LC–MS–MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters

Alkylphenols (APs), alkylphenol ethoxylates (APEOs), ethoxycarboxylate metabolites (APECs) and bisphenol A were determined in surface water using solid-phase extraction (SPE) followed by triple-quadrupole LC–MS–MS. APs were separated by LC from APECs using an acetonitrile–water-gradient without the addition of any buffer. Nonylphenol ethoxycarboxylates (NPECs) interfere in the detection of nonylphenols (NPs) when using an acidic mobile phase, because they produce the same MS–MS fragment ions (219 > 133 and 147). 4n-NP shows the characteristic transition 219 > 106; it is well suited as internal standard. Nonylphenol ethoxylates NPEnOs (n = 1–17) were analysed separately in a second run by positive ionization using an ammonium acetate mobile phase. Textile industry discharges, the corresponding wastewater treatment plant (WWTP) effluents and the receiving rivers in Belgium and Italy were analysed. Among the substances investigated, NPE1C and NPE2O exhibited the highest concentrations in the water samples, up to 4.5 μg l−1 NPE1C in a WWTP effluent and 3.6 μg l−1 NPE2O in a river. The highest NP levels were found in the receiving rivers (max. 2.5 μg l−1). The predicted no-effect concentration (PNEC) for NP of 0.33 μg l−1 for water species was frequently exceeded in the surface waters investigated, suggesting potential adverse effects to the aquatic environment.