The separation and concentration methods for the trimethylselenonium ion (TMSe) in urine samples were developed utilizing the formation of the ion pair of TMSe with tetrakis(4-fluorophenyl)borate. The ion pair could be quantitatively collected by a solvent extraction technique as well as a cellulose nitrate (CN) filter collection technique. The collected TMSe was determined by graphite furnace atomic absorption spectrometry with the addition of palladium as a matrix modifier. In the case of urine analysis for TMSe, the CN filter technique gave better reproducibility than the solvent extraction technique. The detection limit of this method for TMSe was 1 ngSe/ml for 20 ml of urine sample. (C) 1994 Academic Press, Inc.