Carrier- and salt-free42K milked from an42Ar–42K generator was utilized for isotope dilution analysis of potassium in ultra-pure water. Potassium in the sample marked with the42K was shown to be concentrated easily 60 times by crown-ether extraction and acid back-extraction to be determined by atomic absorption spectrophotometry. The same extractions proved to be effective for removing the reagent blank. Cerenkov radiation counting was often suitable for42K measurement. The42K was used also for studying the interaction of ultra-low concentrations of potassium with vessel walls.