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.     

Relations entre déformation et métamorphisme alpin dans les schistes noirs helvétiques : l’apport de la fabrique magnétique

Résumé

La fabrique magnétique des schistes noirs du Jurassique helvétique au pourtour des massifs de l’Aar et du Gothard (Alpes suisses) reflète, en fonction du métamorphisme croissant, l’orientation préférentielle de minéraux magnétiques d’origines diverses : la magnétite primaire, les phyllosilicates et la pyrrhotite métamorphiques. La foliation magnétique est parallèle à la première schistosité pénétrative même si celle-ci est effacée par une seconde schistosité. La linéation magnétique indique retirement lié à la direction de transport des nappes. Dans la partie la plus métamorphique où apparaît la pyrrhotite au cours de la déformation, la fabrique magnétique permet de situer l’apparition de ce minéral dans la tectonique polyphasée. Les propriétés magnétiques anisotropes de la pyrrhotite s’avèrent plus complexes que le modèle usuel de marqueurs planaires et l’interprétation des linéations observées doit en tenir compte.     

Mineralogy and geochemical behaviour during weathering of greenstone belt under tropical dry conditions in the extreme North Cameroon (Central Africa)

Mineralogy, major, trace and rare earth elements of a weathering profile developed on tertiary greenstone belt in the extreme North Cameroon are reported. The aim of which was to investigate mineralogical evolution and element mobilization and redistribution during weathering under dry tropical climate. The weathering profile consists of four main horizons: (1) a spheroidal weathering zone constituted by a corestone–shell complex, (2) a C horizon, (3) a Bw horizon and an Ah horizon. The results indicate that nontronite, a Fe-rich smectite, is the exclusive clay mineral formed in the exfoliated shells and the C horizon. It is associated with kaolinite in the upper horizons. The coexistence of these two clay minerals induced a decrease of CEC and pH which becomes neutral. The weathering index (WI) values reveal that weathering becomes more and more intensive from the corestone up to Bw horizon, which is the most weathered horizon in the weathering profile. Mass balance calculations, using Th as immobile element, indicate that Ti is quite mobile and that Al and Fe are relatively enriched at the bottom and strongly leached at the top of the profile. Alkalis and alkaline earth elements are strong leached through out the profile, except Ca which displays similar trend as Al and Fe. The same goes for LILE (Cs, Sr), TTE (Cr, Co, Ni) and HSFE (Y, Nb, Hf). In opposite, REE are depleted at the bottom and enriched in the upper horizons, with more enrichment for LREE than for HREE. It appears that weathering of greenstone belt causes a fractionation of HREE and induces a concentration of LREEs. Ce and Eu anomalies display opposite behaviour.     

Les laves du mont Bangou : une première manifestation volcanique éocène, à affinité transitionnelle,de la Ligne du Cameroun

Mount Bangou, an Eocene volcano (⁴⁰K–⁴⁰Ar ages between 44.7 and 43.1 ± 1 Ma) is the oldest dated volcano of the Cameroon Line. In this region, two magmatic series, evolving by fractional crystallization, show transitional affinities that are exceptionally known in this sector. Mineral compositions of basaltic rocks (scarce modal olivine and occurrence of normative hypersthene) as well as geochemical characteristics (low Ba, La, Ta contents and high Y/Nb ratios) are in agreement with this trend. The succession of magmas evolving in time from transitional to more typical alkaline compositions is evidenced in a continental setting. To cite this article: J. Fosso et al., C. R. Geoscience 337 (2005).     

Enhanced Oxygen Isotope Determination in Uranium Oxides Using BrF5 Fluorination

A new method for accurate determination of oxygen isotopes in uranium oxides encountered in the nuclear fuel cycle was developed using the conventional BrF₅ fluorination technique. Laser‐assisted fluorination was tested for comparison. We focused on fine powders of triuranium octoxide (U₃O₈), uranium dioxide (UO_2±x with 0 ≤ x ≤ 0.25), uranium trioxide (UO₃.nH₂O, with 0.8 ≤ n ≤ 2) and diuranates (M₂U₂O₇.nH₂O, with M = NH₄, Na or Mg_0.5 and 0 ≤ n ≤ 6). Fluorination at room temperature and heating under vacuum at 150 °C are shown to eliminate both adsorbed and structural water from the powder samples. Precision fit for purpose of δ¹⁸O values (± 0.3‰, 1s) and oxygen yields (close to 100%) were obtained for U₃O₈ and UO₂ where oxygen is only bound to uranium. A lower precision was observed for UO₃.nH₂O and M₂U₂O₇.nH₂O where oxygen is both present in the structural H₂O and bonded to uranium and where the extracted O_2(g) can be contaminated by NF₃ and NO_x compounds. Laser‐assisted fluorination gave shifted δ¹⁸O values between +0.8 and +1.4‰ for U₃O₈, around ?0.8‰ for UO₃.nH₂O and between ?3.9 and ?4.5‰ for M₂U₂O₇.nH₂O (± 0.3‰, 1s) compared with the conventional method.     

Fitting the Linear Model of Coregionalization by Generalized Least Squares

In geostatistical studies, the fitting of the linear model of coregionalization (LMC) to direct and cross experimental semivariograms is usually performed with a weighted least-squares (WLS) procedure based on the number of pairs of observations at each lag. So far, no study has investigated the efficiency of other least-squares procedures, such as ordinary least squares (OLS), generalized least squares (GLS), and WLS with other weighing functions, in the context of the LMC. In this article, we compare the statistical properties of the sill estimators obtained with eight least-squares procedures for fitting the LMC: OLS, four WLS, and three GLS. The WLS procedures are based on approximations of the variance of semivariogram estimates at each distance lag. The GLS procedures use a variance–covariance matrix of semivariogram estimates that is (i) estimated using the fourth-order moments with sill estimates (GLS₁), (ii) calculated using the fourth-order moments with the theoretical sills (GLS₂), and (iii) based on an approximation using the correlation between semivariogram estimates in the case of spatial independence of the observations (GLS₃). The current algorithm for fitting the LMC by WLS while ensuring the positive semidefiniteness of sill matrix estimates is modified to include any least-squares procedure. A Monte Carlo study is performed for 16 scenarios corresponding to different combinations of the number of variables, number of spatial structures, values of ranges, and scale dependence of the correlations among variables. Simulation results show that the mean square error is accounted for mostly by the variance of the sill estimators instead of their squared bias. Overall, the estimated GLS₁ and theoretical GLS₂ are the most efficient, followed by the WLS procedure that is based on the number of pairs of observations and the average distance at each lag. On that basis, GLS₁ can be recommended for future studies using the LMC.