Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

Use of unit response functions for management of regional multilayered aquifers: application to the North Aquitaine Tertiary system (France)

Although there are many numerical applications used in aquifer management, few methodologies seem to be sufficiently adapted to provide solutions for regional-scale problems. Their applications for multilayered aquifers are also too limited. A new groundwater management tool adapted to such large physical systems has been developed, using the unit response function (URF) approach. This tool is based on the link between a numerical groundwater flow model and a mathematical optimisation tool. Pre- and post processing are based on a geographical information system (GIS). The developed tool has been applied to a real management case—the regional Aquitaine multilayered aquifer (France). A representative hydrodynamic model was built using MODFLOW 2000 code. First tests show that the linearity condition needed for the application of URF methodology is respected despite the high complexity of the system. Two management scenarios were tested. Optimal solutions thus obtained allow for viable exploitation alternatives to be proposed, which integrate complex environmental constraints.

---

Résumé Malgré un nombre important d’applications existant dans le domaine de la gestion des aquifères, peu de méthodologies semblent adaptées pour proposer des solutions à des problèmes réels de dimension régionale. Leurs application pour des systèmes multicouches sont souvent trop limitées. Un outil de gestion adapté à ces systèmes de large taille a été développé, basé sur la théorie des Fonctions de Réponses Unitaires (FRU). Cet outil est basé sur le couplage d’un modèle numérique d’écoulement et d’un code d’optimisation mathématique. Les entrées et sorties du modèle sont réalisées à l’aide d’un Système d’Information Géographique (SIG). L’outil développé est appliqué à un cas de gestion réel—le système aquifère régional multicouche aquitain (France). Un modèle hydrodynamique représentatif a été construit, basé sur le code MODFLOW 2000. Les premiers tests montrent que les conditions de linéarité nécessaires à l’application de la méthode FRU sont respectées, malgré l’importante complexité du système. Deux scénarii de gestion sont testés. Les solutions optimales ainsi obtenues permettent de proposer des solutions d’exploitation alternatives viables, intégrant des contraintes environnementales complexes.

---

Resumen Aunque hay muchas aplicaciones numéricas usadas en la gestión de acuíferos, unas pocas metodologías parecen estar adaptadas suficientemente para dar las soluciones a los problemas de escala regional. También son limitadas sus aplicaciones para los acuíferos multicapa. Se ha desarrollado una nueva herramienta para el manejo del agua subterránea, adaptada a tales sistemas físicos grandes, usando el avance de la Función de Respuesta Unitaria (URF). Esta herramienta se basa en la combinación entre un modelo numérico de flujo de agua subterránea y una herramienta de optimización matemática. El pre-proceso y el post-proceso se basan en un Sistema de Información Geográfico (GIS). La herramienta desarrollada se ha aplicado a un caso real de manejo en el acuífero regional multicapa de Aquitania (Francia). Se construyó un modelo hidrodinámico representativo, que usó el código MODFLOW 2000. Las primeras pruebas muestran que la condición de linearidad, necesaria para la aplicación de la metodología URF, se respeta a pesar de la complejidad alta del sistema. Se probaron dos escenarios de manejo. Las soluciones óptimas así obtenidas permiten la proyección de alternativas viables de explotación, las cuales integran restricciones medioambientales complejas.

     

Apports de la méthode sismique réflexion haute résolution à l'identification des structures profondes des formations tertiaires en Médoc (Gironde,France) : implications hydrogéologiques

Near Bordeaux (France), the Oligocene aquifer is a potential target for drinking water supply. A high-resolution seismic campaign and several exploration wells helped to clarify the geometry of this formation and, as a consequence, the Medoc Tertiary aquifers. The major information extracted from these new data is the existence of a soft deformation inducing two different deposit areas, showing different hydrogeological characteristics (thickness, type, hydraulic properties, etc.). The presence of an erosional gap area affecting the Oligocene formations lead us to propose a new image of groundwater flow in the area, in the context of a predicted intensive exploitation of this resource. To cite this article: F. Larroque, A. Dupuy, C. R. Geoscience 336 (2004).     

Using monazite and zircon petrochronology to constrain the P–T–t evolution of the middle crust in the Bhutan Himalaya

The growth and dissolution behaviour of accessory phases (and especially those of geochronological interest) in metamorphosed pelites depends on, among others, the bulk composition, the prograde metamorphic evolution and the cooling path. Monazite and zircon are arguably the most commonly used geochronometers for dating felsic metamorphic rocks, yet crystal growth mechanisms as a function of rock composition, pressure and temperature are still incompletely understood. Ages of different growth zones in zircon and monazite in a garnet‐bearing anatectic metapelite from the Greater Himalayan Sequence in NW Bhutan were investigated via a combination of thermodynamic modelling, microtextural data and interpretation of trace‐element chemical ‘fingerprint’ indicators in order to link them to the metamorphic stage at which they crystallized. Differences in the trace‐element composition (HREE, Y, Eu_N/Eu*_N) of different phases were used to track the growth/dissolution of major (e.g. plagioclase, garnet) and accessory phases (e.g. monazite, zircon, xenotime, allanite). Taken together, these data constrain multiple pressure–temperature–time (P–T–t) points from low temperature (<550 °C) to upper amphibolite facies (partial melting, >700 °C) conditions. The results suggest that the metapelite experienced a cryptic early metamorphic stage at c. 38 Ma at <550 °C, ≥0.85 GPa during which plagioclase was probably absent. This was followed by a prolonged high‐T, medium‐pressure (~600 °C, 0.55 GPa) evolution at 35–29 Ma during which the garnet grew, and subsequent partial melting at >690 °C and >18 Ma. Our data confirm that both geochronometers can crystallize independently at different times along the same P–T path and that neither monazite nor zircon necessarily provides timing constraints on ‘peak’ metamorphism. Therefore, collecting monazite and zircon ages as well as major and trace‐element data from major and accessory phases in the same sample is essential for reconstructing the most coherent metamorphic P–T–t evolution and thus for robustly constraining the rates and timescales of metamorphic cycles.     

Geochemistry of basic dikes in the Lanzo massif (Western Alps): Petrogenetic and geodynamic implications

The Alpine peridotite massif of Lanzo (Italy) contains three generations of basic dikes (gabbros and basalts). The older gabbros are plagioclase-rich mantle segregates while the younger gabbro dikes are cumulates very similar in chemical composition to recent oceanic gabbros and gabbros from ophiolitic complexes. They both were derived from the N-type mid-ocean ridge basalt (MORB) magmas which were progressively more depleted in incompatible elements and were probably generated during a dynamic melting of a rising mantle diapir. The basaltic dikes are the N-type MORB and closely resemble the Alpine-Apennine ophiolitic basalts. They were derived from a different upper mantle source than the parental magmas of the gabbros. The source of the basalts was less depleted in light REE. The presence of basic magmas with N-type MORB affinities in the Lanzo massif is consistent with the close genetic relationship between the Alpine peridotite body and the ophiolites of the Liguro-Piemontese basin.     

Textural, isotopic and REE variations in spinel peridotite xenoliths, Massif Central, France

Sr and Nd isotope analyses and REE patterns are presented for a suite of well-documented mantle-derived xenoliths from the French Massif Central. The xenoliths include spinel harzburgites, spinel lherzolites and some pyroxenites. They show a wide range of textures from undeformed protogranular material through porphyroclastic to equigranular and recrystallised secondary types. Textural differences are strongly linked to trace element geochemistry and variations in radiogenic isotope ratios. Many undeformed protogranular xenoliths are Type IA LREE-depleted with MORB-type ε_Sr values between − 30.7 and − 23.6, and ε_Nd values + 13.9 to + 9.4. A second group of undeformed xenoliths are Type IB LREE-enriched with higher ε_Sr values (− 22.7 to − 10.6) and lower ε_Nd values (+ 11.9 to + 5.6). Deformed xenoliths with porphyroclastic, equigranular and secondary recrystallised textures are all Type IB (LREE-enriched, ε_Nd < 6.4, ε_Sr > 11.8). It is proposed that two separate events have given rise to the observed mixing arrays: (1) MORB-source depleted mantle was enriched by a component derived from an enriched mantle. Deformation and recrystallisation accompanied this event. (2) Subsequently, unenriched MORB-source mantle interacted with magmas chemically akin to the host basalts, and enrichment occurred with little deformation. Hypotheses of Tertiary mantle diapirism resulting in isochemical deformation and refinement of protogranular mantle to equigranular mantle are untenable because of differences in REE patterns and isotopic ratios between different textural groups.     

Geochemistry of the Adamello massif (northern Italy)

The Tertiary Adamello massif, outcropping over an area of more than 550 km² in the southern Alps (northern Italy) is composed mainly of granitoid rocks (granodiorite, tonalite, quartz diorite) with minor amounts of diorite and gabbro. The major and trace element composition of these rocks is comparable to calc-alkaline volcanic rocks of continental margins. The granitoid rocks display spatial and temporal variations in their composition, particularly in Na, P, Sr, La, Nb and Y contents and ⁸⁷Sr/⁸⁶Sr ratios. The variations were probably produced by concurrent contamination/wall-rock assimilation and fractional crystallization of high-alumina basaltic magma.     

Uranium and thorium in paleozoic basalts of Nova Scotia (Canada)

In the Paleozoic basalts of Nova Scotia (Canada) metamorphosed to a greenschist facies grade, U and Th are closely associated with immobile elements (e.g. Zr and Nb). The coherence of these elements with K, typical of igneous rocks is, however, absent, U and Th are apparently not affected by greenschist facies metamorphism as are alkali and alkali earth elements and their variation thus reflects primary magmatic processes. It seems that during the early stages of metamorphism, U and Th were retained together with several other incompatible elements (Zr, Nb, La and Ce) in stable secondary phases or alternatively these elements may be held in primary accessory minerals such as zircon and apatite.     

Carbonate metasomatism in the lithospheric mantle: peridotitic xenoliths from a melilititic district of the Sahara basin

The petrological and geochemical study of harzburgitic and dunitic xenoliths from the melilititic district of In Teria (Algerian Sahara) shows that the lighospheric mantle of this region has been affected by a multi-stage metasomatism. The first metasomatic event is related to the injection of alkali silicated (basaltic or kimberlitic) melt and was responsible for the crystallization of phlogopite at depths ranging between 80 and 100 km and the crystallization of amphibole at about 60 km. During this first event, carbonate probably precipitated in the garnet stability field. In a second stage, the spinal peridotites suffered strong mineral changes resulting in an extensive formation of high-Cr endiopside and leading to conversion of harzburgite and dunite into lherzolite and wehrlite. These changes are associated with an enrichment in the most incompatible trace elements including light REE (rare-earth elements), Ta, Th and variable values of ratios such as Th/La and Ta/La. This second event is atributed to the injection (under conditions of decarbonatation and release of CO₂) of a carbonatitic melt resulting from incipient melting of the garnet peridotites, which were previously carbonated. This interpretation is corroborated by the calculation of a diffusion-percolation model which reproduces well the observed distribution of incompatible trace elements in the spinel peridotites. Given the proposed sequence of events, it appears that most of the specificities of the In Teria xenoliths can be explained by the successive geochemical modifications induced within the lithospheric mantle during reheating.     

Evolution comparée de deux séries alcalines du Pacifique Central: Rôle de la fugacité d’oxygène et de la pression d’eau

A comparative mineralogical and geochemical study of two alkali-basalt series from French Polynesia (Rapa and Nuku-Hiva islands) reveals several important differences, particularly in the degree of Fe enrichment in ferromagnesian minerals and the behaviour of Ti, V and Zn. These differences appear to be connected with the onset of magnetite crystallization, which is early in the Nuku-Hiva suite but later in that of Rapa. The variable influence of this phase is ascribed to differences in IO₂, which is probably ultimately dependent on variations in P_{H 2 O}. In both cases, observed chemical variations may be explained in terms of fractional crystallization, with the occurrence of some oversaturated residual liquids resulting from the separation of mica.