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Evaluation of Spectroscopic Methods for Determination of Hydrogen Peroxide as a Radiolysis Product
p.478
Radiation from spent nuclear fuel (SNF) is one of key factors affecting the dissolution process of SNF and the source term from repository. The dissolution rate of uranium dioxide (UO2) matrix of SNF is expected to control the release of radionuclides from SNF in contact with water under geological disposal conditions. Based on the oxidative dissolution mechanism, the solubility of UO2 can increase significantly if the reducing environment near the fuel surface is altered by water radiolysis caused by radiation from SNF. Therefore, the analysis of water radiolysis products such as radicals (·OH, ·OH2, eaq, ·H) and molecules (H3O+, H2, H2O2) is perquisite for studies on the rate of such dissolution process to determine oxidation/dissolution mechanism and related rate constants. In this study we examined the two-known spectroscopic methods developed for H2O2 determination; one is the luminol-based chemiluminescence (luminol-CL) method and the other is the spectrophotometry using ferrous oxidation-xylenol orange complexation (FOX). Their applicability for quantitative analysis of H2O2 in potential aqueous samples from SNF dissolution studies was evaluated in terms of the analytical dynamic range (ADR), the limit of detection (LOD) and the interfering effects of various metal ions possibly present in real samples. The luminol-CL method exploits the chemiluminescence reaction caused by luminol; when in the presence of a metallic catalyst (e.g., Cu2+, Co2+), luminol emits a blue light (425 nm) at pH 10- 11 in response to oxidizing agents such as hydrogen peroxide. Although a flow-through reaction system is routinely employed to enhance the analytical sensitivity we achieved the ADR up to ~200 μM and LOD < 1 μM by a batch-wise CL detection using conventional cuvette cells and an intensified charge-coupled device (ICCD). Interestingly, it turned out that the interfering effects of other metal ions (e.g., UO2 2+, U4+, Fe2+ and Fe3+) is minimal, which should be advantageous for the luminol-CL method to be employed for samples potentially containing other metal ions. On the other hand, the FOX method spectrophotometrically analyzes H2O2 based on the difference in color (or absorption spectra) of Fe-xylenol orange (XO) complexes. Initially, the Fe2+-XO complex was provided in working solutions at pH 3, which was subsequently mixed with samples having H2O2 and allowed for quantitative oxidation of Fe2+ to Fe3+. Typically, by monitoring the absorbance of Fe3+-XO complex at 560-580 nm (λmax) the ADR up to ~100 μM and LOD ~1.6 μM were achieved. However, it is found that interfering effects from M3+ and M4+ ions are significant; these interfering metal ions can form XO complexes so as to directly contribute the measured absorbance. In contrast, the influence from M2+ ions was found to be negligible. To summarize we conclude that both methods can be applied for H2O2 determination for aqueous samples taken from SNF dissolution tests. However, prior to applying the FOX method the metal ion composition in those samples should be thoroughly identified not to overestimate the H2O2 concentration of samples. More details of underlying chemical reactions in both methods will be discussed in the presentation.
