Publikationsrepositorium - Helmholtz-Zentrum Dresden-Rossendorf

The finding of an appropriate long-term repository for high-level nuclear waste is a highly relevant topic. To that end, it is required to research the interaction of occurring radionuclides with mineral phases contained in possible host rocks and construction materials. On a time scale of up to a million years, especially the scenario of a water intrusion into the repository and thus dissolution of radionuclides has to be considered. To investigate the sorption behavior of actinides and lanthanides, time-resolved laser fluorescence spectroscopy (TRLFS) is a widely used method, because of its trace concentration sensitivity and capability to distinguish multiple species in complex systems. On one hand this method gives the spectral information of the emitted fluorescence light, which allows determining the symmetry and the grade of complexation of the sorbed Ln/Ac. On the other hand the lifetimes of the excited electron states provide information about the surrounding quenchers, mainly water. Typically, TRLFS investigations will focus on the interaction of an actinide with one relevant mineral phase. For a real rock formation, e.g. granite, sorption will however be a competitive process involving multiple mineral phases at the same time.
In this study a new method called time-resolved laser fluorescence microscopy (TRLFM) is introduced, which will add a spatial dimension to TRLFS. By doing so, it is possible to separate the multi-phase system into discrete single-phase systems and therefore to make a step beyond model systems by researching, for example whole natural granite rock with TRLFS. Because of its advantageous fluorescence properties we use europium as an analogue for the trivalent actinides americium and curium. Sorption experiments with Eu(III) on granite under different solution conditions, regarding metal concentration and pH will be presented. These samples are excited by a focused pulsed laser beam at a wavelength of 394 nm, and scanned through the laser’s focal point by an XYZ-Stage with a resolution in the micrometer range. The sample is subsequently mapped by Raman-Microscopy to distinguish the different phases and the TRLFM data is then compared to the combination of Raman-data with TRLFS data of the single phases.
First results show that the different sorption behavior of the single phases can be resolved by this method. Lifetimes and emission spectra have been measured for quartz, feldspar and mica phases on granite plates, which evidence that the spatial resolution is sufficient to distinguish mineral grains in natural granite. XRD and XFA are done for the samples to determine all possible constituents. Partial maps of the europium distribution and speciation are presented together with phase identification by Raman microscopy and a comparison to optical microscopy images.