Low nanogram per liter determination of halogenated nonylphenols,nonylphenol carboxylates,and their non-halogenated precursors in water and sludge by liquid chromatography electrospray tandem mass spectrometry

A new LC-MS-MS method for quantitative analysis of nonylphenol (NP), nonylphenol carboxylates (NPECs), and their halogenated derivatives: brominated and chlorinated nonylphenols (BrNP, ClNP), brominated and chlorinated nonylphenol carboxylates (BrNPE(1)C and ClNPE(1)C) and ethoxycarboxylates (BrNPE(2)C and ClNPE(2)C) in water and sludge has been developed. Electrospray negative ionization MS-MS was applied for the identification of above mentioned compounds. Upon collision-induced dissociation, their deprotonated molecules gave different fragments formed by the cleavage of the alkyl moiety and/or (ethoxy)carboxylic moiety. For halogenated compounds a highly diagnostic characteristic pattern of isotopic doublet signals was obtained and fragmentation yielded, in addition to above mentioned ions, Br](-) and Cl](-), respectively. Quantitative analysis was done in the multiple reaction monitoring (MRM) mode, using two specific combinations of a precursor-product ion transitions for each compound. Additionally, for halogenated compounds two specific channels for each transition reaction, corresponding to two isotopes, were monitored and the ratio of their abundances used as an identification criterion. The method has been validated in terms of sensitivity, selectivity, accuracy, and precision and was applied to the analysis of water and sludge samples from drinking water treatment plant (DWTP) of Barcelona (Catalonia, NE Spain). Halogenated NP and NPECs were detected in prechlorinated water in concentrations up to 315 ng/L, BrNPE(2)C being the most abundant compound. In the DWTP effluent non-halogenated compounds were detected at trace levels (85, 12 and 10 ng/L for NP, NPE(1)C, and NPE(2)C, respectively), whereas concentration of halogenated derivatives never exceeded 10 ng/L. Nonylphenol, brominated and chlorinated NPs were found in flocculation sludge in concentrations of 150, 105, and 145 microg/kg, respectively. Acidic polar metabolites were found in lower concentrations up to 20 microg/kg.