Simplification of organic matter before voltammetric determination of Tl(I) and Tl(III) in water using nanostructured photocatalyst and solar light.

The crucial point of this study was to verify the hypothesis that both thallium species are not affected by the procedure of photolysis when it is applied as a method of simplification of sample matrix containing surfactants, and that this method of sample pretreatment leads to reliable results of Tl speciation analysis. It is important especially because of high instability of Tl(III), which makes partial reduction of Tl(III)DTPA complex unavoidable. After conservation of Tl speciation by addition of DTPA the photolysis assisted with nanostructured hierarchically organized film was performed using "solar lamp" (FeO/WO/FeO film, pH 6, 380-800 nm). The results imply that under proposed photolysis conditions Tl(I) is not oxidized in the presence of water matrix, SDS nor DTPA. Also, even 100-fold excess of Fe(III) ions over Tl(I) ions does not accelerate the oxidation of Tl(I) to Tl(III), and already 2 h of heterogeneous photolysis allow to limit the interferences caused by SDS and obtain reliable results. The data obtained by anodic stripping voltammetry (ASV) were verified using an inter-method comparison with SEC ICP MS. Moreover, after 2 h irradiation the reduction rate of Tl(III)DTPA standard solution increased only slightly from 2-3% to 4-6%. The presence of river water matrix causes a slightly higher (9%) reduction of the trivalent form. These changes are irrelevant in the context of instability of Tl(III) compounds. This study indicates that "soft decomposition" can be applied in speciation analysis of thallium in water matrix.