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.     

On the co-orbital motion in the planar restricted three-body problem: the quasi-satellite motion revisited

In the framework of the planar and circular restricted three-body problem, we consider an asteroid that orbits the Sun in quasi-satellite motion with a planet. A quasi-satellite trajectory is a heliocentric orbit in co-orbital resonance with the planet, characterized by a nonzero eccentricity and a resonant angle that librates around zero. Likewise, in the rotating frame with the planet, it describes the same trajectory as the one of a retrograde satellite even though the planet acts as a perturbator. In the last few years, the discoveries of asteroids in this type of motion made the term “quasi-satellite” more and more present in the literature. However, some authors rather use the term “retrograde satellite” when referring to this kind of motion in the studies of the restricted problem in the rotating frame. In this paper, we intend to clarify the terminology to use, in order to bridge the gap between the perturbative co-orbital point of view and the more general approach in the rotating frame. Through a numerical exploration of the co-orbital phase space, we describe the quasi-satellite domain and highlight that it is not reachable by low eccentricities by averaging process. We will show that the quasi-satellite domain is effectively included in the domain of the retrograde satellites and neatly defined in terms of frequencies. Eventually, we highlight a remarkable high eccentric quasi-satellite orbit corresponding to a frozen ellipse in the heliocentric frame. We extend this result to the eccentric case (planet on an eccentric motion) and show that two families of frozen ellipses originate from this remarkable orbit.     

NanoSIMS analysis of organic carbon from the Tissint Martian meteorite: Evidence for the past existence of subsurface organic‐bearing fluids on Mars

Two petrographic settings of carbonaceous components, mainly filling open fractures and occasionally enclosed in shock‐melt veins, were found in the recently fallen Tissint Martian meteorite. The presence in shock‐melt veins and the deuterium enrichments (δD up to +1183‰) of these components clearly indicate a pristine Martian origin. The carbonaceous components are kerogen‐like, based on micro‐Raman spectra and multielemental ratios, and were probably deposited from fluids in shock‐induced fractures in the parent rock of Tissint. After precipitation of the organic matter, the rock experienced another severe shock event, producing the melt veins that encapsulated a part of the organic matter. The C isotopic compositions of the organic matter (δ¹³C = ?12.8 to ?33.1‰) are significantly lighter than Martian atmospheric CO₂ and carbonate, providing a tantalizing hint for a possible biotic process. Alternatively, the organic matter could be derived from carbonaceous chondrites, as insoluble organic matter from the latter has similar chemical and isotopic compositions. The presence of organic‐rich fluids that infiltrated rocks near the surface of Mars has significant implications for the study of Martian paleoenvironment and perhaps to search for possible ancient biological activities on Mars.     

Robust dual‐sensor data sea‐surface ghost attenuation for quality control purposes

Three‐dimensional receiver ghost attenuation (deghosting) of dual‐sensor towed‐streamer data is straightforward, in principle. In its simplest form, it requires applying a three‐dimensional frequency–wavenumber filter to the vertical component of the particle motion data to correct for the amplitude reduction on the vertical component of non‐normal incidence plane waves before combining with the pressure data. More elaborate techniques use three‐dimensional filters to both components before summation, for example, for ghost wavelet dephasing and mitigation of noise of different strengths on the individual components in optimum deghosting. The problem with all these techniques is, of course, that it is usually impossible to transform the data into the crossline wavenumber domain because of aliasing. Hence, usually, a two‐dimensional version of deghosting is applied to the data in the frequency–inline wavenumber domain. We investigate going down the “dimensionality ladder” one more step to a one‐dimensional weighted summation of the records of the collocated sensors to create an approximate deghosting procedure. We specifically consider amplitude‐balancing weights computed via a standard automatic gain control before summation, reminiscent of a diversity stack of the dual‐sensor recordings. This technique is independent of the actual streamer depth and insensitive to variations in the sea‐surface reflection coefficient. The automatic gain control weights serve two purposes: (i) to approximately correct for the geometric amplitude loss of the Z data and (ii) to mitigate noise strength variations on the two components. Here, Z denotes the vertical component of the velocity of particle motion scaled by the seismic impedance of the near‐sensor water volume. The weights are time‐varying and can also be made frequency‐band dependent, adapting better to frequency variations of the noise. The investigated process is a very robust, almost fully hands‐off, approximate three‐dimensional deghosting step for dual‐sensor data, requiring no spatial filtering and no explicit estimates of noise power. We argue that this technique performs well in terms of ghost attenuation (albeit, not exact ghost removal) and balancing the signal‐to‐noise ratio in the output data. For instances where full three‐dimensional receiver deghosting is the final product, the proposed technique is appropriate for efficient quality control of the data acquired and in aiding the parameterisation of the subsequent deghosting processing.     

Curvature analysis of triangulated surfaces in structural geology

This paper addresses the problem of characterizing the shape of a geological surface on the basis of its principal curvatures. The surface is assumed to be modeled as a set of adjacent triangles defined by the location of their vertices and a method is proposed for estimating numerically the principal curvatures at the vertices of the triangles using a local C² interpolant. Also shown is how principal curvatures can be useful for studying the deformation of a geological surface (with application to 3D balanced unfolding), and analyzing the folding or faulting of the interface between two adjacent layers.     

Surface chemistry and reactivity of biogenic silica

The surface chemistry of cultured diatoms was compared to that of biosiliceous material in Southern Ocean sediments, using potentiometric titrations and aluminum adsorption experiments. Aerosil 200, a well-studied synthetic amorphous silica, served as reference solid. Surface charge development and aluminum adsorption on cultured diatom shells were comparable to Aerosil. The surface chemical properties of biosiliceous material buried to depths of 15-25 cm in Southern Ocean sediments, however, deviated markedly from those of the cultured diatoms. In pH range 4-8.5, the surface charge density was systematically lower for biogenic silica from the sediments. In addition, the aluminum adsorption edge on the biosiliceous sediments was shifted to higher pHs by about 0.4 units. The results indicate that ionizable surface silanol groups on diagenetically altered diatom shells are less abundant and, possibly, less acidic than on freshly cultured diatoms. The observed differences in surface chemical structure are consistent with the progressive loss of reactivity, or aging, of biogenic silica which promotes its preservation in sediments.     

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.     

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.     

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.     

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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