Michel Loubet

Sorption of lanthanides on smectite and kaolinite

Abstract Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3–9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO 3 or NaClO 4 ) under atmospheric conditions or N 2 flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO 2 , but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient ( K D ) above pH 5.5. At 0.025 M, the measured K D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K D . This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.

Fundamental processes controlling the first stage of alteration of a basalt glass by seawater: an experimental study between 200° and 320°C

The first stage of alteration of a basalt glass by seawater has been studied experimentally between 200° and 320°C under vapor pressure, following both the chemical evolution of the reacting solutions during the experiments and the chemical and mineralogical transformations of the altered glass surface via microprobe, scanning transmission electron microscope and resonant nuclear reactions. The alteration is controlled by diffusion of dissolved species through an altered layer and not by surface chemical reaction. Selective removal of cations with respect to SiO2 leads to the formation of a thick, porous protonated surface layer enriched in SiO2. Aqueous diffusion of dissolved species from the reacting glass and from solution through the pores of this layer results in the formation of an amorphous silicate gel which is the precursor of normal crystalline clays (saponites) appearing in a later stage. Computer simulations of the alteration generated with the EQ3/6 computer software package account for the chemical composition of the rim and the sequence of secondary minerals found in the experiments.

Do deep tree roots provide nutrients to the tropical rainforest

The contribution of deep tree roots to the nutrition of a tropicalrainforest were studied along an edaphic transect in French Guyana. Soil typeswere mapped in relation to the texture of the upper horizons and the depth ofoccurrence of the loamy saprolite. The position of mature individuals of fourcommon species, differing by they rooting depth, was identified and tree leaveswere analysed for major nutrients and strontium (Sr) isotopic ratios.On average, the range of leaf isotopic ratio (87Sr/86Sr= 0.714–0.716) was narrow compared to that of bulk soils(87Sr/86Sr = 0.72–0.77). Steep gradients ofincreasing 87Sr/86Sr in roots with soil depth were foundin all investigated profiles, which indicated that the flux of Sr deposited inrain and leached from the litter layer was tightly retained in the upper soillayers. Over the whole of the site, as well as within each soil unit, tree87Sr/86Sr ratios were very similar whatever the species,and close to litter and near-surface roots 87Sr/86Srratios, suggesting no or very little Sr contribution from deep tree roots.Variations of Ca and Sr concentrations in leaves were strongly correlated butnot with leaf 87Sr/86Sr ratios. These results support thetheory that Sr and Ca uptake and cycling are mostly superficial in tropicalrainforests.

Localisation of mineral uptake by roots using Sr isotopes

To assess the contribution of deep soil horizons to the mineral supply of trees, we investigated the natural variation in the87 Sr/86Sr isotopic ratio of plant-available strontium with soil depth. In three sites of North-western Spain, this ratio increased with soil depth. The comparison of isotopic ratios of tree leaves and roots at different depths showed that most of the Sr accumulation in Eucalyptus globulus and Pinus pinaster growing on shallow and poor soils in this rainy climate originated from the upper soil layers. As Ca and Sr behave similarly in the soil-plant system, this conclusion can be applied to Ca. This superficial uptake is attributed to the low availability of Sr and Ca in the soil as well as to the shortness of the drought period as compared to the length of the growth period. This technique appears to offer a promising way of studying relative root distributions in soils and plant competition for nutrients.

Anthropogenic lead distribution in soils under arable land and permanent grassland estimated by Pb isotopic compositions

The role of land use on fate of metals in soils is poorly understood. In this work, we studied the incorporation of lead in two neighboring soils with comparable pedogenesis but under long-term different agricultural management. Distributions of anthropogenic Pb were assessed from concentrations and isotopic compositions determined on bulk horizon samples, systematical 5-10 cm increment samples, and on 24-h EDTA extracts. Minor amounts of anthropogenic lead were detected until 1-m depth under permanent grassland, linked to high earthworm activity. In arable land, exogenous Pb predominantly accumulated at depths < 60 cm. Although the proximity between the two sites ensured comparable exposition regarding atmospheric Pb deposition, the isotopic compositions clearly showed the influence of an unidentified component for the cultivated soil. This work highlights the need for exhaustive information on historical human activities in such anthropized agrosystems when fate of metal pollution is considered.

Sr isotopic evidence for ion-exchange buffering in tropical laterites from the Paraná, Brazil

Sr isotopes have been measured in laterite sequences and in associated waters from the region of Ribeirao Preto (Parana basin, Brasil), in order to characterize the water-rock interactions corresponding to the successive stages of weathering of these continental flood basalts, We analyzed detailed sections of concentric rims of alteration in ball-shaped spheroids developed around cores of fresh basalts. Waters were also analyzed on the different types of facies in this region: unaltered basalts, thick weathered profiles of lateritic material, and surrounding sandstones, The results show that a major part of the initial Sr is removed from the basalt during the earliest stages of weathering, within the narrow grey rims surrounding the unweathered core. Radiogenic Sr is also leached from hydrothermal minerals located in basalt fractures or disseminated in the basalt groundmass at this early stage. Very high water/rock ratios (of at least 100,000) are calculated for this process, from the Sr-87/Sr-86 in the related waters. A general trend of increasing Sr-87/Sr-86 ratios is observed in the increasingly weathered facies (inner yellow cortexes, red kaolinitic soils and matrices) and in their related waters. The very high Sr-87/Sr-86 ratios of the red kaolinitic horizons probably result from isotopic exchange with radiogenic rainwaters or sandstone waters, and also from the presence of residual or neoformed radiogenic minerals. Budget calculations, as well as experimental leaching of kaolinite samples, suggest that significant amounts of radiogenic Sr can be leached from these facies during weathering, Thus, the kaolinitic facies of tropical laterite profiles are able first to trap strontium from surficial waters, then to provide radiogenic Sr to the waters that weather the fresh basalts at the weathering front. Therefore, the thick weathered horizons must be considered as a natural cation-exchange layer, that play an active role in the weathering process.

Variations of plant and soil 87Sr/86Sr along the slope of a tropical inselberg.

Abstract• From the summit downslope a granitic inselberg in French Guiana, soils and vegetation evolve from bare granite covered by cyanobacteria, to a savannah-type vegetation on thin patchy sandy accumulations, then to a low forest on shallow young soils and to a high forest on deep highly weathered ultisols.• We have used element budgets and Sr isotopic variations in soils and plants to investigate the mineral nutrient supply sources of the different plant communities.• Granite and atmospheric deposition have 87Sr/86Sr ratios of 1.3 and 0.71, respectively. The 87Sr/86Sr ratio of cyanobacteria (0.72) suggests granite weathering by cyanobacteria crusts. The 87Sr/86Sr ratio of the savannah-type vegetation is 0.73 and varies between 0.75 and 0.76 in the low and high forest leaf litter regardless of soil depth, age and degree of impoverishment.• These almost constant ratio suggest that forest Sr comes from rainwater and from the summit of this inselberg, where it is released and redistributed along the slope, by surface flow, lateral redistribution of litter, and mineral particles. However, because of its very low content in the rock and soils, Ca is supplied to plants by atmospheric deposition.Résumé• Du sommet vers la base d’un inselberg granitique (Nouragues, Guyane Française), les sols et la végétation évoluent depuis des savanes sur des ilots sableux entre les affleurements rocheux couverts de cyanobactéries, vers une forêt basse sur sols peu épais, riches en minéraux altérables puis une forêt haute sur sols très profonds et altérés.• Les variations isotopiques du strontium des sols et des plantes ont été mesurées pour rechercher les sources de nutriments des différentes communautés végétales.• Les rapports 87Sr/86Sr du granite et des dépôts atmosphériques sont respectivement de 1,3 et 0,71. Le rapport 87Sr/86Sr des cyanobacteries (0,72) suggère une libération de Sr par altération du granite. Le rapport 87Sr/86Sr de la savanne est de 0,73 et varie entre 0,75 et 0,76 dans les litières de forêt basse et haute, quelle que soit la profondeur, et la richesse en minéraux altérables des sols.• La faiblesse et l’homogénéité surprenante de ces rapports suggèrent une alimentation en Sr des forêts essentiellement à partir de dépôts atmosphériques et des sols de la partie haute de l’inselberg, via des écoulements de surface, des redistributions latérales de litière et de particules minerales lors de crises érosives. Cependant, en raison de l’extrême pauvreté de la roche et des sols en calcium, le Ca des communautés végétales provient de la pluie.

La composition isotopique du plomb : un outil privilégié pour l'estimation de la distribution du plomb anthropique et naturel dans les sols

The isotopic composition of lead: a useful tool to estimate the distribu- tion of exogenous and natural lead in soils. Pb isotopic ratios were analysed in soil horizons and in grain size fractions of two soils, with contrasting pedogenesis. For an andosol, the results highlighted a progressive distribution of exogenous Pb with depth and, at the scale of the soil constituents, an increasing incorporation of exogenous Pb with decreasing particle size. For a podzol, the distribution of exogenous Pb was linked to the dynamics of the organic matter. In the BPh horizon, the 100-200 µm fraction was found to be a predominant soil compartment accumulating exogenous Pb ascribed to the precipitation of Pb on organic compounds around quartz grains.