Distribution of analytes over TXRF reflectors

One of the most frequently used methods for trace element analysis in TXRF involves the evaporation of small amounts of aqueous solutions over flat reflectors. This method has the advantage of in-situ pre-concentration of the analytes, which together with the low background due to the total reflection in the substrate leads to excellent detection limits and high signal to noise ratio. The spiking of the liquid sample with an internal standard provides also a simple way to achieve multielemental quantitative analysis. However the elements are not homogeneously distributed over the reflector after the liquid phase has been evaporated. This distribution may be different for the unknown elements and the internal standards and may influence the accuracy of the quantitative results. In this presentation we used μ-XRF techniques to map this distribution. Small (20 μl) drops of a binary solution were evaporated over silicon reflectors and then mapped using a focused X-ray beam with about 100 μm resolution. A typical ring structure showing some differences in the distribution of both elements has been observed. One of the reflectors was also measured in a TXRF setup turning it at different angles with reference to the X-ray beam (with constant incidence and take-off angles) and variations of the intensity relation between both elements were measured. This work shows the influence of the sample distribution and proposes methods to evaluate it. In order to assess the limitations of the accuracy of the results due to the sample distribution more measurements would be necessary, however due to the small size of typical TXRF samples and the tight geometry of TXRF setups the influence of the sample distribution is not large. (author)