Induced modifications of kaolinite under ionizing radiation : an infrared spectroscopic study

Radiation effects on kaolinite were investigated using He+ ions of 1.5 MeV at radiation doses up to 4.3 x 10(8) Gy, which are comparable to the doses expected for clay barriers in high-level nuclear waste repositories. The concentration of paramagnetic radiation-induced defects in kaolinite reaches 2 x 10(16) spins/mg (400 at. ppm), as determined by electron paramagnetic resonance spectroscopy. The broadening of X-ray diffraction patterns and transmission infrared (IR) absorption bands is mostly related to the structural strain induced by radiation-induced point defects. The broadening of IR absorption spectra is analyzed using an autocorrelation approach and is related to a change in the distribution of vibrational frequencies due to crystal heterogeneities. We theoretically analyze how the effective dielectric properties of kaolinite samples depend on macroscopic parameters and how irradiation can modify some of them. Irradiation leads to an increase in the electronic polarizability of kaolinite particles, related to the accumulation of radiation-induced electronic point defects

Radiation-induced defects in clay minerals : a review

Extensive information has been collected on radiation effects on clay minerals over the last 35 years, providing a wealth of information on environmental and geological processes. The fields of applications include the reconstruction of past radioelement migrations, the dating of clay minerals or the evolution of the physico-chemical properties under irradiation. The investigation of several clay minerals, namely kaolinite, dickite, montmorillonite, illite and sudoite, by Electron Paramagnetic Resonance Spectroscopy has shown the presence of defects produced by natural or artificial radiations. These defects consist mostly of electron holes located on oxygen atoms of the structure. The various radiation-induced defects are differentiated through their nature and their thermal stability. Most of them are associated with a pi orbital on a Si-O bond. The most abundant defect in clay minerals is oriented perpendicular to the silicate layer. Thermal annealing indicates this defect in kaolinite (A-center) to be stable over geological periods at ambient temperature. Besides, electron or heavy ion irradiation easily leads to an amorphization in smectites, depending on the type of interlayer cation. The amorphization dose exhibits a bell-shaped variation as a function of temperature, with a decreasing part that indicates the influence of thermal dehydroxylation. Two main applications of the knowledge of radiation-induced defects in clay minerals are derived: (i) The use of defects as tracers of past radioactivity. In geological systems where the age of the clay can be constrained, ancient migrations of radioelements can be reconstructed in natural analogues of high level nuclear waste repositories. When the dose rate may be assumed constant over time, the paleodose is used to date clay populations, an approach applied to fault gouges or laterites of the Amazon basin. (ii) The influence of irradiation over physico-chemical properties of clay minerals. An environmental application concerns the performance assessment of the engineered barrier of nuclear waste disposals. In case of a leakage of transuranic elements from the radioactive waste form, alpha recoil nuclei can amorphize smectite after periods of the order of 1000 years according to a worst case scenario, whereas amorphization from ionizing radiation is unlikely. As amorphization greatly enhances the dissolution kinetics of smectite, the sensitivity of the smectites must be taken into account in the prediction of the long term behavior of engineered barriers

Impact of pyrometallurgical slags on sunflower growth, metal accumulation and rhizosphere microbial communities

Metallurgical exploitation originates metal-rich by-products termed slags, which are often disposed in the environment being a source of heavy metal pollution. Despite the environmental risk that this may pose for living organisms, little is known about the impact of slags on biotic components of the ecosystem like plants and rhizosphere microbial communities. In this study, metal-rich (Cu, Pb, Zn) granulated slags (GS) derived from Cu production process, were used for a leaching test in the presence of the soil pore solution, showing that soil solution enhanced the release of Cu from GS. A pot experiment was conducted using as growing substrate for sunflower (Helianthus annuus) a 50% w/w mix of an agricultural soil and GS. Bioavailability of metals in soil was, in increasing order: Pb < Zn < Cu. Sunflower was able to grow in the presence of GS and accumulated metals preferentially in above-ground tissues. Microbial diversity was assessed in rhizosphere and bulk soil using community level physiological profiling (CLPP) and 16S rRNA gene based denaturing gradient gel electrophoresis (DGGE) analyses, which demonstrated a shift in the diversity of microbial communities induced by GS. Overall, these results suggest that metallurgical wastes should not be considered inert when dumped in the soil. Implications from this study are expected to contribute to the development of sustainable practices for the management of pyrometallurgical slags, possibly involving a phytomanagement approach.Fil: Agnello, Ana Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Fermentaciones Industriales. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Fermentaciones Industriales; Argentina. Université Paris-Est. Laboratoire Géomatériaux et Environnement; FranciaFil: Potysz, A.. University of Wrocław.Institute of Geological Sciences; PoloniaFil: Fourdrin, C.. Université Paris-Est. Laboratoire Géomatériaux et Environnement; FranciaFil: Huguenot, D.. Université Paris-Est. Laboratoire Géomatériaux et Environnement; FranciaFil: Chauhan, P.S.. Council of Scientific and Industrial Research. National Botanical Research Institute; Indi

Water radiolysis in exchanged-montmorillonites: the H2 production mechanisms.

International audienceThe radiolysis of water confined in montmorillonites is studied as a function of the composition of the montmorillonite, the nature of the exchangeable cation, and the relative humidity by following the H2 production under electron irradiation. It is shown that the main factor influencing this H2 production is the water amount in the interlayer space. The effect of the exchangeable cation is linked to its hydration enthalpy. When the water amount is high enough to get a basal distance higher than 1.3 nm, then a total energy transfer from the montmorillonite sheets to the interlayer space occurs, and the H2 production measured is very similar to the one obtained in bulk water. For a basal distance smaller than 1.3 nm, the H2 production increases with the relative humidity and thus with the water amount. Lastly, electron paramagnetic resonance measurements evidence the formation of a new defect induced by ionizing radiation. It consists of a hydrogen radical (H2 precursor) trapped in the structure. This implies that structural hydroxyl bonds can be broken under irradiation, potentially accounting for the observed H2 production

The complex atmospheric corrosion of α/δ bronze bells in a marine environment

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Water Radiolysis in Exchanged-Montmorillonites: The H₂ Production Mechanisms

The radiolysis of water confined in montmorillonites is studied as a function of the composition of the montmorillonite, the nature of the exchangeable cation, and the relative humidity by following the H₂ production under electron irradiation. It is shown that the main factor influencing this H₂ production is the water amount in the interlayer space. The effect of the exchangeable cation is linked to its hydration enthalpy. When the water amount is high enough to get a basal distance higher than 1.3 nm, then a total energy transfer from the montmorillonite sheets to the interlayer space occurs, and the H₂ production measured is very similar to the one obtained in bulk water. For a basal distance smaller than 1.3 nm, the H₂ production increases with the relative humidity and thus with the water amount. Lastly, electron paramagnetic resonance measurements evidence the formation of a new defect induced by ionizing radiation. It consists of a hydrogen radical (H₂ precursor) trapped in the structure. This implies that structural hydroxyl bonds can be broken under irradiation, potentially accounting for the observed H₂ production

Irradiation effects in hydrated zirconium molybdate

International audienceHydrated zirconium molybdate is a precipitate formed during the process of spent nuclear fuel dissolution. In order to study the radiation stability of this material, we performed gamma and electron irradiation in a dose range of 10–100 kGy. XRD patterns showed that the crystalline structure is not affected by irradiation. However, the yellow original sample exhibits a blue–grey color after exposure. The resulting samples were analyzed by means of EPR and diffuse reflectance spectroscopy. Two sites for trapped electrons were evidenced leading to a d1 configuration responsible for the observed coloration. Moreover, a third defect corresponding to a hole trapped on oxygen was observed after electron irradiation at low temperature