose, die einer hoch-bis mitteldruckbetonten Faziesserie (Eklogite, Disthen) angehört und eine jüngere weniger druckbetonte Metamorphose (Andalusit±Disthen±Cordierit) erkennbar. Einzelne lokale geologische Situationen erlauben eine scharfe chronologische Trennung dieser zwei Ereignisse; das Caledonische Alter ( 500m.y.) der älteren und das Hercynische Alter ( 320 m.y.) der jüngeren Metamorphose wird durch radiometrische Altersdaten demonstriert. Es gibt Hinweise, daß die Caledonische Metamorphose zu einem komplexen geologischen Ereignis mit allen Kennzeichen eines orogenen Zyklusses gehört, das im wesentlichen während des Ordoviziums stattgefunden hat. Diese genetischen Vorstellungen scheinen als mögliches Modell für die gesamten Ostalpen annehmbar.

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With 3 Figures     

Petrogenesis of voluminous mid-Tertiary ignimbrites of the Sierra Madre Occidental,Chihuahua, Mexico

The mid-Tertiary ignimbrites of the Sierra Madre Occidental of western Mexico constitute the largest continuous rhyolitic province in the world. The rhyolites appear to represent part of a continental magmatic arc that was emplaced when an eastward-dipping subduction zone was located beneath western Mexico.In the Batopilas region of the northern Sierra Madre Occidental the mid-Tertiary Upper Volcanic sequence is composed predominantly of rhyolitic ignimbrites, but volumetrically minor lava flows as mafic as basaltic andesite are also present. The basaltic andesite to rhyolite series is calc-alkalic and contains 1% K₂O at 60% SiO₂. Trace element abundances of a typical ignimbrite with 73% SiO₂ are Sr 225 ppm, Rb 130 ppm, Y 32 ppm, Th 12 ppm, Zr 200 ppm, and Nb 15 ppm. The entire series plots as coherent and continuous trends on variation diagrams involving major and trace elements, and the trends are distinct from those of geographicallyassociated rocks of other suites. We interpret these and other geochemical variations to indicate that the rocks are comagmatic. Mineral chemistry, Sr isotopic data, and REE modelling support this interpretation.Least squares calculations show that the major element variations are consistent with formation of the basaltic andesite to rhyolite series by crystal fractionation of observed phenocryst phases in approximate modal proportions. In addition, calculations modelling the behavior of Sr with the incompatible trace element Th favor a fractional crystallization origin over a crustal anatexis origin for the rock series. The fractionating minerals included plagioclase (> 50%), and lesser amounts of Fe-Ti oxides, pyroxenes, and/or hornblende. The voluminous ignimbrites represent no more than 20% of the original mass of a mantle-derived mafic parental magma.     

Application of mineral thermometers and barometers to granitoid igneous rocks: the Etive Complex, W Scotland

Summary The Etive complex, one of the Caledonian Newer Granites of Scotland, is a ring complex of Devonian age, ranging in composition from pyroxene-diorite to leucogranite. Six samples, representing the major rock units in the southern parts of the Etive complex were chosen for mineral chemical studies and for estimation of the pressure and temperature conditions of magmatic crystallisation. Application of Al- in-hornblende barometry and crossite contents of amphiboles indicates a pressure <3kbar for the intrusion, in good agreement with published independent pressure estimates of 2kbar from mineral equilibria in metasedimentary hornfelses in the Etive thermal aureole. Thermometry, using ternary and binary feldspar systems, yields low temperatures, which probably reflect late-stage, post-magmatic re-equilibration of these minerals. Several geothermometers have been applied to the Quarry Diorite, the outermost intrusion of the complex. The highest temperature for the rocks comes from orthopyroxene–clinopyroxene solvus thermometry, and is 1000°C; this is interpreted to reflect the initial crystallisation of the diorite magma immediately after its emplacement. The maximum temperature from hornblende-plagioclase thermometer is 816°C, which probably reflects late-stage crystallisation of the magma.     

Late Hercynian U-vein mineralization in the Alps: fluid inclusion and C,O, H isotopic evidence for mixing between two externally derived fluids

Late Hercynian U-bearing carbonate veins within the metamorphic complex of La Lauzière are characterized by two parageneses. The first is dominated by dolomite or ankerite and the second by calcite and pitchblende. Fluids trapped in the dolomites and ankerites at 350–400° C are saline waters (20 to 15 wt % eq. NaCl) with D –34 to –49. In the calcite they are less saline (17 to 8 wt % eq. NaCl) and trapped at 300–350° C with D –50 to –65. All fluids contain trace N₂, CO₂ and probably CH₄. The carbonates have ¹³C –8 to –14. and derived their carbon from organic matter. Evolution of the physico-chemical conditions from dolomite (ankerite) to calcite deposition was progressive.H and O-isotope studies indicate the involvement of two externally derived fluids during vein development. A D-rich ( –35) low fO₂, saline fluid is interpreted to have come from underlying sediments and entered the hotter overlying metamorphic slab and mixed with more oxidizing and less saline U bearing meteoric waters during regional uplift. This evidence for a sedimentary formation water source for the deep fluid implies that the metamorphic complex overthrusted sedimentary formations during the Late-Hercynian.     

Use of the lattice parameter b 0 of dioctahedral illite/muscovite for the characterization of P/T gradients of incipient metamorphism

The P/T gradient or baric type of low-grade metamorphic terranes can be characterized on the basis of cumulative frequency curves of the lattice parameter b ₀ of dioctahedral micas (Sassi and Scolari 1974), which essentially reflects celadonite content and increases with pressure. The method is here applied to illite/muscovite of sub-greenschist (incipient metamorphism) and low-greenschist facies terranes from the marginal zones of the Swedish Caledonides, Swiss Alps and Venezuelan Andes, where the grade of metamorphism was determined on the basis of illite crystallinity.Complications in the determinations of b ₀ arising from (a) shifts in the spacing of the apparent 060 diffraction peaks of the illites due to the presence of inter-stratified expandable layers, and (b) persistence of more crystalline clastic micas are pointed out.In contrast to the earlier-reported decrease of b ₀ with progressive metamorphism at higher grades, b ₀ tends to increase with grade during incipient metamorphism: it is markedly lower in the diagenetic and low-grade anchimetamorphic grades in the Cambro-Silurian of the Caledonides of Jämtland, western Sweden (zone A), and the Lower Tertiary of the Helvetic zone of the Swiss Alps, than in the higher grade anchizone and epizone of the former terrane.Mean b ₀ values for the intermediate and highest (epizone) grades of the Swedish Caledonides are respectively 9.030 and 9.037 Å compared to the mean value of 9.035 Å for the medium-high pressure, Barrovian-type, terrane of Otago, N.Z. Mean b ₀ of 9.005 Å for the mainly epizonal slates of the Venezuelan Andes lies between those for the low-pressure terranes of Bosost ( 8.992 Å), and the low-medium pressure terrane of northern New Hampshire (9.010 Å). These baric estimates agree well with those for the metamorphic facies series at higher grade produced by the same events.Cumulative b ₀ curves are concluded to be useful for the characterization of P/T gradients of incipient metamorphism, particularly in the higher grade part of the anchizone and the epizone.     

Calibration of Al/Si order variations in anorthite

New single crystal diffraction data for natural and heat-treated anorthite crystals (Angel et al. 1990) allow the determination of their states of Al/Si order in terms of a macroscopic order parameter,Q _OD , for the transition. Numerical values ofQ _OD obtained from estimates of site occupancies are shown to vary with the scalar spontaneous strain, _s , as _s Q _OD ² , and with the ratio of the sums of typeb (superlattice) reflections and typea (sublattice) reflections asI _b/I _a Q _OD ² . An empirical calibration for pure anorthite is obtained giving varies between 0.92 and 0.87 in samples equilibrated at T1300° C, but then falls off relatively rapidly with increasing temperature, reaching 0.7 near the melting point ( 1557° C). The observed temperature dependence does not conform to the predictions of the simplest single order parameter models; coupling ofQ _OD withQ of the transition is suspeeted.     

Formation of Mud-Volcanic Fluids in Taman (Russia) and Kakhetia (Georgia): Evidence from Boron Isotopes

Temperatures of the formation of mud-volcanic waters are determined based on concentrations of some temperature-dependent components (Na–Li, Mg–Li). Estimates obtained for the Taman and Kakhetia regions are similar and range from 45 to 170°, which correspond to depths of 1–4.5 km. The calculated temperatures correlate with the chemical (Li, Rb, Cs, Sr, Ba, B, I, and HCO₃) composition of water and ¹³ (₂) and ¹³ (CH₄) values in spontaneous gases. The isotope values indicate that mechanisms of the formation of ¹³-rich gases, i.e., gases with high ¹³ values (up to +16.0 in ₂ and –23.4 in CH₄) in mud-volcanic systems of Taman and Kakhetia are governed by fluid-generation temperatures rather than the supply of abyssal gases. The ¹¹ value was determined for the first time in mud-volcanic products of the Caucasus region. This value ranges from +22.5 to +39.4 in the volcanic water of Georgia, from –1.2 to +7.4 in the clayey pulp of Georgia, and from –7.6 to +13.2 in the clayey pulp of Taman. It is shown that the ¹¹ value in clay correlates with the fluid-generation temperature and ¹¹ correlates with ¹³ in carbon-bearing gases. These correlations probably testify to the formation of different phases of mud-volcanic emanations in a single geochemical system and suggest the crucial role of temperature in the development of isotope-geochemical features.     

Transformation kinetics of polycrystalline aragonite to calcite: new experimental data,modelling, and implications

Experimental data are used to model the transformation rate of polycrystalline aragonite (grain diameter 80 m) to calcite. Optimized values for nucleation and growth rates were obtained by numerically fitting the overall transformation rates from 280° to 380°C and 0.10 MPa to an expression for a grain-boundary-nucleated and interface-controlled transformation. The nucleation rate is 4–5 orders of magnitude faster than for calcite nucleated within aragonite grains, and the growing in rate is slower below 300°C than for calcite growing in aragonite single crystals. The activation enthalpy for growth in polycrystalline aggregate is 247kJ/mol compared to 163 kJ/mol for growth in single crystals. Permanent deformation of the phases limits the elastic strain energy due to the 7% volume change and reduces the coherency of the calcite/aragonite interace. Theoretical expressions are used to extrapolate the data for nucleation and growth to other temperatures, and data from 0.10 to 400 MPa are used to evaluate the effect of pressure on the grain-boundary nucleation rate. Because of permanent deformation of the phases, the effective strain energy for nucleation is 0.55 kJ/mol, which is less than a quarter of the value for purely elastic deformation. These data are used to predict the percent transformation for various P-T-t paths; without heating during uplift partial preservation of aragonite in dry blueschist facies rocks can occur if the calcite stability field is entered at 235° C, and the kinetic data are also consistent with published P-T-t paths which include heating during uplift. The predicted percent transformation is relatively insensitive to variations in the initial grain size of the aragonite, but strongly dependent on the effective strain energy.     

Changes in stable isotope ratios of metapelites and marbles during regional metamorphism,Mount Lofty Ranges,South Australia: implications for crustal scale fluid flow

The Mount Lofty Ranges comprises interlayered marbles, metapsammites, and metapelites that underwent regional metamorphism during the Delamarian Orogeny at 470–515 Ma. Peak metamorphic conditions increased from lowermost biotite grade (350–400°C) to migmatite grade (700°C) over 50–55 km parallel to the lithological strike of the rocks. With increasing metamorphic grade, ¹⁸O values of normal metapelites decrease from 14–16 to as low as 9.0, while ¹⁸O values of calcite in normal marbles decrease from 22–24 to as low as 13.2 These isotopic changes are far greater than can be accounted for by devolatilisation, implying widespread fluid-rock interaction. Contact metamorphism appears not to have affected the terrain, suggesting that fluid flow occurred during regional metamorphism. Down-temperature fluid flow from synmetamorphic granite plutons (¹⁸O=8.4–8.6) that occur at the highest metamorphic grades is unlikely to explain the resetting of oxygen isotopes because: (a) there is a paucity of skarns at granite-metasediment contacts; (b) the marbles generally do not contain low-XCO₂ mineral assemblages; (c) there is insufficient granite to provide the required volumes of water; (d) the marbles and metapelites retain a several permil difference in ¹⁸O values, even at high metamorphic grades. The oxygen isotope resetting may be accounted for by along-strike up-temperature fluid flow during regional metamorphism with time-integrated fluid fluxes of up to 5x10⁹ moles/m² (10⁵ m³/m²). If fluid flow occurred over 10⁵–10⁶ years, estimated intrinsic permeabilities are 10^-20 to 10^-16m². Variations in ¹⁸O at individual outcrops suggest that time-integrated fluid fluxes and intrinsic permeabilities may locally have varied by at least an order of magnitude. A general increase in XCO₂ values of marble assemblages with metamorphic grade is also consistent with the up-temperature fluid-flow model. Fluids in the metapelites may have been derived from these rocks by devolatilisation at low metamorphic grades; however, fluids in the marbles were probably derived in part from the surrounding siliceous rocks. The marble-metapelite boundaries preserve steep gradients in both ¹⁸O and XCO₂ values, suggesting that across-strike fluid fluxes were much lower than those parallel to strike. Up-temperature fluid flow may also have formed orthoamphibole rocks and caused melting of the metapelites at high grades.This paper is a contribution to IGCP Project 304 Lower Crustal Processes     

Pyritization of Iron in Sediments from the Continental Slope of the Northern Gulf of Mexico

In sediments from the continental slope of the Northern Gulf of Mexico, generally,the degree of iron pyritization (DOP) is low (<0.1) and dissolved sulfide is belowdetection limits (5 M), whereas dissolved Fe is typically about 50 to100 M. Therefore, the dissolution of kinetically reactive iron minerals generallydominates over the rate of sulfide production in sediments throughout this region.However, in sediments where hydrocarbons have been added via seepage from thesubsurface, dissolved-Fe is undetectable, DOP can approach 1, and high concentrationsof dissolved sulfide (up to 11 mM) are commonly present. Even though thesesediments have high total reduced sulfide (TRS) concentrations (typically 150 to370 mol gdw^-1), their average C/S ratio is about 4 times that of normal marine sediments reflecting the major input of hydrocarbons. DOP is significantly (20%) higher when calculated using reactive-Fe extracted by citrate dithionite than by cold 1N HCl. This difference is primarily due to the greater extraction efficiency of the cold HCl method for silicate-Fe. TRS tends to rise to a maximum, and remains close to constant even at high (mM) dissolved sulfide concentrations. These TRS concentrations, therefore, represent the size of the ``kinetically' reactive-Fe pool during early diagenesis.     

Electrical conductivity,thermopower and <Superscript>57</Superscript>Fe Mössbauer spectroscopy of aegirine (NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)

DC and AC electrical conductivities were measured on samples of two different crystals of the mineral aegirine (NaFeSi₂O₆) parallel () and perpendicular () to the [001] direction of the clinopyroxene structure between 200 and 600 K. Impedance spectroscopy was applied (20 Hz–1 MHz) and the bulk DC conductivity _DC was determined by extrapolating AC data to zero frequency. In both directions, the log _DC – 1/T curves bend slightly. In the high- and low-temperature limits, differential activation energies were derived for measurements [001] of E_A 0.45 and 0.35 eV, respectively, and the numbers [001] are very similar. The value of _DC [001] with _DC(300 K) 2.0 × 10^{–6 –1}cm^–1 is by a factor of 2–10 above that measured [001], depending on temperature, which means anisotropic charge transport. Below 350 K, the AC conductivity () (/2=frequency) is enhanced relative to _DC for both directions with an increasing difference for rising frequencies on lowering the temperature. An approximate power law for () is noted at higher frequencies and low temperatures with () ^s, which is frequently observed on amorphous and disordered semiconductors. Scaling of () data is possible with reference to _DC, which results in a quasi-universal curve for different temperatures. An attempt was made to discuss DC and AC results in the light of theoretical models of hopping charge transport and of a possible Fe²⁺ Fe³⁺ electron hopping mechanism. The thermopower (Seebeck effect) in the temperature range 360 K < T <770 K is negative in both directions. There is a linear – 1/T relationship above 400 K with activation energy E 0.030 eV [001] and 0.070 eV [001]. ⁵⁷Fe Mössbauer spectroscopy was applied to detect Fe²⁺ in addition to the dominating concentration of Fe³⁺.     

Molybdenum mineralization at Alpeiner Scharte, Tyrol (Austria): results of in-situ U–Pb zircon and Re–Os molybdenite dating

Summary Vein-type Mo mineralization at Alpeiner Scharte occurs in the Penninic units of the western Tauern Window in the Eastern Alps. Three types of previously undated metagranitoids (central gneisses) are distinguished and preserve intrusive contacts with pre-Alpine metamorphosed supracrustal rocks. The granitic protoliths represent fractionated late to post-orogenic, calc-alkaline, I-type magmas with minor S-type components. The Mo veins are restricted to a biotite and alkali feldspar-rich gneiss variety and occur in E–W trending normally sub-vertical quartz veins with adjacent thin discontinuous garnet- and biotite-rich zones; the latter are interpreted as metamorphosed vein selvages. Prior to this work the age of the intrusive host rocks as well as the age of Mo mineralization were unknown.The pre-Alpine Mo deposit and its host rocks were affected by four Alpine deformation events (D₁–D₄) and Young-Alpine regional metamorphism. The P-T conditions of this metamorphic event were 550°C and 8kbar and are in agreement with results of previous regional studies.Zircon grains from two orthogneiss samples were dated with the U–Pb method using ion probe techniques. Zircons from the metagranitic host rock of the Mo-veins yielded an emplacement age of 306.8±3.8Ma (2). A second sample from a more leucocratic gneiss lacking Mo-veins gave 305.0±6.6Ma (2). Re–Os dating of molybdenite from the veins yielded an age of 306.8±3.1Ma, in good agreement with the U–Pb zircon ages.This study confirms one of two alternative hypotheses discussed in the literature. It supports the idea that vein-type Mo-mineralization in the western Tauern Window is genetically related to Late Carboniferous (Westphalian) granitoids that were emplaced during the late to post-orogenic stage of the Variscan orogeny. They do not constitute an Alpine metamorphic-hydrothermal deposit. This study further confirms the strength of the Re–Os molybdenite chronometer, in that it was unaffected by subsequent Alpine medium grade regional metamorphism.Present address: Kremstalstraße 32, A-4501 Neuhofen an der Krems, Austria     

Geochemistry and argon thermochronology of the Variscan Sila Batholith,southern Italy: source rocks and magma evolution

The Sila batholith is the largest granitic massif in the Calabria-Peloritan Arc of southern Italy, consisting of syn to post-tectonic, calc-alkaline and metaluminous tonalite to granodiorite, and post-tectonic, peraluminous and strongly peraluminous, two-mica±cordierite±Al silicate granodiorite to leucomonzogranite. Mineral ⁴⁰Ar/³⁹Ar thermochronologic analyses document Variscan emplacement and cooling of the intrusives (293–289 Ma). SiO₂ content in the granitic rocks ranges from 57 to 77 wt%; cumulate gabbro enclaves have SiO₂ as low as 42%. Variations in absolute abundances and ratios involving Hf, Ta, Th, Rb, and the REE, among others, identify genetically linked groups of granitic rocks in the batholith: (1) syn-tectonic biotite±amphibole-bearing tonalites to granodiorites, (2) post-tectonic two-mica±Al-silicate-bearing granodiorites to leucomonzogranites, and (3) post-tectonic biotite±hornblende tonalites to granodiorites. Chondrite-normalized REE patterns display variable values of Ce/Yb (up to 300) and generally small negative Eu anomalies. Degree of REE fractionation depends on whether the intrusives are syn- or post-tectonic, and on their mineralogy. High and variable values of Rb/Y (0.40–4.5), Th/Sm (0.1–3.6), Th/Ta (0–70), Ba/Nb (1–150), and Ba/Ta (50–2100), as well as low values of Nb/U (2–28) and La/Th (1–10) are consistent with a predominant and heterogeneous crustal contribution to the batholith. Whole rock ¹⁸O ranges from +8.2 to +11.7; the mafic cumulate enclaves have the lowest ¹⁸O values and the two-mica granites have the highest values. ¹⁸O values for biotite±honblende tonalitic and granodioritic rocks (9.1 to 10.8) overlap the values of the mafic enclaves and two-mica granodiorites and leucogranites (10.7 to 11.7). The initial Pb isotopic range of the granitic rocks (²⁰⁶Pb/²⁰⁴Pb 18.17–18.45, ²⁰⁷Pb/²⁰⁴Pb 15.58–15.77, ²⁰⁸Pb/²⁰⁴Pb 38.20–38.76) also indicates the predominance of a crustal source. Although the granitic groups cannot be uniquely distinguished on the basis of their Pb isotope compositions most of the post-tectonic tonalites to granodiorites as well as two-mica granites are somewhat less radiogenic than the syn-tetonic tonalites and granodiorites. Only a few of the mafic enclaves overlap the Pb isotope field of the granitic rocks and are consistent with a cogenetic origin. The Sila batholith was generated by mixing of material derived from at least two sources, mantle-derived and crustal, during the closing stages of plate collision and post-collision. The batholith ultimately owes its origin to the evolution of earlier, more mafic parental magmas, and to complex intractions of the fractionating mafic magmas with the crust. Hybrid rocks produced by mixing evolved primarily by crystal fractionation although a simple fractionation model cannot link all the granitic rocks, or explain the entire spectrum of compositions within each group of granites. Petrographic and geochemical features characterizing the Sila batholith have direct counterparts in all other granitic massifs in the Calabrian-Peloritan Arc. This implies that magmatic events in the Calabrian-Peloritan Arc produced a similar spectrum of granitic compositions and resulted in a distinctive type of granite magmatism consisting of coeval, mixed, strongly peraluminous and metaluminous granitic magmas.     

U-Pb zircon age and Nd isotopic composition of granitoids,charnockites and supracrustal rocks from Heimefrontfjella,Antarctica

Heimefrontfjella and Mannefallknausane, in Dronning Maud Land, Antarctica, comprise an amphibolite-facies terrain and a granulite terrain, separated by a major mylonite zone. The amphibolite terrain is made up of mafic to felsic metavolcanics and metasediments, intruded by granitoid plutons: the granulite terrain has supracrustal rocks with similar lithologies, intruded by felsic plutonic rocks that crystallized as charnockites.U-Pb zircon ages (conventional and ion microprobe) demonstrate that magmatic activity was confined to a relatively short interval between 1130 and 1045 Ma and was followed in the amphibolite terrain by metamorphism around 1060 Ma. Specific ages are as follows: metarhyolite in the amphibolite terrain, 1093 ± 38 Ma; granitoids in the amphibolite terrain, 1045 ± 9 Ma to 1107 ± 16 Ma, charnockites in the granulite terrain, 1073 ± 8 Ma to 1135 ± 8 Ma, metamorphic zircons in garnet amphibolite and a post-metamorphic pegmatite, both 1060 ± 8 Ma. Older zircons were found only in a metasediment which yielded discordant zircon fractions with²⁰⁷Pb/²⁰⁶Pb ages between 1250 and 1450 Ma, and in a granulite facies metaquartzite, which contained concordant zircons with the following ages: 1104 ± 5 Ma, 1215 ± 15 Ma, 1400 Ma, 1700 Ma, 2000 Ma. The youngest age is interpreted as the age of granulite metamorphism, the older ages as those of detrital zircons.A Sm-Nd mineral isochron age of the garnet amphibolite (960 ± 120 Ma) agrees within error with the U-Pb age of metamorphic zircons (1060 ± 8 Ma). Initial _Nd values (T = 1.1 Ga) for 15 samples range from +4 to–4. The highest came from a metabasalt and two granitoids from Milorgfjella, the northern area; the lowest from the granulite-facies metasediment and from a charnockite, both from Vardeklettane, a nunatak in the south. The positive but subdued values preclude generation directly from depleted MORB-type mantle _Nd + 6 to + 7 at 1.1 Ga) and indicate generation from a source containing older crustal material.

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Zusammenfassung Die Gebiete um Heimefrontfjella und Mannefallknausane in Dronning Maud Land, Antarktis, bestehen aus amphibolith- und granulitfaziellen Grundgebirgskomplexen, die durch eine große Mylonitzone voneinander getrennt sind. Der amphibolithfazielle Komplex besteht aus mafisch bis felsischen Metavulkaniten und Metasedimenten, die von Granitplutonen intrudiert werden. Der Granulitkomplex enthält Suprakrustalgesteine ähnlicher Art, die von Charnockiten intrudiert werden.U-Pb-Alter, die mit der konventionellen Multikorn-Methode und an der Ionen-Mikrosonde an Einzelkörner bestimmt wurden, engen die magmatische Aktivität zwischen 1130 und 1045 Ma ein. Auf diese Periode folgte in dem amphibolithfaziellen Gebiet eine Regionalmetamorphose um 1060 Ma. Die Einzelalter sind wie folgt: in dem amphibolithfaziellen Komplex ergab ein Metarhyolith 1039 ± 38 Ma, während die Granitoide zwischen 1045 ± 9 Ma und 1107 ± 16 Ma variieren. In dem Granulitkomplex wurden die Charnockite auf 1073 ± 8 Ma bis 1135 ± 8 Ma datiert, während metamorphe Zirkone aus einem Granatamphibolith sowie aus einem posttektonischen Pegmatit identische Alter von 1060 ± 8 Ma ergaben. Ältere Komponenten wurden lediglich in einer Metasediment-Probe gefunden, die diskordante Zirkone mit²⁰⁷Pb/²⁰⁶Pb Altern zwischen ca. 1250 und 1450 Ma enthielt, sowie in einem granulitfaziellen Metaquarzit, in dem konkordante Zirkone die folgenden Alter ergaben: 1104 ± 5 Ma, 1215 ± 15 Ma, 1400 Ma, 1700 Ma, 2000 Ma. Das jüngste Zirkonalter aus dem Metaquarzit interpretieren wir als Zeitpunkt der Granulitmetamorphose, während die höheren Alter detritische Komponenten repräsentieren.Eine Sm-Nd Mineralisochrone für einen Granatamphibolith hat ein Alter von 960 ± 120 Ma, das innerhalb der experimentellen Fehler mit einem U-Pb-Alter von 1060 ± 8 Ma für metamorphe Zirkone übereinstimmt. Initiale _Nd-Werte (T = l.1 Ga) für 15 Proben variieren zwischen +4 und -4. Die höchsten Werte wurden für einen Metabasalt und zwei Granitoide von Milorgfjella im nördlichen Arbeitsgebiet bestimmt. Die niedrigsten Werte stammen aus dem granulitfaziellen Metaquarzit und von einem Charnockit, beide aus Vardeklettane, einem Nunatak im Süden. Die leicht positiven Werte lassen eine juvenile Bildung der Wirtsgesteine aus einem MORB-ähnlichen Mantel (_Nd + 6 bis + 7 um 1.1 Ga) nicht zu und deuten ein Ausgangsmaterial mit Komponenten älterer kontinentaler Kruste an.

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Résumé Les régions de Heimefrontfjella et Mannefallknausane situées dans le Dronning Maud Land en Antartique sont formées par deux zones principales à degrés métamorphiques différents: une à faciès amphibolitique et une autre à faciès granulitiques, séparées par une zone mylonitique. Des roches métavolcaniques à composition variant de basique à felsique ainsi que des roches d'origine sédimentaire composent la zone amphibolitique. Elles sont recoupées par des plutons granitiques. La zone granulitique est formée également par des roches d'origine volcanique et sedimentaire qui sont, elles, recoupées par des charnockites.Les mesures d'U-Pb sur zircons (utilisant la méthode conventionnelle et la microsonde ionique) montrent que l'activité magmatique s'est confinée à une période relativement courte entre 1130 Ma et 1045 Ma. Elle a été suivie par un métamorphisme, il y a 1060 Ma, dans la zone amphibolitique. De façon plus détaillée, les âges sont les suivants: dans la zone amphibolitique, rhyolite datée à 1093 ± 38 Ma, granitoïdes datés à 1045 ± 9 Ma et 1107 ± 16 Ma; dans la zone granulitique, charnockites datées entre 1073 ± 8 Ma et 1135 ± 8 Ma, zircons métamorphiques provenant d'une amphibolite à grenat datés à 1060 ± 8 Ma et pegmatite postmétamorphique datée à 1060 ± 8 Ma. Deux roches ont fourni des zircons donnant des âges plus anciens: un sédiment métamorphisé et un metaquartzite. Les âges²⁰⁷Pb/²⁰⁶Pb obtenus pour les fractions discordantes des zircons du metasediment varient entre 1250 et 1450 Ma alors que le metaquartzite contient des zircons concordants avec les âges suivants: 1104±5 Ma, 1215±15Ma, 1400 Ma, 1700 Ma et 2000 Ma. L'âge le plus jeune obtenu pour le métaquartzite est interprété comme représentant l'âge du métamorphisme granulitique alors que les âges plus anciens représentent les âges de zircons détritiques.Une isochrone Sm-Nd sur minéraux a été obtenue sur une amphibolite à grenat. Elle définit un âge de 960 ± 120 Ma qui correspond, aux erreurs près, à l'âge U-Pb des zircons métamorphiques (1060 ± 8 Ma). Les _Ndinitiaux (T = 1,l Ga) obtenus pour 15 échantillons varient entre +4 et –4. Les valeurs les plus élevées ont été obtenues pour un basalte et deux granitoïdes de Milorgfjella situés dans la partie nord; les valeur _Nd les plus faibles proviennent du métasédiment dans la zone granulitique et d'une charnockite. Ces deux échantillons se situent dans le nunatak Vardeklettane dans le Sud. Les _Nd étant positifs mais toutefois plus faibles que la valeur du manteau appauvri à cette période (entre +6 et +7 à 1,1 Ma), une extraction directe du manteau ne peut être retenue et nous suggérons que la région source contenait du matériau crustal plus ancien.

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Heimfreontfjella Mannefallknausane Dronning Maud, , , . , . , ., , 1130 1045 Ma. 1060 . : — 1093±38 Ma, 1045±9 Ma 1107±16 Ma. 1073±8 Ma 1135±8 Ma, - 1060±8 Ma. , , 1250 1450 Ma. : 1104±5 Ma, 1215±15 Ma, 1400 Ma, 1700 Ma 2000 Ma. , , , . Sm-Nd, -, 960±120 Ma, , - 1060±8 Ma. Nd (T=1,1 ) 15 + 4 — 4. Milogrfjella . , Vardeklettane . , MORB (Nd + 6 + 7, 1,1 ); .

     

Formation of Ni–Cu–Platinum Group Element sulfide mineralization in the Sudbury Impact Melt Sheet

Summary The Ni–Cu–Platinum Group Element (PGE) sulfide deposits of the Sudbury Structure have provided a major portion of the worlds total nickel production and their host rocks have been the subject of numerous research studies, yet a number of perplexing problems remain to be solved. On the one hand, studies seeking to explain the formation of the Sudbury Structure have now converged on a genetic model which proposes that the Main Mass and Offset Dykes of the Sudbury Igneous Complex (SIC) were produced by crystallization of an impact-generated melt sheet. On the other hand, these models have yet to be fully reconciled with the production of the very large volume of magmatic Ni, Cu, Co, and PGE-rich sulfide mineralization and the associated mafic rock types. This paper explores this problem using new precious metal data from the Main Mass and Offset Dykes. These data are used to understand the relationships between these rocks, and to provide constraints on how the Ni–Cu–PGE sulfide ore deposits fit into the geological evolution of the Sudbury Structure.In the two drill cores selected for study in this project, the Mafic Norite has 1–5 modal percent pyrrhotite plus chalcopyrite, and elevated Ni (40–1000ppm), Cu (40–1140ppm), and PGE (1.9–7.8ppb Pd, 1.8–7.3ppb Pt); this is overlain by Felsic Norite that contains pyrrhotite, and has a wide range in concentration of Ni (13–257ppm), Cu (7–328ppm), and PGE (<0.01–6.4ppb Pd, <0.01–5ppb Pt). For a similar range of MgO, the upper portion of the Felsic Norite unit has 5–10 times lower Ni and Cu abundances than within-plate basalts and local crustal rocks, and PGE abundance levels are mostly below analytical determination limits. Stratigraphic studies of other compositional profiles around the SIC demonstrate that this depletion signature of Ni, Cu, and PGE is widespread and developed not only above mineralized embayments and offsets, but also above barren sections of the lower contact of the SIC.The depletion of the upper part of the Felsic Norite in Ni, Cu and PGE is presumably due to equilibration of the magma with magmatic sulfide, and accumulation of this dense sulfide liquid. Results of modeling indicate that the parental magma giving rise to the Mafic and Felsic Norites had initial Ni and Cu contents of 210 and 110ppm, respectively. In addition, Ni, Cu and PGE tenors calculated in 100% sulfide from the Copper Cliff Offset average 13% Cu, 6% Ni, 18ppm Pd, and 19ppm Pt indicating that these sulfides had formed by fractionation from magmas that contained 310ppm Ni, 310ppm Cu, 18ppb Pd and 19ppb Pt. These values are factors of 3 to 5 higher than the Ni, Cu, Pd, and Pt contents of the Onaping Formation with average values of 55ppm Ni, 48ppm Cu, and 4.9ppb Pd as well as the marginal sulfide-poor phase of the Worthington Offset quartz diorite, which has average values of 61ppm Ni, 59ppm Cu, 2.8ppb Pd and 4.0ppb Pt. Both the Onaping Formation and the marginal quartz diorite are believed to represent the initial composition of a large component of the melt sheet. There is therefore a fundamental problem in reconciling the initial metal contents of the SIC magma as indicated by the marginal phases of the Offset dykes and that of the Onaping Formation with the composition of the SIC magma at the times of formation of the sulfides as indicated by their Ni, Cu and PGE tenors.It is proposed that because the SIC melt sheet was initially superheated with a temperature of 1700°C, it was able to dissolve 5 times as much S as it could at its liquidus temperature of 1200°C. It was also initially composed of an emulsion of mafic and felsic melts (Marsh and Zieg, 1999), which may have formed discrete magma cells. As the temperature of the melt sheet decreased, some of these magma cells became S-saturated and the resultant Ni–Cu–PGE sulfides settled downwards and on reaching magma cells lower in the melt sheet were re-dissolved thereby raising the Ni, Cu and PGE contents of the lower magma cells. It was from these enriched magma cells that precipitation of the ore-forming Ni–Cu–PGE sulfide melts eventually took place.The mineral potential of Offset and embayment structures appears to be empirically linked to the thickness of the overlying noritic rocks; for example, the most heavily mineralized embayments and Offset Dykes are located in areas where the Felsic Norite is thickest. It appears unlikely that the entire 1–3km-thick melt sheet was convectively mixing throughout its lateral extent, and so the heterogeneity in sulfide distribution was retained after crystallization and cooling.