Patrick Trocellier

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn2SiO4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn2SiO4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.

Metamictization and chemical durability of detrital zircon.

Abstract We have investigated the effect that metamictization has on the weathering of zircon in detrital continental sediments and tropical soils of the Amazon basin, Brazil. The degree of radiation damage in the near-surface region of the zircon grains was determined by Raman microprobe. In each of the four series investigated (i.e., sediment, podzol, topsoil, and subsoil horizons of lateritic soil), the degree of radiation damage ranges from less than 1014 to ~3.5 × 1015 α−decay/mg. The maximum degree of radiation damage coincides with the first percolation threshold of the metamictization process at ~3.5 × 1015 α-decay/mg. Below this threshold, amorphous volumes in the structure of damaged zircon are not connected to each other. The ranges of U, Th, and Pb contents (in ppm) measured by proton induced X-ray emission (PIXE) microanalysis are 100 < U < 7000, 100 < Th < 18000, and 100 < Pb < 1300. Chemical ages, assessed from U, Th, and total-Pb, range between 0.15 Ga and 2.8 Ga. This range is roughly consistent with the ages reported for the Precambrian shields of the Amazon basin (0.45-3.5 Ga). Corresponding radiation doses range between <2 × 1015 and 3 × 1016 α-decay/mg. Comparison of calculated doses with the degree of structural damage indicates that most of the zircon grains have experienced significant annealing. However, the degree of annealing differs from one grain to another. Thus, the acute maximum limit observed for the degree of radiation damage of the whole zircon series is better explained by low-temperature alteration or weathering processes than by thermal resetting. Following this interpretation, our results provide evidence for a dramatic decrease in the chemical durability of zircon in natural weathering environments when the radiation dose exceeds 3.5 × 1015 α-decay/mg. Below the first percolation threshold, the zircon population survives the soil formation intact, but more damaged zircons are dissolved during weathering/ alteration processes.

Adsorption of aqueous Zn(II) species on synthetic zeolites

To supply a good quality drinkable water tends to become a strategic task in both developed and under development countries in the world due to the number of potential contamination sources. One of the major problems is derived from the presence of heavy toxic metals like zinc or lead resulting from industrial activities. Zeolites are known as very efficient mineral substrates for fixing aqueous ionic species through their wide range of channels present in the crystalline structure and due to their strong surface reactivity. MicroPIXE coupled with microRBS (3.05 MeV 4He+ ions) have been used to quantify the incorporation of zinc within two commercial zeolites containing alkali elements (zeolite X and clinoptilolite) in the concentration range of: 0.0002–0.05 M at neutral pH. At the beginning of the interaction between zeolite and Zn(II) solution, the adsorption process exhibits a direct proportionality between the content of zinc fixed on the mineral substrate and the aqueous concentration up to 0.01 M. Beyond this point a saturation effect seems to occur, indicating the strong decrease of available adsorption sites. Sodium or potassium ions are probably exchanged with Zn(II) ions during this process. The compared behaviour of the two zeolites is then discussed in terms of kinetic effects based on ionic radius values. A co-adsorption test carried on with a 50–50% Zn(II) 0.001 M–Pb(II) 0.001 M solution shows that lead does not occupy the same sites as zinc because the content of zinc fixed on the zeolite sample exactly corresponds to the result obtained with a pure 0.001 M Zn(II) solution. All these data clearly showed that zeolite surface reactivity is greatly influenced by the mineral cage-like structure and particularly the presence of pockets, spaces and channels.

Combined effects of nuclear and electronic energy losses in solids irradiated with a dual-ion beam

Single and dual-beam irradiations of oxide (c-ZrO2, MgO, Gd2Ti2O7) and carbide (SiC) single crystals were performed to study combined effects of nuclear (Sn) and electronic (Se) energy losses. Rutherford backscattering experiments in channeling conditions show that the Sn/Se cooperation induces a strong decrease of the irradiation-induced damage in SiC and MgO and almost no effects in c-ZrO2 and Gd2Ti2O7. The healing process is ascribed to electronic excitations arising from the electronic energy loss of swift ions. These results present a strong interest for both fundamental understanding of the ion-solid interactions and technological applications in the nuclear industry where expected cooperative Sn/Se effects may lead to the preservation of the integrity of nuclear devices.

Surface chemistry of weathered zircons

We have investigated the surface morphology and chemistry of zircon in sediments and soils of the Amazon basin (Brazil). The extent of metamictization in the near-surface region of these zircons was previously determined by Raman micro-probe. Scanning electron microscopy (SEM) reveals scarce dissolution features and numerous marks related to the sedimentary transport of the zircon grains, which attest to the high resistance of these zircons to tropical weathering. Rutherford backscattering (RBS) micro-analysis and X-ray photoelectron spectroscopy (XPS) failed to reveal any strong chemical change at the surface of the zircon grains. In particular no Zr enrichment was detected, which excludes the occurrence of a protecting layer of Zr oxide or hydroxide at the zircon surface. This result suggests that the slow weathering rate of zircon could be the principal factor limiting the Zr mobility in the investigated weathering environments.

Aqueous alteration of lanthanum alumino-silicate glasses

Abstract The aqueous alteration behavior of glasses in the system Y–La–Al–Si–O–N has been investigated using the Soxlhet test. The altered surface was then studied by means of solid and solution analyses. In the case of La–Al–Si–O–N glasses, the formation of a crystallized lanthanum hydroxycarbonate was determined by X-ray diffraction (XRD) analysis. In the case of Y–La–Al–Si–O–N, X-ray photoelectron spectroscopy analysis (XPS) reveals a complete disappearance of silicon and aluminum at the glass surface (depth analyzed: 20 A). Rutherford backscattering spectrometry (RBS) gives some evidence that the glass surface is covered with a phase consisting mainly of yttrium and lanthanum compounds. Solution and solid analyses provide evidence that yttrium increases the chemical durability of the glass. Nitrogen seems to enhance glass corrosion by increasing the pH of the solution.

Immobilization of radionuclides in single-phase crystalline waste forms : A review on their intrinsic properties and long term behaviour

Abstract Crystalline solids considered as potential host matrices for specific immobilization of radionuclides are reviewed. First of all, fundamental data on their physical, mechanical, cristallographic and thermodynamical properties are compiled. Then, based on the available literature, their long term behaviour is described in terms of dissolution rate, radiation effects and surface sorption properties. A comparative discussion about their respective performance is presented. Finally, some further experimental work required to complete the data base are suggested and new experimental investigations to be carried out are proposed.

Theoretical and experimental study of low-energy 4He-induced 1H elastic recoil with application to hydrogen behavior in solids

Abstract The elastic recoil differential cross section of the 4He/1H interaction is calculated between 0.5 and 8 MeV for 4He ions in the frame of the partial-wave method. The results are then compared with data previously published and experimental data obtained in the range 1.5–1.9 MeV and 20 ° –40 °. To interpret recoil spectra for hydrogen depth profiling in the near-surface region of solids, a simulation algorithm is schematically presented. Applications to a silicon matrix and a geological sample are also shown.

Nuclear reaction analysis of helium diffusion in britholite

We have derived the helium bulk diffusion constants in britholite (Ca9Nd(PO4)5(SiO4)F2) from non-destructive 3He depth profiling using the resonant 3He(d, p)4He nuclear reaction. Results have been obtained on a polycrystalline sintered ceramics implanted with 3 MeV 3He+ ions at a depth around 9 μm then annealed in air at temperatures between 200 and 400 °C. The activation energy for helium diffusion is around 1.1 eV. These data are in good agreement with literature data based on ERDA depth profiling of 27 keV 4He+ ions implanted in natural (Durango) or synthetic fluorapatite single crystals.

Application of nuclear reaction geometry for 3He depth profiling in nuclear ceramics

Abstract Direct observation of nuclear reactions leading to the emission of charged particles (p or α) allows to determine specifically the spatial distribution of isotopes of light elements from 1H to 23Na and despite low cross section values some heavier isotopes from 24Mg to 68Zn. After a brief overview of the analytical capabilities offered by μNRA, this contribution is focussed on the measurement of the thermal diffusion coefficient of 3He in crystalline ceramics. The experimental method is based on the observation of the 3He(d, p)α reaction. Due to the severe energy loss along the outgoing path, the choice of the detection of the high energy proton or recoil α nucleus depends on the average depth of the 3He distribution. For near surface distributions (