Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.     

Present limitations of accurate satellite Doppler positioning for tectonics. An example: Djibouti

One of the possibilities of the Doppler positioning from satellite is to provide geodetic measurements continuous in time without the need for reference stations. If measurements of sufficient accuracy can be achieved they may be used to study local surface displacements in relation to tectonic activity. A Doppler receiver of the MEDOC network is located near Djibouti in the Ghoubhat-Asal rift region which corresponds to the accreting plate boundary between the Arabian and African plates. In November 1978, a seismic and volcanic crisis occured in this area. Surface geodetic measurements and levellings performed in 1973 and 1978–79, just after the crisis, reveal a 60–80 cm sinking of the graben floor and a lateral extension of about 2 meters. Here we analyse Doppler measurements for the period January 1977 to November 1980. Point positions are computed for 7 to 10 day intervals using a precise ephemeris, and a moving window analysis is applied to the data. An apparent 2 meter uplift preceding the November 1978 seismic crisis is detected at Djibouti, whereas no similar phenomenon is observed at the two closest stations, Pretoria and Uccle-Brussels. However, field observations rule out a tectonic origin for this uplift. In Djibouti, the correlation between the apparent vertical station position and the electron density in the ionospheric F-layer reveals that a bias may be induced by the third order term of the ionospheric refractive index not previously taken into account, or more probably by the ray curvature through the ionosphere. This bias is particularly strong for our data set, from a station located close to the magnetic equator, and related to a period of rapid increase in the solar activity. Although our analysis fails to detect any tectonic displacement related to the rift seismic activity, it shows that similar tectonic studies by the Doppler method will be possible once the residual ionospheric errors are removed, for example by use of higher radio frequencies.     

Three-dimensional model and late stage warping of the Plattengneis Shear Zone in the Eastern Alps

The Plattengneis shear zone is a 250–600 m thick, flat lying, Cretaceous, eclogite facies, mylonitic shear zone, with north-over-south transport direction, that is exposed over almost 1000 km² in the Koralpe region along the eastern margin of the Alps. Although the shear zone is one of the largest in the Alps, its role in the Eoalpine metamorphic evolution and the subsequent exhumation of the region, remain enigmatic and its large-scale geometry is not well understood. The outcrop pattern suggests that the shear zone is made up of a single sheet that is folded into a series of open syn- and antiforms with wavelengths of about 10 km. Eclogite bodies occur above, within and below the shear zone and there is no metamorphic grade change across the shear zone. In the south, the fold axes strike east–west and plunge shallowly to the east. In the north, the fold axes are oriented in north–south direction and form a dome shaped structure of the shear zone. Total shortening during this late stage warping event was of the order of 5%. Indirect evidence constrains this folding event to have occurred between 80 and 50 Ma and the fold geometry implies that the final exhumation in the Koralpe occurred somewhat later than further north. Interestingly, the shear zone appears to strike out of the topography in the south and dip into the topography in the north, so that north of the shear zone only hanging-wall rocks are exposed and south of it only foot-wall rocks. Possibilities for the geometric relationship of the Plattengneis shear zone with the surrounding south dipping detachments are discussed.     

Metamorphism at the northwest contact of the Stanhope Pluton,Quebec Appalachians: Mineral equilibria in interbedded pelite and calc-schist

The interbedding of pelite and calc-schist in part of the contact aureole of a Devonian (biotite K-Ar age 346±4 Ma) granite pluton that straddles the Quebec-Vermont border offers an opportunity to compare metamorphic conditions prevailing in both rock types, and to test for internal consistency among several different geothermometers and geobarometers.Microprobe analyses and recent thermodynamic data are used with simple activity-composition models to estimate P-T-X _fluid conditions near the sillimanite zone. Calculations yield the following results: P=2 to 3 kb, and T =400° to 600° C in the inner one kilometre of the aureole; was around 0.8. Estimates are based on the calc-silicate isobaric invariant assemblages tremolite-K-feldspar-plagioclase-clinozoisite-phlogopite-calcite-quartz and diopside-tremolite-plagiolase-clinozoisite-calcite-quartz, and the paragonite-andalusite-sillimanite-albite-quartz equilibrium. The solid-solid reaction phlogopite+2 diopside + 4 quartz=tremolite+K-feldspar in the calc-schist (combined with the andalusite-sillimanite equilibrium), and phase relations in the granite yield apparently inconsistent results.The implied 6 to 10 km of cover at the time of intrusion may have been provided by subsequently eroded thrust sheets.     

Une mégaséquence d'émersion: la Lettenkohle (Trias Est de la France). Mise en évidence de marées par l'imbrication bipolaire de plaques de dessiccation

Résumé Dès la partie moyenne du Muschelkalk supérieur, les faciès marins francs deviennent de moins en moins profonds. Avec l'avènement de la Lettenkohle, la transgression marine à son maximum dans le Muschelkalk supérieur, semble s'épuiser. Le caractère régressif est attesté par le relais de faciès récifaux, par des dépÔts littoraux et des marais cÔtiers. Cette évolution est marquée par l'édification d'une mégaséquence d'émersion complète. Des indices de marées sous forme d'imbrications bipolaires de plaques de dessiccation ainsi que des chenaux tidaux ont été observés. Certaines structures tidales ont été comparées avec celles de l'estran du Mont-Saint-Michel en Normandie (France).

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From the Middle Upper Muschelkalk the marine facies are becoming less deep. At the beginning of the Lettenkohle the marine transgression which had reached a maximum in the Upper Muschelkalk now seems to decline. Regression is evidenced by progressive replacement of reef facies by coastal deposits and supratidal marshes. The process results in the erection of the coarsening upward cycle of a progressive complete emergence.The trace of tides, i.e. bipolar desiccation clast fabric as well as tidal channels have been observed. Some tidal structures are compared with those of the depositional environment of Mont Saint Michel (Normandie).

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Zusammenfassung Schon im mittleren Oberen Muschelkalk zeigen die vollmarinen Fazies eine allmähliche Verringerung der Meerestiefe. Mit dem Auftreten der Lettenkohle scheint die im Oberen Muschelkalk optimale Transgression langsam abzuklingen. Ein progressiver übergang von einer marinen Riffbildung zu einem Küstenlandmoor veranschaulicht eine Regression. Dieser Vorgang bildet die Megasequenz einer progressiven totalen Emersion.Gezeiteneinflüsse werden an eingeregelten Trockenri\klasten und Rinnen beobachtet. Wattgefüge werden mit denen des heutigen Wattablagerungsmilieu des Mont Saint Michel in der Normandie verglichen.

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. . . , . - . , , Mont Saint Michel .

     

Mobility of potentially harmful metals in latosols impacted by the municipal solid waste deposit of Londrina,Brazil

The contamination of soils by metals issuing from municipal solid waste (MSW) disposal in tropical environments has hardly been studied with regard to the particular problems associated with them, i.e., generally a high permeability of soils despite the abundance of clay, and the role of reactive Fe compounds. From a previous geotechnical and chemical survey, three latosol profiles differently affected by MSW leachates in the region of Londrina (Paraná, Brazil) were selected. The aims were to evaluate the extent of their contamination, to better understand the fate of potentially harmful metals in tropical soils and rank the determining factors. Samples between 0.5 and 7 m depth were analyzed for their physical, mineralogical and chemical properties, and their micro-morphology was described by optical and transmission electron microscopy. Two steps of a sequential extraction procedure helped to assess the mobility of elements and to better discriminate between metals originating from pedogenesis and issued from MSW. These combined approaches showed that exposed soil profiles have been impacted at various depths, down to 7 m, through increased metal content, especially enhanced mobility of Zn, Co, Mn, Cu and Fe, and through increased salinity and organic matter. The mobility of potentially harmful metals should decrease with pH, which significantly increased in some impacted horizons, but other factors can reverse this trend.     

Calcium,Na, K and Mg Concentrations in Seawater by Inductively Coupled Plasma‐Atomic Emission Spectrometry: Applications to IAPSO Seawater Reference Material,Hydrothermal Fluids and Synthetic Seawater Solutions

We report a measurement procedure to determine simultaneously the major cation concentrations (Na, Ca, K and Mg) of seawater‐derived solutions by inductively coupled plasma‐atomic emission spectrometry. The best results were obtained when the IAPSO (‘standard’) seawater reference material was diluted by thirty times with Milli‐Q^® water. We obtained an average reference value r_K (the ratio of the mass fraction of potassium to that of chlorine, i.e., (g kg^?1)/(g kg^?1)) for IAPSO seawater of 0.0205 ± 0.0006 (2.9% RSD), not significantly different from 0.0206 ± 0.0005 (2.4% RSD) for seawater composition reported in the literature. The measured Na, Ca and Mg concentrations correspond to r_Na, r_Ca and r_Mg values of 0.5406 ± 0.0026 (0.5% RSD), 0.02192 ± 0.00048 (2.2% RSD) and 0.06830 ± 0.00047 (0.7% RSD), respectively, in line with previous values measured by wet‐chemistry and atomic absorption spectrophotometry or wet‐chemical titration. Our measurement procedure was used successfully on synthetic seawater solutions and high‐temperature hydrothermal fluids.     

Fluid migration at the basement/sediment interface along the margin of the Southeast basin (France): implications for Pb–Zn ore formation

This study investigates the isotopic composition (C, O, S and Sr) of carbonates, sulphates and sulphide cements in the rock matrix and fracture fillings in geological formations of the Southeast basin of France, using core samples collected during the Deep Geology of France programme (GPF Ardèche theme). The Southeast basin belongs to the Alpine Tethyan margin. It is one of the thickest sedimentary basins in Europe, reaching upwards of 9 km in certain locations. The main fluid transfer from the basin is related to the large Pb–Zn Mississippi Valley-type district along the southern margin of the Massif Central block. A synthesis of the tectonic, mineralogical and petrographic investigations on the GPF boreholes shows that a major fluid circulation event occurred across the Alpine margin of Tethys during the Early Jurassic (Hettangian–Bathonian). It produced a general cementation of the rock porosity through precipitation of dolomite, sulphate and barite. Fracture fillings yield isotopic signatures distinct from the matrix cements. Matrix cements have particular characteristics, i.e. δ³⁴S and δ¹³C that agree with a marine origin. The δ³⁴S values of Permo-Carboniferous to Triassic sulphides from fracture cements are interpreted as resulting from the thermo-chemical reduction of sulphates. Fracture sulphates in the same geological formations yield δ³⁴S values that define a relatively homogeneous end-member, whose composition is similar to sulphates in the Largentière Pb–Zn ore deposit. The source of S is attributed to the Permo-Carboniferous succession. The borehole fracture fillings are attributed to a major fluid circulation stage compatible with the Early Jurassic stage identified from the geological investigation of the boreholes. The formation of the Largentière deposit is considered as resulting from the mixing of this Early Jurassic fluid with continental hydrothermal fluids circulating in a basement horst, along its margin with the sedimentary basin. Other Pb–Zn deposits may also be related to fluid migration along the basement/sedimentary cover interface in the eastern and western parts of the Massif Central. This regional fluid circulation event may represent a geodynamic marker of the Jurassic extensional phase.     

Coleopteran evidence for a mosaic of environments at high altitude in the eastern Pyrénées,France, during the climatic transition between the Allerød and Younger Dryas

Late‐glacial environmental and climatic implications are inferred from an insect fauna from organic sediments infilling a palaeochannel on the banks of the River Têt, eastern Pyrénées, France. A pine cone in association with the insect fauna has been radiocarbon dated to 10 920 ± 60 yr BP, namely close to the Allerød – Younger Dryas boundary. Two distinct insect associations appear to be recognisable here. One is an assemblage typical of the high altitude forest and a second is characteristic of an alpine grassland. The close coexistence of these two assemblages is attributed to the climatic cooling towards the start of the Younger Dryas Stadial, when the forest cover broke up into remnant patches interspersed by alpine grassland. It is suggested that in a region of such high relief a mosaic of habitats may have been caused by patchy differences in insolation aspect, especially during a period of climatic deterioration. Copyright © 1999 John Wiley & Sons, Ltd.