17β-estradiol (E2) and 17α-ethinyl estradiol (EE2), which are environmental estrogens have been determined with LC-MS in freshwater. Their sensitive analysis needs derivatisation and therefore is very hard to achieve in multiresidue screening. We analysed samples from all the large and some small rivers (River Danube, Drava, Mur, Sava, Tisza and Zala) of the Carpathian Basin and from Lake Balaton. Freshwater was extracted on solid phase and derivatised using dansyl-chloride. Separation was performed on a Kinetex XB-C18 column. Detection was achieved with a benchtop orbitrap mass spectrometer using targeted MS analysis for quantification. Limits of quantification were 0.05 ng/L (MS1) and 0.1 ng/L (MS/MS) for E2, and 0.001 ng/L (MS1) and 0.2 ng/L (MS/MS) for EE2. River samples contained n.d.-5.2 ng/L E2 and n.d.-0.68 ng/L EE2. Average levels of E2 and EE2 were 0.61 and 0.084 ng/L respectively in rivers, water courses and Lake Balaton together, but not counting city canal water. EE2 was less abundant, but it was still present in almost all of the samples. In beach water samples from Lake Balaton we measured 0.076-0.233 E2 and n.d.-0.133 EE2. A relative high amount of EE2 was found in river Zala (0.68 ng/L) and in Hévíz-Páhoki canal (0.52 ng/L), which are both in the catchment area of Lake Balaton (Hungary).
HighlightsMethod is proposed for simultaneous determination of 17β-estradiol and 17α-ethinyl estradiol. Derivatization is necessary to reach low LOQ. Low ng/L presence of estrogens in selected European Rivers has been detected.