Quantitative SERS sensors for environmental analysis of naphthalene.

In the investigation of chemical pollutants, such as PAHs (Polycyclic Aromatic Hydrocarbons) at low concentration in aqueous medium, Surface-Enhanced Raman Scattering (SERS) stands for an alternative to the inherent low cross-section of normal Raman scattering. Indeed, SERS is a very sensitive spectroscopic technique due to the excitation of the surface plasmon modes of the nanostructured metallic film. The surface of quartz substrates was coated with a hydrophobic film obtained by silanization and subsequently reacted with polystyrene (PS) beads coated with gold nanoparticles. The hydrophobic surface of the SERS substrates pre-concentrates non-polar molecules such as naphthalene. Under laser excitation, the SERS-active substrates allow the detection and the identification of the target molecules localized close to the gold nanoparticles. The morphology of the SERS substrates based on polystyrene beads surrounded by gold nanoparticles was characterized by scanning electron microscopy (SEM). Furthermore, the Raman fingerprint of the polystyrene stands for an internal spectral reference. To this extent, an innovative method to detect and to quantify organic molecules, as naphthalene in the range of 1 to 20 ppm, in aqueous media was carried out. Such SERS-active substrates tend towards an application as quantitative SERS sensors for the environmental analysis of naphthalene.

Non-intrusive and reliable speciation of organically bound tritium in environmental matrices.

Measurements of tritium in its various forms within the environment and especially in organic matter are keys to improving the current understanding of its environmental behavior and distribution. Validated or standardized analytical procedures for tritium determination methods have now been developed for several forms of tritium in environmental samples, yet an analytical lack remains regarding the quantifications of exchangeable and non-exchangeable forms of organically bound tritium (OBT) fractions. The present work therefore aims to provide a means of developing a standardized method for OBT fraction determination by evaluating the robustness and relevance of two methods (intrusive and non-intrusive methods) developed for non-exchangeable OBT quantification on a broad panel of pertinent environmental matrices. The validity and reliability of a non-intrusive method has thus been confirmed through a robust comparative study. Moreover, its relevance for standardization purposes is discussed, while the fundamental weakness of the conventional and most widespread method is highlighted and directly quantified for the first time in relying on many demonstrated biases.

New insights into the accessibility of native cellulose to environmental contaminants toward tritium behavior prediction.

Tritium speciation and behavior in the environment directly rely on accessible OH groups of organic molecules and their hydrogen exchangeability properties. As one of the most widespread biomolecule, cellulose role in reducing the exchange capacity of the hydrogen atom has been previously highlighted experimentally in various environmental matrices. In this paper, a robust and reliable T/H gas-solid isotopic exchange procedure has been implemented to assess the OH group accessibility of native celluloses with an increasing degree of crystallinity. A linear relationship was found between hydroxyl reactivity and the crystallinity index (CrI) of native celluloses, as determined by the analysis of their crystalline structure from XRD characterization. The application of the obtained linear experimental model to cellulosic materials was then evaluated and an acceptable minimum value of 12% for the CrI parameter on environmental matrices could thus be established. The authors have therefore proposed an environmental matrices relevant and efficient analytical process in order to determine the accessibility of native cellulose hydroxyl groups to tritium in the environment from a single and quick sample characterization procedure.

Cellulose, proteins, starch and simple carbohydrates molecules control the hydrogen exchange capacity of bio-indicators and foodstuffs.

Over the past several years, it has become increasingly acknowledged that Organically Bound Tritium (OBT) is the most pertinent tritium form for understanding its behavior and distribution within the biosphere. The fate of tritium actually depends on the accessibility and exchangeability of hydrogen atoms for isotopic exchanges in natural organic matter, especially in widespread biomass biomolecules like carbohydrates or proteins. The present work is therefore aimed at providing a means for improving the knowledge of tritium speciation and distribution on environmental matrices by evaluating the impact of molecular structure of various carbohydrate molecules on OBT behavior. We are thus proposing to assess the exchange capacities of hydrogen from a gas-solid isotopic exchange methodology in wheat grains, water-milfoil and apple environmental matrices using starch, cellulose/proteins and simple carbohydrates as their respective main constituents. For wheat grains, a good agreement was obtained between experimental and theoretical values as a result of the predominantly simple molecular structure of starch. For both water-milfoil and apple, the disparities between experimental and theoretical values showed the occurrence of the buried form of tritium, correlated with the 3D molecular complexity of their main constituents. The key role played by these determinant constituents on hydrogen exchange capacity could thus be experimentally demonstrated on several environmental matrices. These distinct hydrogen exchange capacities were then proven to exert an influence on the NE-OBT distribution on environmental matrix constituents, in yielding critical information to better the understanding of tritium distribution and behavior in the environment.

An integrated approach combining soil profile, records and tree ring analysis to identify the origin of environmental contamination in a former uranium mine (Rophin, France).

Uranium mining and milling activities raise environmental concerns due to the release of radioactive and other toxic elements. Their long-term management thus requires a knowledge of past events coupled with a good understanding of the geochemical mechanisms regulating the mobility of residual radionuclides. This article presents the results on the traces of anthropic activity linked to previous uranium (U) mining activities in the vicinity of the Rophin tailings storage site (Puy de Dôme, France). Several complementary approaches were developed based on a study of the site's history and records, as well as on a radiological and chemical characterization of soil cores and a dendrochronology. Gamma survey measurements of the wetland downstream of the Rophin site revealed a level of 1050 nSv.h-1. Soil cores extracted in the wetland showed U concentrations of up to 1855 mg.kg-1, which appears to be associated with the presence of a whitish silt loam (WSL) soil layer located below an organic topsoil layer. Records, corroborated by prior aerial photographs and analyses of 137Cs and 14C activities, suggest the discharge of U mineral particles while the site was being operated. Moreover, lead isotope ratios indicate that contamination in the WSL layer can be discriminated by a larger contribution of radiogenic lead to total lead. The dendroanalysis correlate U emissions from Rophin with the site's history. Oak tree rings located downstream of the site contain uranium concentrations ten times higher than values measured on unaffected trees. Moreover, the highest U concentrations were recorded not only for the operating period, but more surprisingly for the recent site renovations as well. This integrated approach corroborates that U mineral particles were initially transported as mineral particles in Rophin's watershed and that a majority of the deposited uranium appears to have been trapped in the topsoil layer, with high organic matter content.

Towards speciation of organically bound tritium and deuterium: Quantification of non-exchangeable forms in carbohydrate molecules.

An original methodology to quantitatively explore exchangeability of hydrogen isotopes in carbohydrate molecules is proposed. To access the speciation of organically bound hydrogen isotopes, isotopic exchanges were carried out under a soft path regime in the vapor phase at 20 °C with set (D,T/H) vapor pressure ratios. When steady states were reached, the fraction of exchangeable hydrogen of microcrystalline cellulose, alpha-cellulose and wheat grains were obtained and ranged from 13 to 31% (versus a theoretical value of 30%). In cellulose, and more specifically in microcrystalline cellulose, the molecular hydrogen bonds as well as the different conformations of the network seemed to decrease the hydroxyl groups of glucose units available for isotopic exchange. On the contrary, the assumed enzymatic hydrolysis of the constitutive molecules of wheat starch into low-molecular weight carbohydrate molecules enhanced the exchangeable pool. An average value of the activity between non-exchangeable organically bound tritium (NE-OBT) and non-exchangeable organically bound hydrogen was calculated for wheat grains, (TH)NE  = 0.55 ±â€¯0.03 Bq.g-1 of hydrogen atoms.

19F high magnetic field NMR study of beta-ZrF4 and CeF4: from spectra reconstruction to correlation between fluorine sites and 19F isotropic chemical shifts.

High magnetic field and high spinning frequency one- and two-dimensional one-pulse MAS 19F NMR spectra of beta-ZrF4 and CeF4 were recorded and reconstructed allowing the accurate determination of the 19F chemical shift tensor parameters for the seven different crystallographic fluorine sites of each compound. The attributions of the NMR resonances are performed using the superposition model for 19F isotropic chemical shift calculation initially proposed by Bureau et al. (Bureau, B.; Silly, G.; Emery, J.; Buzaré, J.-Y. Chem. Phys. 1999, 249, 85-104). A satisfactory reliability is reached with a root-mean-square (rms) deviation between calculated and measured isotropic chemical shift values equal to 1.5 and 3.5 ppm for beta-ZrF4 and CeF4, respectively.