Determination of endocrine-disrupting phenolic compounds and estrogens in surface and drinking water by HRGC-(NCI)-MS in the picogram per liter range

A method for the analysis of phenolic estrogenic active compounds in surfac e and drinking water in the picogram per liter range is described. Besides the widely used monomer bisphenol A, 4-tert-octylphenol [4-(1,1,3,3-tetrame thylbutyl)phenol] and the technical isomer mixture of 4-nonylphenol; phenol ic steroid hormones such as the endogenous estrogens estrone, 17 alpha -est radiol, and 17 beta -estradiol; and the exogenous estrogen 17 alpha -ethiny lestradiol were determined in water at the 20-200 pg/L level. Water samples from 1 to 5 L were extracted by solid-phase extraction (SPE) on a cartridg e system containing LiChrolut EN as sorbent. The phenols and steroids were converted into their pentafluorobenzoylate esters in an extractive derivati zation reaction. The derivatives were then determined by high-resolution ga s chromatography with negative chemical ionization mass spectrometric detec tion (HRGC-(NCl)-MS) in the selected ion mode (SIM). All results were also confirmed by HRGC with electron capture detection (ECD). This highly sensit ive and specific method gives a limit of detection (LOD) of 20 pg/L for bis phenol A and 4-tert-octylphenol in drinking water samples and 50 pg/L in ST W effluent, respectively. The LODs for technical 4-nonylphenol, 17a-ethinyl estradiol, and other estrogens are in the range of 50 pg/L in drinking wate r to 200 pg/L in STW effluent, respectively. In all river water samples in southern Germany, bisphenol A was found in concentrations ranging from 500 pg/L up to 16 ng/L, 4-nonylphenol was from 6 up to 135 ng/L, and the steroi ds were from 200 pg/L up to 5 ng/L. In drinking water, bisphenol A was foun d in concentrations ranging from 300 pg/L to 2 ng/L, 4-nonylphenol was from 2 to 15 ng/L, 4-tert-octylphenol was from 150 pg/L to 5 ng/L, and the ster oids were from 100 pg/L to 2 ng/L. Mean recoveries over the whole analytica l protocol, measured in bidistilled water, generally exceeded 70%. These re sults indicate that environmental endocrine-disrupting estrogens are not co mpletely removed in the process of sewage treatment but are carried over in to the general aquatic environment. After ground passage, they can eventual ly be found in drinking water.