Besides the dominant species in plants-Tl(I), noticeable amounts of Tl(III) (about 10% of total Tl content) were found in extracts of plants cultivated in the presence of tailing sediments, which are the main source of anthropogenic thallium already present in the environment. It is an important step of gaining knowledge about the detoxification mechanisms developed by Sinapis alba. This plant species is highly tolerant to Tl and it is able to cumulate high amounts of Tl and transport it into the above-ground organs. For more adequate estimation of accumulating abilities of S. alba, the elements' bioavailability was taken into consideration. The obtained bioconcentration factors of Cd (AF=0.6) and Zn (AF=1-2) were significantly lower than of Tl (AF=100-200). The biomass production was similar to the biomass of control cultivation. The results were based on ICP MS measurements of total elements' content and HPLC ICP MS for speciation analysis. The quality of obtained results was evaluated based on the intermethod comparison with voltammetry as a reference method. Comparison of data obtained using ICP MS and electrochemical methods (after a proper chemical treatment) was also used for indication of Tl(III) presence and for proving that Tl(I) was not transferred into Tl(III) during analytical procedures.