Formation temperatures of clays from the volcaniclastic series of Site 841 ODP: an oxygen isotopic record of a paleothermal flux into the Tonga forearc

Oxygen isotopic compositions of clay minerals were determined on representative samples of the volcano-sedimentary series from Site 841 ODP (Tonga forearc). This isotopic study has demonstrated an abnormally high crystallisation temperature of the clay minerals with respect to temperature expected in burial diagenesis. Formation temperatures obtained using ¹⁸O reach up to 200 °C in a Fe-chlorite-corrensite paragenesis found in the vicinity of basaltic andesite sills intruded into the Miocene tuffs. The paleothermal flux resulting from the cooling of the sills has produced very low grade contact metamorphism in the Miocene Tonga forearc deposits. The consequence of this was the formation of a large amount of hydrous silicates characterised near the sills by a Fe-clays-analcime mineralogical association. Received: 26 September 1997 / Accepted: 22 September 1998     

Impact of coherent eddies on airborne measurements of vertical turbulent fluxes

During the Hydrological-Atmospheric Pilot Experiment (HAPEX)-Sahel, which took place in Niger in the transitional period between the wet and dry seasons, two French aircraft probed the Sahelian boundary layer to measure sensible and latent heat fluxes. The measurements over the Niamey area often revealed organised structures of a few km scale that were associated with both thermals and dry intrusions. We study the impact of these coherent structures using a single day’s aircraft-measured fluxes and a numerical simulation of that day with a mesoscale model. The numerical simulation at high horizontal resolution (250 m) contains structures that evolve from streaks in the early morning to cells by noon. This simulation shows distribution, variance and skewness similar to the observations. In particular, the numerical simulation shows dry intrusions that can penetrate deeply into the atmospheric boundary layer (ABL), and even reach the surface in some cases, which is in accordance with the observed highly negatively skewed water vapour fluctuations. Dry intrusions and thermals organised at a few km scale give skewed flux statistics and can introduce large errors in measured fluxes. We use the numerical simulation to: (i) evaluate the contribution of the organised structures to the total flux, and (ii) estimate the impact of the organised structures on the systematic and random errors resulting from the 1D sampling of the aircraft as opposed to the 2D numerical simulation estimate. We find a significant contribution by the organised structures to the total resolved fluxes. When rolls occur, and for a leg length of about 30 times the ABL depth, the 1D sampled flux is shown to be sometimes 20% lower than the corresponding 2D flux when the 1D sampling direction is the same as the main axis of the rolls, whereas the systematic error is much lower when the direction of the leg is transverse to the rolls. In the case of cells, an underestimate of around 10% can still be observed with the 1D approach independent of direction, due to poor sampling of the energy-containing scales.     

Phase changes and thermodynamic properties of CaTiO3. Spectroscopic data,vibrational modelling and some insights on the properties of MgSiO3 perovskite

The effect of pressure (up to 21 GPa at room temperature) and temperature (up to 1570 K at room pressure) on the Raman spectrum of CaTiO₃ is presented. No significant changes, which could be attributed to a major structural change, are observed in the spectra up to 22 GPa. The pressure shifts of the Raman modes can be related to a significant compression of the Ti-O bond. Discontinuous changes in the spectra upon heating may be related to phase changes observed by calorimetry and X-ray diffraction. The important temperature shifts of some low-frequency modes can be related to an increase in the Ti-O-Ti angle in agreement with the X-ray data showing a decrease of the structural distortion with increasing temperature. These data are compared to those available for MgSiO₃-perovskite and show that CaTiO₃ is a good structural analogue for MgSiO₃-perovskite. The present spectroscopic data are used to calculate the specific heat and entropy of CaTiO₃. The role of the low frequency modes in the calculations is emphasized. Good agreement is observed between calculated and experimentally determined values in the 0–1300 K temperature range. A similarly defined model is proposed for MgSiO₃-perovskite. It is found that the entropy lies between 57 and 64 J/mol/K at 298 K and between 190 and 200 J/mol/K at 1000 K in agreement with the values inferred from experimental equilibrium data. Finally we briefly discuss the values of the Grüneisen parameters of both perovskites inferred from macroscopic and microscopic data.     

Timescales of interface-coupled dissolution-precipitation reactions on carbonates

In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy (AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals (calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid (e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe²⁺ ions that subsequently become oxidized and then precipitate in the form of Fe^III oxyhydroxides. For dolomite and magnesite, dissolution in the presence of pure water (undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution, the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.     

Textural evolution of polyhedral olivine experiencing rapid cooling rates

Dynamic crystallization experiments in the CaO–MgO–Al₂O₃–SiO₂ (CMAS) system have been used to investigate the change in crystal shape when pre-existing polyhedral olivine crystals are cooled rapidly (1,639–2,182°C/h). Polyhedral olivines are crystallized initially in a first step using a slow cooling rate (2°C/h), then skeletal and dendritic overgrowths develop on the polyhedral crystals during a subsequent fast cooling event. During this second episode small dendritic olivines also nucleate within the liquid phase. Observation of the experimental sample by optical microscopy shows that the polyhedral olivine shape progressively changes to a skeletal and then to a dendritic morphology in the following sequence: polyhedral ⇒ hopper polyhedral ⇒ dendritic polyhedral. This evolutional sequence is discussed in terms of changes in the crystal growth conditions during cooling and a general relation between these olivine dynamic crystallization experiments and the integrated model of crystal growth by Sunagawa (Bull Minér 104:81–87, 1981, Morphology of crystals, Terra Scientific Publishing Company, 1987) is proposed.     

Minéraux serpentineux extraits de péridotites serpentinisées des Alpes Occidentales

Complete physical and chemical data presented concern serpentine minerals choosen from epizonal to non metamorphic domains. It is tried to correlate well-studied serpentine minerals, generally coming from particular outcrops with the rock-forming ones known only through the microscope.It appears that ribbons filling serpentine veins in a serpentinized dunite, the whole mesh-structure of a non metamorphic serpentine, and bastite lamellae are made of lizardite. Antigorite, only serpentine mineral present in metamorphic domains, shows no significative difference between high-pressure facies (glaucophane schist) and low-pressure facies (green-schist). The data allow a better understanding of the serpentinization process. The geochemically antinomic behaviour of iron and magnesium is emphasized.     

Identification of zones of preferential groundwater tracer transport using a mobile downhole fluorometer

A mobile downhole fluorometer was used to detect zones of preferential groundwater tracer transport into an observation well. Identification of such zones is not possible if individual samples are collected over the wells entire screened interval. Laboratory-based tests using the fluorometer, and a purpose-built apparatus demonstrated that the fluorometer could be used with tracers to characterise well water flow regimes. During field investigations in a porous aquifer, the fluorometer monitored tracer concentrations in an observation well with a 12-m-long screen, 10 m down the hydraulic gradient from a fully penetrating injection well. Test results showed that the tracer occurred in the observation well over a discrete 2.5-m-thick interval. Single-well dilution test and vertical-flow data indicated that water entered the well at additional depths, but no tracer was detected at these levels. A numerical model reproducing dilution test concentration profiles indicated that water entered the well in many of these horizons at comparable velocities to those in the tracer-bearing zone. These data suggest that groundwater flow direction varied with depth in the aquifer under investigation. Moreover, simulations of tracer arrival indicated that the tracer distribution observed in the observation well was derived from a horizon that may be no thicker than 0.5 m.

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Resumen Se utilizó un fluorómetro móvil descendente para detectar zonas de transporte preferencial de trazadores de agua subterránea en un pozo de observación. La identificación de tales zonas no es posible si se colectan muestras individuales en todo el intervalo enmallado del pozo. En base a pruebas de laboratorio utilizando el fluorómetro y un aparato especial construido se demostró que el fluorómetro podría utilizarse con trazadores para caracterizar ambientes de flujo de agua en los pozos. Durante investigaciones de campo en un acuífero poroso, el fluorómetro monitoreó concentraciones de trazadores en un pozo de observación con una malla de 12 m de largo, 10 m abajo del gradiente hidráulico de un pozo de inyección que penetra totalmente el acuífero. Los resultados de las pruebas muestran que el trazador se presentó en el pozo de observación en un intervalo discreto de 2.5 m de espesor. Pruebas de dilución en un solo pozo y datos de flujo vertical indicaron que el agua entró al. pozo en profundidades adicionales, pero que no se detectó el trazador en esos niveles. Un modelo numérico que reproduce los perfiles de concentración de las pruebas de dilución indica que el agua entró al. pozo en muchos de estos horizontes en velocidades comparables a las existentes en la zona portadora de trazadores. Estos datos sugieren que la dirección de flujo de agua subterránea varió con la profundidad en el acuífero bajo investigación. Por otra parte, las simulaciones de llegada del trazador indicaron que la distribución del trazador observada en el pozo de observación se derivó de un horizonte cuyo espesor puede no ser mayor de 0.5 m.

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Résumé Un fluorimètre a été utilisé pour détecter les zones découlement préférentiel dun traceur dans un puits dobservation. Les identifications de telles zones nest pas possible si les échantillons individuels sont collectés sur toute les longueurs des parties crépinées du puits. Les tests de laboratoire utilisant un fluorimètre et un dispositif adéquat ont montré que les fluorimètres pouvaient servir à définir les régimes découlement de leau dans les puits. Durant les investigations de terrain dans un aquifère poreux, le fluorimètre a enregistré les concentrations du traceur dans un puits dobservation avec une crépine de 12 m. de long, 10 m sous le gradient hydraulique dans un puits à pénétration totale. Les résultats des tests ont montré que le traceur apparaissait dans un interval discret de 2.5 m de long. Un test de dilution en puits unique et des données découlement vertical ont indiqué que leau rentrait dans le puits à dautres profondeurs, mais le traceur na pas été détecté à ces niveaux. Un modèle numérique reproduisant le test de dilution et le profil de concentration a indiqué que leau entrait dans le puits à ces niveaux à des vitesses comparables de celle du traceur. Ces données suggèrent que lécoulement des eaux souterraines varie avec la profondeur dans laquifère sous la zone dinvestigation. Dailleurs, les simulations de larrivée du traceur ont montré que la distribution des concentrations du traceur dans le puits ne pouvaient pas être dues à une couche plus fine que 0.5 m.

     

A conceptual hydrogeological model of ophiolite hard-rock aquifers in Oman based on a multiscale and a multidisciplinary approach

Ophiolites are found all over the world: from the Alps to the Himalayas, in Cuba, Papua-New Guinea, New Caledonia, Newfoundland, etc. They are composed of hard rocks—basalt, dolerite, gabbro and peridotite, which are formed at the mid-oceanic ridges, with specific ridge-related tectonic fracturing and intense hydrothermal alteration. Their geological and thus their hydrogeological properties differ from those of both granite or classical gabbro and classical basaltic lava. A conceptual hydrogeological model of these hard-rock aquifers was developed based on the convergent results of a multidisciplinary approach at several spatial scales, from rock-sample (centimetre) to catchment (kilometre), on well-preserved ophiolite rocks in Oman. In ophiolite rocks, groundwater circulation takes place mostly in the fissured near-surface horizon (50 m thick), and, to a lesser degree, in the tectonic fractures. Hydrograph analysis (Water Resour Res 34:233–240, 1977), interpretation of numerous pumping tests using both classical Theis and dual porosity models [Water Resour Res 32:2733–2745, 1996; Comput Geosci J (in press)], and mercury porosity and hydraulic conductivity lab-measurements support the aquifer parameter estimates. The hydraulic conductivity K of the fissured horizon is estimated at 10^–5 to 10^–6 m/s for gabbro and dolerite, and 10^–7 m/s for peridotite. The storage coefficient S of the peridotite aquifer is estimated at 10^–3 and appears to be controlled mainly by microcracks (20 to 100 m wide). Tectonic fractures in the ophiolite have similar hydrodynamic properties regardless of lithology (10^–1<T<10^–4 m²/s and 10^–1<S<10^–3) though the probability of obtaining productive wells is two to three times greater in gabbro and dolerite than in peridotite. Some of the tectonic fractures produce small hydrothermal, hyperalkaline springs in the peridotite. The water budget and hydrochemistry of the Oman ophiolite are characterized and support the conceptual hydrogeological model. Despite low annual rainfall, a relatively low hydraulic conductivity and a significant storage coefficient explain why most of the streams in peridotite are perennial.

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Résumé Les ophiolites se trouvent partout dans le monde : des Alpes à lHymalaya, à Cuba, Papouasie Nouvelle-Guinée, Nouvelle Calédonie, etc. Les ophiolites sont composées de roches dures basaltiques, de dolérites, gabbros et péridotites, qui sont formées aux rides mi-océaniques, avec, en relation avec les rides, une fracturation tectonique et une altération hydrothermale intense. Leurs propriétés géologiques et hydrogéologiques diffèrent de celles des granites ou des gabbros classiques ou des laves basaltiques classiques. Un modèle hydrogéologique conceptuel des aquifères de hard-rock a été développé sur les résultats convergents dune approche multidisciplinaire à différentes échelles spatiales, de léchantillon de roche de quelques centimètres à la taille du bassin versant en kilomètres, des ophiolites bien conservées dOman. Dans les roches ophiolitiques, la circulation des eaux souterraines est surtout localisée dans les fissures dun horizon de surface de plus dune cinquantaine de mètres et à un degré moindre dans les fractures tectoniques. Lanalyse des hydrographes (Water Resour Res 34:233–240, 1977), linterprétation des nombreux essais de pompage utilisant des modèles classiques de Theis et des modèles à double porosité (Water Resour Res 32:2733–2745, 1996; Comput Geosci J (Soumis), la porosité au mercure et la conductivité hydraulique calculée en laboratoire supportent lestimation des paramètres de laquifère. La conductivité hydraulique K de lhorizon fissuré est estimée entre 10^–5 et 10^–6 m/s pour les gabbros et les dolérites, et 10^–7 m/s pour les péridotites. Le coefficient demmagasinement S de laquifère de péridotite est estimé à 10^–3 et semble être contrôlé par les micro-fractures (20 à 100 m de largeur). Les fractures tectoniques dans les ophiolites possèdent des propriétés hydrodynamiques en regard de la lithologie (10-1<T<10-4 m²/s et 10-1/S/10-3) bien que la probabilité dobtenir des puits productifs est trois plus grand dans le grabbro et la dolérite que la péridétite. Quelques unes des fractures tectoniques produisent de petites sources hydrothermales hyperalcalines dans la péridotite. Le bilan hydrologique et hydrochimique de lophiolite dOman caractérise le modèle hydrogéologique conceptuel. Malgré des faibles précipitations annuelles, une relativement basse conductivité hydraulique et un coefficient demmagasinement significatif expliquent pourquoi la plus part des cours deau sur les péridotites ne sont jamais taris.

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Resumen Las rocas ofiolitas se encuentran en muchas partes del mundo desde los Alpes a los Himilaya, Newfoundland, Nueva Caledonia etc. Son rocas duras compuestas de basalto, dolerita, gabro y peridotita que son formadas por los cordones medio-oceánicos y por fracturación relacionada con los cordones tectónicos específicos y alteración hidrotermal intensa. La geología y los propiedades hidrogeológicas varian entre las de granito y gabro clásico y lava de basalto clásico. Se desarrolló un modelo conceptual de los acuíferos de las rocas duras Basado en los resultados convergentes de un enfoce multidisciplinario a varias escalas a partir de muestras de roca (centímetro) a cuenca kilómetro) enfocado en las rocas ofilíticas bien preservados en Oman. En las rocas ofiolíticas la circulación de agua ocurre principalmente en el horizonte de fisuras cercanas a la superficie (>50 m de espesor) y en un grado menos importante en fracturas tectónicas. Los estimados de los parámetros de estos acuíferos se basan en análisis de hidrógrafos (Water Resour Res 34:233–240, 1977), en la interpretación de pruebas de bombeo usando los modelos clásicos de Theis y de porosidad doble (Hamm y Bidaux 1996; Lods y Gouze, [en prensa]), y porosidad de mecurio y conductividad hidraúlica medida en el laboratorio. La conductividad hidraúlica K del horizonte fisurado se estima en 10E-5 a 10E-6 m-s para gabro y dolerita y 10E-7 para peridotita. El coeficiente de abastecimiento S del acuífero peridotita se estima en 10–3 y parece ser controlado principalmente por microfracturas (20 to 100 m de ancho). Las fracturas tectónicas en la ofiolita tienen propiedades hidrodinámicas similares independientes de la litología (10–1<T<10–4 m²/s and 10–1<S<10–3) pero la probabilidad de obtener pozos productivos es dos o tres veces mayor en gabro que en dolerita o peridotita. Algunas de las fracturas tectónicas producen pequeñas descargas de agua hidrotermal hiperalcalina en la peridotita. El presupuesto e hidroquímica de las ofilitas de Omán se caracteriza y apoya en el modelo conceptual hidrogeológico. La baja lluvia anual, una conductividad hidraúlica relativamente baja y un coeficiente de abastecimiento importante explican porqué la mejoría de los drenajes en peridotita es peremne.

     

Monitoring chemical contamination levels in the Mediterranean based on the use of mussel caging

Within the framework of the biointegrator network (RINBIO), 92 man-made cages containing mussels (Mytilus galloprovincialis), distributed over 1800 km of the French Mediterranean coast, made it possible to assess chemical contamination by heavy metals (Cd, Hg, Zn, Pb, Cu, Ni, Cr, As) and organic compounds (DDT, PCBs, HAP). The caging technique was adopted to compensate for the scarcity of natural shellfish stocks in the Mediterranean and to enable comparison of the sites regardless of their physicochemical and trophic characteristics. Models linking a biometric parameter (the condition index) to pollutant levels make it possible to adjust raw data on contamination for a reference individual, by making a clear distinction between physiological factors (growth) and environmental ones. The results demonstrate significant levels of pollutants in sites heretofore unsampled; the pollution occurs at limited areas, and the sources have been identified. Moreover, average contamination levels are comparable to those measured in wild species and in other areas. Overall, the research demonstrates the reliability of this methodological approach for monitoring marine pollution, especially in the Mediterranean.