Constantes de formation des complexes hydroxydés de l'aluminium en solution aqueuse de 20 a 70°C

Stability constants of hydroxocomplexes of Al(III):Al(OH)²⁺ and A1(OH)₄^? have been measured in the 20–70°C temperature range by reactions involving only dissolved species. The stability constant ${}^1\text{K}{}_1$ of the first complex ion is studied by measuring pH of solutions of aluminium salts at several concentrations. ${}^1\text{β}{}_4$ of aluminate ion is deduced from equilibrium constants of the reaction between the trioxalato aluminium (III) complex ion and Al³⁺ in acid medium, and between the same complex ion and A1(OH)₄^? in alkaline medium. The K values and the associated ΔH are ${}^1\text{K}{}_1\text{= 10}{}^{\mathrm{?5.00}}$ and ΔH₁ = 11.8 Kcal; ${}^1\text{β}{}_4\text{= 10}{}^{\mathrm{?22.20}}$ and ΔH₄ = 42.45 Kcal. These last results are not in agreement with the values of recent tables for $\text{ΔG}{}^0\text{?}$ and $\text{ΔH}{}^0\text{?}$ of Al³⁺ and Al(OH)₄^?. We suggest a consistent set of data for dissolved and solid Al species and for some aluminosilicates.     

Combined amino acid speciation in lake sediment and porewater (Aydat Lake, France)

Dissolved and particulate fractions extracted from a lake diatom ooze were examined for individual amino acids. The study focused on combined amino acids, the predominant form in the interstitial dissolved pool (> 90%). An abundance of glycine and -alanine was observed in porewater samples of sediments both squeezed manually and gathered with in-situ dialysis (peeper). Sedimentpress squeezing and leaching of the sediment by water gave higher total quantities and different compositions (with more aliphatic and aromatic protein amino acids, -alanine being predominant). These two methods modify the original composition, presumably due to the formation of Fe-oxides and dissolution of sediment organic fractions, the alteration being aggravated if squeezing is delayed.Filtration after acidification of porewaters enabled us to distinguish two compartments: a protein-like agglutinated fraction, and a filtrate with a high glycine and -alanine content. Further division of the filtrate by adsorption on XAD or cation-exchange resins did not reveal additional fractions with different individual amino acid compositions. A link is suggested between the agglutinated fraction and the special composition of the porewaters extracted with sediment-press.Dissolved organic carbon (DOC) and total dissolved hydrolysable amino acids (TDHAA) ( 10 mg/l and 13 M, respectively) did not increase with depth, as opposed to dissolved inorganic carbon and volatile carbon. Amino acid-C accounted for less than 4% of DOC in porewaters.Individual amino acid compositions in the sediments were similar in all grain size fractions. Chemically extracted fractions had specific compositions: (l) organic fractions (alkali extracts and HF-insoluble residues) have a similar protein amino acid composition; (2) acid extracts have more acidic amino acids (HCI) or more glycine and non protein amino acids (BF). The similarity of amino acid compositions in the sediment HF-soluble fraction and the dissolved pool is discussed with respect to interactions between iron-silicate authigenic phases and porewaters.     

Apatite fission track analysis in the Argentera massif: evidence of contrasting denudation rates in the External Crystalline Massifs of the Western Alps

Apatite fission track dating from a central transect in the Argentera massif (southernmost External Crystalline Massif = ECM) yielded ages between 8.05 ± 0.6 and 2.4 ± 0.2 Myr, with a positive age/altitude correlation above 3 Ma, 1200 m. Recognising a thermal peak at c . 250°C, 33 Ma, based on stratigraphic, metamorphic and ³⁹Ar/⁴⁰Ar data, the present results suggest a slow cooling rate (8–5°C) for the Argentera massif during the Oligocene–early Pliocene. This rate compares with that from the Pelvoux massif, but contrasts with those observed in the northern ECM (Mont-Blanc and Aar: up to 14°C Myr⁻¹) for the same time interval. This can be related to the different location of the ECM within the collided European margin. At about 3–4 Ma, the denudation rate would have increased up to c . 1 mm yr⁻¹ in the Argentera massif, reaching the same value as in the Belledonne and northern ECM, likely a consequence of Penninic thrust inversion.     

Chemical evolution of waters during long term interaction with granitic rocks in northern Switzerland

As part of an assessment of crystalline rock as a potential host for a nuclear waste repository, water samples were collected from more than 50 locations from the crystalline basement where it is under sedimentary cover in Northern Switzerland and where it is at the surface in the Black Forest. These samples describe the changing chemistry of water in an extended flow system from dilute recharge waters far from chemical equilibrium with its host rock to saline waters at temperatures of 50 to 100°C with residence times far in excess of 105 a that have reached chemical equilibrium with their host rock.This unique set of samples allows an analysis of the chemical evolution of granitic waters from surficial waters far from equilibrium to almost equilibrated waters. Mobile ions, rare gases and isotopic data are used to estimate the extent of reaction between waters and their host rock. The evolution of controlled elements is interpreted as a function of this extent of reaction. Silica contents correspond to approximate equilibrium even in the recharge waters. The relative concentrations of Ca and especially Mg are significantly lower in the borehole waters than in recharge waters indicating a trend towards equilibrium. The Na/K ratios correspond to equilibrium only in the most evolved, older, waters which are shown to be at full equilibrium.     

Biogeochemical modelling of anaerobic vs. aerobic methane oxidation in a meromictic crater lake (Lake Pavin, France)

Methane is a powerful greenhouse gas and its concentration in the atmosphere has increased over the past decades. Methane produced by methanogenic Archae can be consumed through aerobic and anaerobic oxidation pathways. In anoxic conditions found in freshwater environments such as meromictic lakes, CH₄ oxidation pathways involving different terminal electron acceptors such as , , and oxides of Fe and Mn are thermodynamically possible. In this study, a reactive transport model was developed to assess the relative significance of the different pathways of CH₄ consumption in the water column of Lake Pavin. In most cases, the model reproduced experimental data collected from the field from June 2006 to June 2007. Although the model and the field measurements suggest that anaerobic CH₄ oxidation may contribute to CH₄ consumption in the water column of Lake Pavin, aerobic oxidation remains the major sink of CH₄ in this lake.     

Asthenospheric and lithospheric sources for Mesozoic dolerites from Liberia (Africa): trace element and isotopic evidence

Combined elemental, and Sr and Nd isotopic data are presented for Mesozoic dolerite dikes of Liberia (Africa) which are related to the initial stage of opening of the Atlantic Ocean.The large scatter of both trace element and isotopic data allows the identification of five groups of dolerites which cannot be related to each other by simple processes of mineral fractionation from a common source. On the contrary, the observed chemical and isotopic variation within some dolerites (Groups I and II) may result either from variable degrees of melting of an isotopically heterogeneous source or mixing between enriched and depleted oceanic type mantle. For the other dolerites (Groups III–V) mixing with a third mantle source with more radiogenic Sr and with element ratios characteristic of subduction environments is suggested. This third source is probably the subcontinental lithospheric mantle.Finally, no significant modification by interaction with continental crust is apparent in most of the analyzed samples.     

Marine Sr (Ca) input in Quaternary volcanic rock weathering profiles from the Mediterranean coast of Morocco: Sr isotopic approach

Carbonate commonly accumulates in weathering profiles developed on noncalcareous parent material under arid and semiarid climatic conditions. Such weathering profile types are widespread in Morocco, making it critical to know the sources of the calcium in order to understand the genesis of carbonate-rich soils. In this study, we use ⁸⁷Sr/⁸⁶Sr as a geochemical tracer of the Ca sources in weathering profiles developed on volcanic rocks (basalt, tuff, andesite and latite) in the Mediterranean coast of Morocco. The results show that the most of the Sr, and hence Ca, is of an external origin, derived from (i) sea-water for the profiles located near to the coast or (ii) sea-water plus Liassic carbonate outcropping in the catchment for the profiles more distant from the coastline. The contribution of the host rock is small, being less than 25%. The ratio of the Sr (Ca) from the parent material to that from the external sources is controlled by the degree of porosity developed in the profile.     

The transition from alkali basalts to kimberlites: Isotope and trace element evidence from melilitites

Eighteen Cenozoic melilitite samples from Spain, France, West Germany and Czechoslovakia have been analyzed for major and trace elements (including REE) together with their Sr and Nd isotopic compositions. Leaching experiments produced significant shifts of their⁸⁷Sr/⁸⁶Sr ratio indicative of a contamination by a crustal component. Most samples fall within the Sr-Nd mantle array with ?_Nd values in the 1.5–6 range. These values are considered as minimum for the melilitite mantle source hence demonstrating its time integrated LRE depletion. The Ni and Cr contents of the samples are typical of primary magmas and exclude extensive crystallization of olivine and pyroxene in a closed system. However, the chemical relationships suggest that dilution of the liquids by mafic minerals of the conduits during their ascent has been important. The REE patterns show some variations which are interpreted by this dilution effect. Once normalized to Yb they are closely similar and perfectly distinguishable from those of alkali basalts and kimberlites. All of these rocks have Ce/Yb ratios which are high but distinctive for each rock type: 40 to 200 times the chondritic ratio for kimberlites, 20 to 30 for melilitites, 8 to 15 for alkali basalts. As contamination is likely to have modified somewhat the isotopic characteristics of most of these rocks, there is no overwhelming evidence that their source is chemically different. The Ba and Rb contents together with the REE patterns of the melilitites would constrain the degree of melting to be very small (<0.2%). The calculation of batch melting and steady zone refining models suggests that kimberlites, melilitites and alkali basalts may have been derived by equilibration of deep melts with different upper mantle levels characterized by decreasing garnet/clinopyroxene ratios. The strongly incompatible elements are enriched in the melt during its ascent by leaching of the wall rocks. For the steady zone refining model, the degree of melting concept loses its significance and the difficult requirement of extracting small liquid fractions from a molten source disappears. Within the frame of this model, the preenrichment of the kimberlite, melilitite and alkali basalts source in incompatible elements by metasomatic fluids is no longer necessary.