Photochemical Synthesis and Versatile Functionalization Method of a Robust Porous Poly(ethylene glycol methacrylate-co-allyl methacrylate) Monolith Dedicated to Radiochemical Separation in a Centrifugal Microfluidic Platform.

The use of a centrifugal microfluidic platform is an alternative to classical chromatographic procedures for radiochemistry. An ion-exchange support with respect to the in situ light-addressable process of elaboration is specifically designed to be incorporated as a radiochemical sample preparation module in centrifugal microsystem devices. This paper presents a systematic study of the synthesis of the polymeric porous monolith poly(ethylene glycol methacrylate-co-allyl methacrylate) used as a solid-phase support and the versatile and robust photografting process of the monolith based on thiol-ene click chemistry. The polymerization reaction is investigated, varying the formulation of the polymerisable mixture. The robustness of the stationary phase was tested in concentrated nitric acid. Thanks to their unique "easy-to-use" features, centrifugal microfluidic platforms are potential successful candidates for the downscaling of chromatographic separation of radioactive samples (automation, multiplexing, easy integration in glove-boxes environment, and low cost of maintenance).

How mobile is iodide in the Callovo-Oxfordian claystones under experimental conditions close to the in situ ones?

The iodide behaviour towards the Callovo-Oxfordian claystone was studied using batch and diffusion experiments under conditions which limited the artefacts cited in the literature to be responsible for the iodide uptake (i.e. the experiments were carried out under anoxic conditions with N(2)/CO(2) atmosphere with a monitoring of the iodine redox-state). The results show that all the radioactive iodine was (125)I(-), with no measurable activity for (125)IO(3)(-), which is known to have a higher affinity for the rock than iodide. Moreover, the batch experiments revealed no sorption, independently of the initial iodide concentration (from 10(-6) to 10(-3) mol L(-1)) and the contact time (up to 106 days). Conversely, the diffusion experiments indicated a weak but measurable retention. The through-diffusion experiments led to distribution ratio values only significant (R(D)~0.05 mL g(-1)) for initial iodide concentration ≤ 10(-4) mol L(-1). Higher R(D) values were estimated from out-diffusion experiments, ranging from about 0.05 mL g(-1) for an initial concentration of 10(-3) mol L(-1) to 0.14 mL g(-1) for the lowest one. A retention phenomenon that could be reversible and kinetically-controlled was proposed to explain the differences in the extent of the iodide retardation of the two types of diffusion experiments.