Enhancing sensitivity of liquid chromatographic/ion-trap tandem mass spectrometric determination of estrogens by on-line pre-column derivatization

A rapid and sensitive liquid chromatographic/ion-trap mass spectrometric method has been developed for the simultaneous determination of estriol, α-, β-estradiol, 17α-ethynylestradiol and estrone. The substances were extracted from river water samples (typically 250 ml) and cleaned-up using two-stage solid-phase extraction (SPE). 12-(Difluoro-1,3,5-triazinyl)-benz[f]isoindolo-[1,2b][1,3]benzothiazolidine was applied as a derivatizing agent. The recovery for each compounds ranged from 75 to 88% and the repeatability represented as RSDs ranged from 5.6 to 8.4%. Limits of detection (LOD, 3 × S/N) were 67–285 pg/l.