Philippe Behra

Anomalous mercury isotopic compositions of fish and human hair in the Bolivian Amazon.

We report mercury (Hg) mass-dependent isotope fractionation (MDF) and mass-independent isotope fractionation (MIF) in hair samples of the Bolivian Esse Ejjas native people and in several tropical fish species that constitute their daily diet. MDF with delta(202)Hg ranging from -0.40 to -0.92 per thousand for fish and +1.04 to +1.42 per thousand for hair was observed. Hair samples of native people with a fish-dominated diet are enriched by +2.0 +/- 0.2 per thousand in delta(202)Hg relative to the fish consumed. Both odd Hg isotopes, (199)Hg and (201)Hg, display MIF in fish (from -0.14 to +0.38 per thousand for Delta(201)Hg and from -0.09 to +0.55 per thousand for Delta(199)Hg) and in hair (from +0.12 to +0.66 per thousand for Delta(201)Hg and from +0.14 to +0.81 per thousand for Delta(199)Hg). No significant difference in MIF anomalies is observed between Hg in fish and in human hair, suggesting that the anomalies act as conservative source tracers between upper trophic levels of the tropical food chain. Fish Hg MIF anomalies are 10-fold lower than those published for fish species from midlatitude lakes. Grouping all Amazonian fish species per location shows that Delta(199)Hg:Delta(201)Hg regression slopes for the clear water Itenez River basin (0.95 +/- 0.08) are significantly lower than those for the white water Beni River basin (1.28 +/- 0.12). Assuming that the observed MIF originates from aquatic photoreactions, we calculated limited photodemethylation of monomethylmercury (MMHg) in the Beni River floodplains and insignificant photodemethylation in the Itenez River floodplains. This is possibly related to lower residence times of MMHg in the Itenez compared to the Beni River floodplains. Finally, a significantly negative Delta(201)Hg of -0.14 per thousand in Beni River fish suggests that the inorganic Hg precursor to the MMHg that bioaccumulates up the food chain defines an ecosystem specific non-zero Delta(201)Hg baseline. Calculation of photodemethylation intensities from Hg or MMHg MIF, therefore, requires a baseline correction.

Operator-splitting procedures for reactive transport and comparison of mass balance errors

Operator-splitting (OS) techniques are very attractive for numerical modelling of reactive transport, but they induce some errors. Considering reactive mass transport with reversible and irreversible reactions governed by a first-order rate law, we develop analytical solutions of the mass balance for the following operator-splitting schemes: standard sequential non-iterative (SNI), Strang-splitting SNI, standard sequential iterative (SI), extrapolating SI, and symmetric SI approaches. From these analytical solutions, the operator-splitting methods are compared with respect to mass balance errors and convergence rates independently of the techniques used for solving each operator. Dimensionless times, NOS, are defined. They control mass balance errors and convergence rates. The following order in terms of decreasing efficiency is proposed: symmetric SI, Strang-splitting SNI, standard SNI, extrapolating SI and standard SI schemes. The symmetric SI scheme does not induce any operator-splitting errors, the Strang-splitting SNI appears to be O(N2OS) accurate, and the other schemes are first-order accurate.

Hg speciation and stable isotope signatures in human hair as a tracer for dietary and occupational exposure to mercury.

Exposure of humans and wildlife to various inorganic and organometallic forms of mercury (Hg) may induce adverse health effects. While human populations in developed countries are mainly exposed to marine fish monomethylmercury (MMHg), this is not necessarily the case for developing countries and diverse indigenous people. Identification of Hg exposure sources from biomonitor media such as urine or hair would be useful in combating exposure. Here we report on the Hg stable isotope signatures and Hg speciation in human hair across different gold miner, indigenous and urban populations in Bolivia and France. We found evidence for both mass-dependent isotope fractionation (MDF) and mass-independent isotope fractionation (MIF) in all hair samples. Three limiting cases of dominant exposure to inorganic Hg (IHg), freshwater fish MMHg, and marine fish MMHg sources are used to define approximate Hg isotope source signatures. Knowing the source signatures, we then estimated Hg exposure sources for the Bolivian gold miner populations. Modeled IHg levels in hair correspond well to measured IHg concentrations (R = 0.9), demonstrating that IHg exposure sources to gold miners can be monitored in hair samples following either its chemical speciation or isotopic composition. Different MMHg and inorganic exposure levels among gold miners appear to correspond to living and working conditions, including proximity to small towns, and artisanal vs large scale mining activity.

XPS study of the sorption of Hg(II) onto pyrite FeS2

In this study, the sorption of Hg(II) onto pyrite was investigated as a function of the aqueous solution pH. X-ray photoelectron spectroscopy (XPS) was used to characterize the surfaces, and to identify the adsorbed species when possible. After 12 h of equilibration at a given initial pH (between 6 and 10.5), slabs of pyrite were in contact with Hg(II) solution (210 μM, constant ionic strength fixed with 0.01 M NaNO 3 ) for 24 h. The final pH ranged between 4.1 and 3.6. The solid samples were then dried and transferred into the XPS machine for surface analyses (Hg 4f, S 2p, O 1s and Fe 2p levels). Taking advantage of the differential charge effect when the surface was partly covered with Fe(III) oxyhydroxides, it was shown that Hg could be sorbed onto both pyritic zones and oxidized patches. On pyritic zones where no charge effect was observed, the Hg 4f 7/2 level was pointed out at 100.7 eV, ruling the presence of Hg(0) at the surface out. The S 2p level analyses clearly showed that the main component was S 2 2- , with some traces of polysulphur. Neither S(II) nor S(VI) were detected in any experiment, excluding the formation of HgS, sulphate and thiosulphate. Most observations were understood as the formation of two surface complexes between mercury and either the pyritic functional groups or the oxyhydroxide sites.

Sorption of tributyltin onto a natural quartz sand

The aim of this study is to understand the sorption of tributyltin (TBT) onto natural quartz sand by classical batch experiments and spectroscopic surface analyses. At pH<6, the major species of TBT is the cation TBT(+). Due to the presence of both the cationic part and the butyl chains, TBT should present amphiphilic properties. For concentrations lower than 40 microM, TBT sorption occurs as a homovalent 1:1 cation exchange between either H(+) or Na(+) and TBT(+). The increasing affinity of TBT with respect to the different materials follows the series kaolinite<<natural sand<treated sand<pure quartz. From XPS analyses, where the chemical environment of Sn did not change, indicating possible complete reversibility of the TBT sorption, it seems that inner-sphere surface complexes could be formed due to the increase in the 3d-level binding energy. At TBT concentrations higher than 100 microM, we showed by flotation experiments and XPS analysis that the surface becomes hydrophobic. After one monolayer was formed, the TBT sorption could thus be due to hydrophobic interaction between the butyl chains of the sorbed TBT and those of the TBT still available from the bulk solution. This mechanism is consistent with surface condensation and the shape of the sorption isotherm.

The Effect of Oxide Coating Dissolution on Cd Transport Through a Natural Quartz Sand

The role of flow rate on Cd transport through a natural aquifer sand was investigated using a laboratory column set-up with particular reference to dissolution processes of external coatings. Clays and (hydr)oxides dissolution was investigated by tests performed feeding the column with Cd-free solutions at three different flow rates (0.2, 1 and 5 mL min−1). Flow rate significantly affected only the dissolution of Fe-containing coatings by releasing into the liquid phase different amounts of Fe. Cd transport experiments showed a strong effect of flow rate on Cd breakthrough curves and the lowest Cd adsorption was observed at the lowest flow rate. This behavior was fully explained in terms of competition between dissolved Fe and applied Cd for the same adsorption sites. Comparison of the Cd transport behavior on a pure quartz sand allowed confirmation of the strong influence of clay and (hydro)oxide coatings in determining the surface properties of the heterogeneous natural materials. An equilibrium model was proposed to describe the dynamic Cd behavior under the different experimental conditions (flow rates and Cd concentrations).

Modélisation du transport réactif en milieu poreux : schéma itératif associé à une combinaison d'éléments finis discontinus et mixtes-hybrides

The sequential iterative approach (SIA) scheme is the most efficient method for modelling reactive transport in porous media with the operator-splitting approach. A combination of finite discontinuous and finite mixed-hybrid elements is a powerful method for solving solute transport in porous media, but the use of this method for SIA scheme induces numerical difficulties. In this paper, a new method is developed to solve reactive transport by using both the SIA scheme and a combination of finite discontinuous and finite mixed elements. The proposed method is tested by modelling a column experiment. To cite this article: J. Carrayrou et al., C. R. Mecanique 331 (2003).

Sorption Mechanisms at the Solid-Water Interface

Soils, solid phases or colloids have been for a long time considered as efficient barriers to trap pollutants during their migration. Meanwhile, this statement has been more and more questioned, and it becomes necessary not only to protect the resource « water » but also to prevent all deterioration of its quality. The cycling of water is a complex system which has to be better understood in order to predict the environmental impact of key parameters on the different compartments of the natural system.