A thermodynamic model for Fe–Mg dioctahedral K white micas using data from phase-equilibrium experiments and natural pelitic assemblages

The purpose of this study is to derive a solid-solution model for potassic white micas (KWM) encountered in rocks of various bulk compositions, over a wide range of P-T conditions. A compilation of phengite compositions lead us to propose a seven-thermodynamic-component (muscovite, Fe²⁺-Al-celadonite, Mg-Al-celadonite, annite, phlogopite, pyrophyllite and paragonite) ionic solid-solution model which accounts for the Tschermak, Fe-Mg, di/trioctahedral, pyrophyllitic and paragonitic substitutions observed in nature. A four-site mixing model with symmetric Margules parameters to model the Tschermak substitutions, asymmetric Margules parameters to model the other substitutions, and ideal intersite interaction has been adopted. In contrast to previous models, the relevant thermodynamic data and solid-solution properties are calibrated with independent sets of published experiments conducted for the KMASH, KFASH, KFMASH, and KNASH systems, as well as about 200 natural data involving KWM assemblages. The constraints span a wide range of pressure and temperature conditions (150 to 750 °C, 0.5 to 30 kbar), so that our model does not need to be extrapolated outside the calibration range to be used for P-T thermobarometric purposes. The calculated thermodynamic data are interconsistent with the TWQ thermodynamic database and solid-solution models, including that recently published for chlorites.     

Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model

The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized.     

Geochemistry of oceanic carbonatites compared with continental carbonatites: mantle recycling of oceanic crustal carbonate

Major and trace element and Sr-Nd-Pb-O-C isotopic compositions are presented for carbonatites from the Cape Verde (Brava, Fogo, Sáo Tiago, Maio and Sáo Vicente) and Canary (Fuerteventura) Islands. Carbonatites show pronounced enrichment in Ba, Th, REE, Sr and Pb in comparison to most silicate volcanic rocks and relative depletion in Ti, Zr, Hf, K and Rb. Calcio (calcitic)-carbonatites have primary (mantle-like) stable isotopic compositions and radiogenic isotopic compositions similar to HIMU-type ocean island basalts. Cape Verde carbonatites, however, have more radiogenic Pb isotope ratios (e.g. ²⁰⁶Pb/²⁰⁴Pb=19.3-20.4) than reported for silicate volcanic rocks from these islands (18.7-19.9; Gerlach et al. 1988; Kokfelt 1998). We interpret calcio-carbonatites to be derived from the melting of recycled carbonated oceanic crust (eclogite) with a recycling age of ~1.6 Ga. Because of the degree of recrystallization, replacement of calcite by secondary dolomite and elevated ‘¹³C and ‘¹⁸O, the major and trace element compositions of the magnesio (dolomitic)-carbonatites are likely to reflect secondary processes. Compared with Cape Verde calcio-carbonatites, the less radiogenic Nd and Pb isotopic ratios and the negative Ɨ/4 of the magnesio-carbonatites (also observed in silicate volcanic rocks from the Canary and Cape Verde Islands) cannot be explained through secondary processes or through the assimilation of Cape Verde crust. These isotopic characteristics require the involvement of a mantle component that has thus far only been found in the Smoky Butte lamproites from Montana, which are believed to be derived from subcontinental lithospheric sources. Continental carbonatites show much greater variation in radiogenic isotopic composition than oceanic carbonatites, requiring a HIMU-like component similar to that observed in the oceanic carbonatites and enriched components. We interpret the enriched components to be Phanerozoic through Proterozoic marine carbonate (e.g. limestone) recycled through shallow, subcontinental-lithospheric-mantle and deep, lower-mantle sources.     

An Early-Cambrian UPb apatite cooling age for the high-temperature regional metamorphism in the Piancó area,Borborema Province (NE Brazil): initial conclusions

The Borborema Province (BP) of northeastern Brazil is a complex crustal assemblage, which has undergone a polycyclic evolution during the Proterozoic. In the Piancó-Alto Br??gida belt, a metamorphosed leucosome vein inserted in amphibolites has a trace element pattern suggesting a T-MORB protolith. Apatites yield a REE pattern indicating growth in equilibrium with garnet, thus pointing to its metamorphic origin. UPb analyses yield an age of 540±5 Ma interpreted as a cooling age following amphibolite facies regional metamorphism associated with granitic emplacement at ca. 580 Ma. The resulting slow cooling rates (ranging from ca. 2.5 to 5 °C Ma^?1) are consistent with underplating of mafic magmas, or crustal thickening caused by nappe stacking, as possible processes governing the metamorphic evolution of the BP. To cite this article: B. Dhuime et al., C. R. Geoscience 335 (2003).     

Asymptotic Analysis and Layer Decomposition for the Couplex Exercise

This document explores the possibilities of multiscale expansions and domain decomposition to solve part of the Couplex 1 exercise. We concentrate on the hydrostatic pressure and show that the slenderness of the domain and the large variations of the Darcy constants allows an analytical approximation which our test reveals to be true to relative errors smaller than 10^–3. The numerical tests are done in 2D with freefem+ and in 3D with freefem3D. Some considerations are also given for Iodine transport.     

Field and petrological evidence for a Late Palaeozoic (Upper Carboniferous–Permian) age of the Erfaulet orthogneiss (Gran Paradiso,western Alps)

In the Gran Paradiso massif (western Alps), the boundary between the Erfaulet orthogneiss and the overlying metasediments (Money Complex) is interpreted as a Late Palaeozoic intrusive contact. Major arguments in favour of this hypothesis are: (i) the obliquity of the sedimentary layering with respect to the contact; (ii) the presence of aplitic dykes within the Money Complex; (iii) the lack of a mylonitic zone; and (iv) rare relics of an early generation of garnet in the Money metasediments, interpreted as evidence of the contact metamorphism of the Erfaulet granite. To cite this article: B. Le Bayon, M. Ballèvre, C. R. Geoscience 336 (2004).     

Petrography of Middle Jurassic to Early Cretaceous sandstones in the Kutch Basin,western India:Implications on provenance and basin evolution

This paper investigates the provenance of Middle Jurassic to Early Cretaceous sediments in the Kutch Basin, western India, on the basis of mineralogical investigations of sandstones composition(Quartz-Feldspar-Lithic(QFL)fragment), Zircon-Tourmaline-Rutile(ZTR) index, and mineral chemistry of heavy detrital minerals of the framework.The study also examines the compositional variation of the sandstone in relation to the evolution of the Kutch Basin, which originated as a rift basin during the Late Triassic and evolved into a passive margin basin by the end Cretaceous. This study analyzes sandstone samples of Jhumara, Jhuran and Bhuj Formations of Middle Jurassic,Upper Jurassic and Lower Cretaceous, respectively, in the Kutch Mainland. Sandstones record a compositional evolution from arkosic to subarkosic as the feldspar content decreases from 68% in the Jhumara Formation to 27%in the Bhuj Formation with intermediate values in the Jhuran Formation. The QFL modal composition indicates basement uplifted and transitional continental settings at source. Heavy mineral content of these sandstones reveals the occurrence of zircon, tourmaline, rutile, garnet, apatite, monazite and opaque minerals. Sub-rounded to well-rounded zircon grains indicate a polycyclic origin. ZTR indices for samples in Jhumara, Jhuran and Bhuj Formations are 25%, 30% and 50% respectively. Chemistry of opaque minerals reveals the occurrence of detrital varieties such as ilmenite, rutile, hematite/magnetite and pyrite, in a decreasing order of abundances. Chemistry of ilmenites in the Jhumara Formation reveals its derivation from dual felsic igneous and metabasic source, while those in Jhuran and Bhuj Formations indicate a metabasic derivation. Chemistry of garnet reveals predominantly Fe-rich(almandine) variety of metabasic origin. X-ray microscopic study provides the percentage of heavy minerals ranging from 3% to 5.26%. QFL detrital modes reflect the evolution of the basin from an active rift to a passive margin basin during the Mesozoic. Integration of results from QFL modal composition of the sandstones, heavy mineral analysis and mineral chemistry, suggests sediment supply from both northern and eastern highlands during the Middle Jurassic. The uplift along the Kutch Mainland Fault in the Early Cretaceous results in curtailment of sediment input from north.