Simulation of radiolysis in the near field of a nuclear repository and the spectrophotometric investigation of the formation of radiolysis by-products by applying high energy beam-like experiments

In the event of inundation of a nuclear waste repository located in a geological salt formation, chloride brines in contact with nuclear waste will be exposed to different kind of radiation depending on waste-form conditions. Ionizing radiations, however, have the ability to significantly affect the groundwater chemistry of the brines through the formation of free radicals, ionic- and molecular species; among them the typical byproducts of a-radiolysis: hypochlorite (OC1-) and hypochlorous acid (HOCl). In the absence of effects which arc supposed to dominate the redox conditions in the repository (corrosion of metals, microbial activity) the presence of OC1- is known to increase the redox potential of the brines and further to influence the stability of actinide waste-forms by accelerating their dissolution arid - most importantly - to oxidize actinides to their higlier oxidation states, whicli are gcncrally the most soluble ones. We are presenting a new approach to determine the radiation-induced formation rates of hypochlorite and hypochlorous acid as a first step to assess long-term steady-state repository conditions. To ovt:rcome the serious constraints of conventional radiocheinical work with GBq activity levels, we are simulating a-irradiation of chloride brines by the adaptation of ion-beam-line experiments. Therefore, we irradiate liquid chloride brine targets with 5 MeV protons, and 5 MeV helium ions. The irradiation-induced formation rates of OCX- and HOC1 were determined by UV-Vis spectrophotometry. To give an example, the measured G values for the HOCl formation in 3.7 M MgC12.6H20, pW 4.42, irradiated by 5 MeV protons was determined to be 0.0374 {+-} 0.0022, and 0.0536 {+-} 49 by irradiating with 5 MeV helium. The distinguished ltnowledge about the radiation-induced production of oxo-chloride species is the first step towards the assumption of their steady-state concentrations in the irradiation field of the repository