Rémi Barillon

Surface reactivity of α-Al2O3 and mechanisms of phosphate sorption: In situ ATR-FTIR spectroscopy and ζ potential studies

We have investigated the effect of solution parameters on the adsorption of phosphate ions and on charges and structures, i.e., on the nature of species, at the alpha-Al(2)O(3) colloid/solution interface by using the batch method, zeta potential measurements, and in situ ATR-FTIR spectroscopy. The uptake of phosphate decreases with the extent of surface deprotonation (i.e., pH), imparts negative charges to the colloid surface, and induces IEP shifts showing chemical sorption. Use of complementary techniques provides evidence that phosphate is sorbed at low pH (3.3) by a combination of surface reactions of complexation and precipitation, whose relative contributions depend on phosphate loading. Surface complexation includes fast reactions of ligand exchange with single coordinated hydroxyls, and electrostatic attraction of H(2)PO(4)(-) ions at positively charged surface sites. This is supported by experiments at low coverage showing sharp and linear decrease of zeta potential (i.e., surface charge) with amount of phosphate sorbed. At high coverage, zeta potential values are low and independent of phosphate loading. Formation of surface precipitates of Al-phosphate is inferred from the assignment of the ATR-FTIR absorption band at 1137cm(-1), whose intensity increases with phosphate solution content and reaction time, to the P-O-stretching vibration mode for phosphate sorbed at high concentrations on alpha-Al(2)O(3). In situ ATR-FTIR spectroscopy reveals also structural reorganizations of surface hydroxyls with time, due to surface hydration and to surface precipitation continuing over extended periods along alumina dissolution.

pH dependence of uranyl retention in a quartz/solution system: an XPS study

We have investigated the pH dependence of U(VI) retention in quartz/10(-4) M uranyl solution systems, under conditions favoring formation of polynuclear aqueous species and of colloids of amorphous schoepite as U(VI) solubility-limiting phases. X-ray photoelectron spectroscopy was used to gain insights into the coordination environments of sorbed/precipitated uranyl ions in the centrifuged quartz samples. The U4f XPS spectra made it possible to identify unambiguously the presence of two uranyl components. A high binding energy component, whose relative proportion increases with pH, exhibits the U4f lines characteristic of a reference synthetic metaschoepite. Such a high binding energy component is interpreted as a component having a U(VI) oxide hydrate character, either as polynuclear surface oligomers and/or as amorphous schoepite-like (surface) precipitates. Its pH dependence suggests that a binding of polynuclear species at quartz surfaces and/or a formation of amorphous schoepite-like (surface) precipitates is favored when the proportion of aqueous polynuclear species increases. A second surface component exhibits binding energies for the U4f core levels at values significantly lower (DeltaE(b)=1.2 eV) than for metaschoepite, evidencing uranyl ions in a distinct coordination environment. Such a low binding energy component may be attributed to monomeric uranyl surface complexes on the basis of published EXAFS data. Such a hypothesis is supported by a major contribution of the low binding energy component to the U4f XPS spectra of reference samples for uranyl sorbed on quartz from very acidic 10(-3) M uranyl solutions where UO(2)(2+) ions predominate.

Characterization of chemical and optical modifications induced by proton beams in CR-39 detectors

Abstract Chemical and optical modifications induced by 22.5 MeV protons slowed down into a 4.4 mm polyallyl diglycol carbonate (CR-39) stack, which was composed of 16 detectors of different thicknesses, are studied. Irradiation was performed perpendicular to the stack surface, in a vacuum chamber, with proton fluences ranging from 10 11 to 10 14 particles/cm 2 . These transformations are analyzed using fourier transform infrared (FTIR) absorption spectroscopy in the total attenuation reflection mode and UV–visible spectroscopy by following CO, CC and O–H bands evolution and by following the shift in the absorption edge towards the higher wavelengths. The chemical changes occurring in the CR-39 absorption spectra (both FTIR and UV) are analyzed versus the ion beam fluence, the beam penetration depth into the stack and the average deposited energy density. The results show that degradation of CR-39 presents a maximum in the depths ranging between 3500 and 4000 μm .

TRLFS evidence for precipitation of uranyl phosphate on the surface of alumina: environmental implications.

We studied the ligand-enhanced sorption of uranyl ions (1-12 μM) on α-alumina colloids suspended in (and pre-equilibrated with) solutions at various concentrations of phosphate ions (P(T) = 0-900 μM). A highly sensitive technique, time resolved laser-induced fluorescence spectroscopy (TRLFS), was used to examine the chemical speciation of uranyl sorbed at trace concentrations (0.4-4 μmol U·g⁻¹). The suspensions with P(T) ≥ 100 μM exhibited high uranyl adsorption, and a very high intensity of fluorescence that increased with the sorbed amounts of phosphate and uranyl. These samples exhibited similar spectral and temporal characteristics of fluorescence emission, evidencing a uniform speciation pattern and a single coordination environment for sorbed U, despite large variation in parameters such as aqueous uranyl speciation, U loading, and extent of coverage of alumina by secondary Al phosphates precipitating on the surface. The results pointed formation of surface precipitates of uranyl phosphates, which are characterized by high quantum yield, peak maxima at positions similar to those of U(VI) phosphate minerals and four lifetimes indicating distortions, in-homogeneities or varying number of water molecules in the lattice. The findings have major implications for our understanding of the mechanisms of immobilization of U at trace levels on surfaces of oxides submitted to phosphated solutions in soils with low pH.

Structural Modification along Heavy Ion Tracks in Poly(allyl diglycol carbonate) Films

To identify the chemical modifications along nuclear tracks in poly(allyl diglycol carbonate) (PADC), we have made a series of Fourier transform infrared (FT-IR) measurements for films with a thickness of about 3 µm that have been exposed to C, Ne, Ar, and Fe ions in air. The amount of carbonated ester bonds lost due to the exposure was estimated from the changes in the absorbance of C=O and C–O–C bonds with the heavy ion fluence. The G-value for the breaking of carbonate ester bonds and the corresponding track core radii were obtained as a function of stopping power. The calculated radial dose distribution indicated that the core was formed at regions where the local dose was higher than 106 Gy.

Mechanisms of uranyl and phosphate (co)sorption: Complexation and precipitation at α-Al2O3 surfaces

This study presents new in situ electrophoretic and ATR-FTIR data on the surface species controlling the cosorption of uranyl and phosphate ions in alpha-Al(2)O(3) suspensions at acidic pH (3.3). It was shown that the uranyl sorption (i) was promoted in the presence of phosphate, (ii) induced significant changes in zeta potential of P-loaded alumina, and (iii) was governed by two mechanisms, surface complexation and surface precipitation, with the predominant species being mainly dependent on phosphate surface coverage. Formation of surface precipitates of uranyl phosphate at high phosphate surface coverage was inferred from the high negative charges imparted to the surface by uranyl and phosphate (co)sorption, and from assignments of IR bands at 1107, 1024, and 971 cm(-1) to P-O-stretching vibrations for phosphate coordinated to uranyl, at the alumina surface. The ATR-FTIR study showed that the precipitates of uranyl phosphate formed at the surface of alpha-Al(2)O(3) for aqueous concentrations of uranyl at trace levels. It also evidenced that formation of surface precipitates of U(VI)-phosphate was occurring along with the transformation of alumina into secondary surface precipitates of Al-phosphate, at very high phosphate concentrations. These findings are relevant to the mechanisms of adsorption of trace uranyl on naturally occurring oxide surfaces, in soils with low pH where cosorption of phosphate and uranyl ions is known to play a crucial role in the long-term retention of U.

Variation of the critical registration angle of alpha particles in CR39: Implications for radon dosimetry

Abstract This paper describes a methodology to characterize the response of a detector to alpha particles of different incidences and energies using an experimental irradiation system and an etching model. Implications for radon dosimetry are discussed. For each incident energy there is a particular angle above which alpha particles no longer induce an observable etched track. This angle also depends on the etching and on the conditions of observation of the detector. It is necessary to known the variation of that critical angle with incident alpha particle energy for given etching and observation conditions in order to determine the theoritical detection efficiency of a radon detector. This variation was studied for a CR39 detector (Tastrack, G.B.) over the energy range of the alpha particles emitted by radon (5,5 MeV) and its two short-life daughters : Po218 (6 MeV) and Po214 (7,7 MeV).

Applicability of Polyimide Films as Etched-Track Detectors for Ultra-Heavy Cosmic Ray Components

The track registration property in polyimide Kapton has been examined for heavy ions, including 2.3 GeV Fe and 24 GeV Xe ions. Conventional track formation criteria fail to predict the thresholds of etch pit formation, while a chemical criterion stating that etchable tracks are formed when two adjacent diphenyl ethers are broken in the vicinity of the ions trajectory should be more appropriate. Discriminative detections of ultra-heavy components in cosmic rays, such as Bi, Th, and U ions, are possible by measuring the recorded track length.

Thresholds of Etchable Track Formation and Chemical Damage Parameters in Poly(ethylene terephthalate), Bisphenol A polycarbonate, and Poly(allyl diglycol carbonate) Films at the Stopping Powers Ranging from 10 to 12,000 keV/µm

The damage structure of latent tracks in poly(ethylene terephthalate) (PET) has been examined by Fourier transform infrared (FT-IR) measurements. Results are compared with those from previous studies on bisphenol A polycarbonate (PC) and poly(allyl diglycol carbonate) (PADC). These polymers are exposed to protons and heavy ions (He, C, Ne, Si, Ar, Fe, Kr, and Xe) in air with energies less than 6 MeV/n, as well as gamma rays from an intense Co-60 source. Chemical damage parameters, namely, damage density, which is the number of losses of considered functional groups per unit length of tracks, radial size of the track core, in which the considered chemical groups are lost, and radiation chemical yields (G values) for each group are evaluated as a function of the stopping power. It has been confirmed that latent tracks will be etchable when the radial track core size is larger than the distance between two adjacent breaking points of polymer chains. The predominant breaking points are the C–O bonds in ether, ester, and carbonate ester bonds.

Mechanisms of uranyl sorption

Abstract Detailed knowledge of the reactions at the water/colloid/mineral interface is crucial to model accurately actinide behaviour in nature. In this paper, we review current knowledge of the sorption of actinides and of the mechanisms of sorption, with a particular focus on uranyl. Of major interest is the influence of the aqueous uranyl species (e.g., carbonate complexes, polynuclear species, colloids) on the uranyl sorption species. We present extended X-ray absorption fine structure (EXAFS) and X-ray photoelectron spectroscopy (XPS) studies on the coordination of uranyl onto an amorphous Al phase and onto quartz, respectively. Our XPS investigations show that two components having uranyl ions in very distinct coordination environments co-exist on quartz at high uranyl surface coverage, independently of the presence of uranyl carbonate complexes or uranyl colloids in solution. One component corresponds to polynuclear surface species and/or schoepite-like surface precipitates. In the case of similar uranyl concentrations and of high carbonate solution concentrations, polymeric uranyl species are formed on quartz, whereas no such surface species occurs on the Al phase. Uranyl is found on the Al phase as mononuclear uranyl carbonato surface complexes only. These results are of importance because they suggest that mineral surface characteristics strongly control the uranyl surface species in aquifers.