U-Pb-Hf isotopic data from detrital zircons in late Carboniferous and Mid-Late Triassic sandstones,and also Carboniferous granites from the Tauride and Anatolide continental units in S Turkey: implications for Tethyan palaeogeography

ABSTRACT

Zircons from Carboniferous sandstones (three samples) and Mid-Late Triassic sandstones (four samples) from the Tauride and Anatolide continental units were analysed for U-Pb-Hf isotopes. For comparison, zircons were also analysed from Carboniferous granites of the Afyon Zone, Anatolides (three samples). A NE African/Arabian source is inferred for both the Carboniferous sandstones of the Taurides (Alada?) and the Anatolides (Konya Complex). In contrast, the Carboniferous Karaburun Melange is characterised by a NW African provenance. A prominent Devonian population occurs in the Carboniferous Karaburun Melange, characterised by mainly positive ε_Hf(t) values that differ significantly from those of the Devonian granites of the Sakarya continental crustal unit (Pontides). Middle-Late Triassic Tauride sandstones include minor Palaeozoic and Early Mesozoic zircons. In contrast, Devonian and Carboniferous zircons are relatively abundant in Late Triassic sandstones of the Karaburun Peninsula. The Hf isotopic compositions of 25 Carboniferous-aged zircons from three samples of Mid-Late Triassic sandstone and one of Late Carboniferous age (one sample) overlap with the ε_Hf(t) values of Carboniferous arc-type granites in the Anatolides. Taking account of the available U-Pb and Lu-Hf isotopic data from comparative crustal units, the Devonian zircon populations from the melanges in the Karaburun Peninsula and the Konya Complex are inferred to have a westerly source (e.g. granitic rocks of Aegean region or central Europe). A tectonic model is proposed in which Palaeozoic Tethys sutured during the late Carboniferous in the west (Aegean region westwards), leaving an eastward-widening oceanic gulf in which sandstone turbidites accumulated, including Devonian zircons.     

The breakdown of potassium feldspar at high water pressures

The equilibrium position of the reaction between sanidine and water to form “sanidine hydrate” has been determined by reversal experiments on well characterised synthetic starting materials in a piston cylinder apparatus. The reaction was found to lie between four reversed brackets of 2.35 and 2.50 GPa at 450 °C, 2.40 and 2.59 GPa at 550 °C, 2.67 and 2.74 GPa at 650 °C, and 2.70 and 2.72 GPa at 680 °C. Infrared spectroscopy showed that the dominant water species in sanidine hydrate was structural H₂O. The minimum quantity of this structural H₂O, measured by thermogravimetric analysis, varied between 4.42 and 5.85 wt% over the pressure range of 2.7 to 3.2 GPa and the temperature range of 450 to 680 °C. Systematic variation in water content with pressure and temperature was not clearly established. The maximum value was below 6.07 wt%, the equivalent of 1 molecule of H₂O per formula unit. The water could be removed entirely by heating at atmospheric pressure to produce a metastable, anhydrous, hexagonal KAlSi₃O₈ phase (“hexasanidine”) implying that the structural H₂O content of sanidine hydrate can vary. The unit cell parameters for sanidine hydrate, measured by powder X-ray diffraction, were a = 0.53366 (±0.00022) nm and c = 0.77141 (±0.00052) nm, and those for hexasanidine were a = 0.52893 (±0.00016) nm and c = 0.78185 (±0.00036) nm. The behaviour and properties of sanidine hydrate appear to be analogous to those of the hydrate phase cymrite in the equivalent barium system. The occurrence of sanidine hydrate in the Earth would be limited to high pressure but very low temperature conditions and hence it could be a potential reservoir for water in cold subduction zones. However, sanidine hydrate would probably be constrained to granitic rock compositions at these pressures and temperatures. Received: 6 May 1997 / Accepted: 2 October 1997     

Petrology of the 1979 eruption of Soufriere volcano,St. Vincent,Lesser Antilles

Major element, trace element, and Sr isotope data are used to study the temporal variation in the chemistry of the ejecta from the 1979 eruption of Soufriere volcano, St. Vincent, and to compare the compositions of the 1979 and 1971/2 magmas. Both the 1971/2 and 1979 products were basaltic andesites almost identical in petrography. A small temporal variation in chemistry is apparent in the 1979 samples but these cannot be related to the 1971/2 lava by fractional crystallisation of phenocryst phases, and the two eruptions may therefore have sampled different batches of magma. ⁸⁷Sr/⁸⁶Sr ratios of the two magmas were identical within analytical error.Microprobe analyses of phenocryst phases and glasses from the 1979 ejecta are presented. Clinopyroxene phenocryst cores with very high Mg/Fe ratios indicate that the basaltic andesites are products of fractionation of magnesian parents. Such magmas are represented by lavas on St. Vincent similar to the microphyric alkali picrites found to the south in Grenada. A common origin for the basaltic andesites of both islands by fractional crystallisation of picritic magmas is suggested. Dacitic glass is abundant in the groundmass of scoria blocks from the eruption. It does not represent the liquid originally in equilibrium with the phenocryst phases, but rather this liquid modified by quench crystallisation. Published interpretations suggesting that dacitic glass compositions in tephra from eruptions of the Soufriere are evidence of mixed-magma eruptions are therefore rejected.     

Experimental hydrogen isotope studies III: Diffusion of hydrogen in hydrous minerals,and stable isotope exchange in metamorphic rocks

Diffusion parameters for hydrogen diffusion in epidote-group minerals and micas have been measured under hydrothermal conditions, or calculated from existing experimental data, for bulk hydrogen isotope exchange experiments between hydrous minerals and water. Activation energies in the range 14 to 31 kcals/g-atom H are comparable to those derived by application of kinetic theory to experimental hydrogen isotope exchange data, and to those for oxygen diffusion in minerals under hydrothermal conditions. Diffusion of hydrogen in epidote is about four orders of magnitude faster than in muscovite, and about two orders of magnitude faster than in zoisite. Hydrogen diffusion in micas is about five orders of magnitude faster than oxygen diffusion, and hydrogen transport occurs dominantly parallel to the layers rather than parallel to the c-axis as for oxygen.Rapid hydrogen transport in minerals may proceed by hydrolysis of Si-O and Al-O bonds, followed by exchange of hydrolyzed oxygens with slower-diffusing (OH) or H₂O. Water appears to be essential for stable isotope exchange between minerals in slowly cooling metamorphic rocks.Stable isotope data for regional metamorphic mineral assemblages suggests that water is usually present in small amounts during cooling of prograde regional metamorphic systems, and estimated closure temperatures for cessation of stable isotope exchange are often more comparable to those calculated from diffusion data than to likely temperatures of metamorphism.Alpine deformation of the Hercynian Monte Rose Granite (Frey et al. 1976) permitted access of water and initiated stable isotope exchange amongst coexisting minerals. The diffusional behaviour of species in relict Hercynian muscovites is consistent with available experimental diffusion data.     

Amino acid racemization dating of fossil bones,I. inter-laboratory comparison of racemization measurements

Enantiomeric measurements for aspartic acid, glutamic acid, and alanine in twenty-one different fossil bone samples have been carried out by three different laboratories using different analytical methods. These inter-laboratory comparisons demonstrate that D/L aspartic acid measurements are highly reproducible, whereas the enantiomeric measurements for the other amino acids show a wide variation between the three laboratories. At present, aspartic acid measurements are the most suitable for racemization dating of bone because of their superior analytical precision.     

Experimental hydrogen isotope studies,II. Fractionations in the systems epidote-NaCl-H2O,epidote-CaCl2-H2O and epidote-seawater,and the hydrogen isotope composition of natural epidotes

The hydrogen isotope fractionation factors between epidote and aqueous 1 M and 4 M NaCl, 1 M CaCl₂ solutions, and between epidote and seawater, have been measured over the temperature range 250–550°C over which the degree of dissociation of dissolved species varies significantly. Measured fractionations at 350°C are decreased by up to 12‰, 9‰ and 7‰ relative to pure water in seawater, 1 M CaCl₂ and 1 M NaCl respectively, while above 500°C fractionations are not measurably dependent on fluid composition. Water—solution fractionation factors are derived which are generally applicable to the correction of mineral—water hydrogen isotope fractionations for the composition of the fluid phase.The hydrogen isotope compositions of natural epidotes are interpreted in the light of experimental fractionation data for situations where temperature, δD (fluid), and, in some cases, fluid chemistry, are independently known. Epidotes from active geothermal systems have hydrogen isotope quench temperatures consistent with or close to measured well temperatures unless the measured temperature has declined substantially since epidote formation or there is uncertainty in the D/H ratio of the water associated with the epidote because of isotopic heterogeneity in the well waters. Hydrothermal and metamorphic epidotes show closure temperatures of 175–225°C and 200–250°C. There is no evidence that retrograde metamorphic fluids, if present, are isotopically different from prograde fluids.The water-solution fractionations indicate strong solute-solvent interactions between 250 and 450°C and imply that both dissociated and associated species contribute to the fractionation effects through modification of the orientations and structure of the water molecules. Solute-solvent interactions become negligible at temperatures around 550°C.     

Crystallization of chromite from nickel-iron sulphide melts

An experiment, in which an iron-nickel-copper sulphide melt was heated with synthetic chromite and then cooled, showed that substantial quantities of chromite had dissolved in the melt and had then recrystallized as euhedral crystals rimmed with magnetite. This experiment suggests that the unusual chromite (low in Mg and Al) which is associated with the sulphide phase in Western Australian nickel ores may have formed in a similar way.J.M.R. carried out the experimental part of this investigation as a post-graduate student at Flinders University, South Australia, working under a CSIRO extramural grant.