Mixed-mode solid-phase extraction followed by liquid chromatography–tandem mass spectrometry for the determination of tri- and di-substituted organophosphorus species in water samples

A procedure for the determination of three phosphoric acid diesters, eight triesters and triphenylphosphine oxide (TPPO) in water samples is presented. Analytes were simultaneously concentrated using a mixed-mode (reversed-phase and anionic-exchange) solid-phase extraction (SPE) sorbent and then sequentially eluted with methanol (triesters and TPPO) followed by a 20 mM tetrabutylammonium hydrogen sulphate (TBAHS) methanolic solution, case of diesters. After that, they were determined, in two different runs, by liquid chromatography–electrospray ionization–tandem mass spectrometry (LC–ESI–MS/MS), operating the ESI source in the positive (triesters and TPPO) and negative (diesters) ionization modes. The efficiency of the extraction step varied between 70 and 105%, except in the case of tris(2-ethylhexyl) phosphate (TEHP), and it was barely affected by the type of water sample. Moreover, low signal suppression effects were noticed in the ESI ionization of extracts obtained from different environmental water samples. As a result, the standard addition methodology was only required for the accurate quantification of tri-substituted organophosphorus (OPs) species in wastewater samples. Limits of quantification of the optimized method ranged from 0.2 to 10 ng L−1, depending on the sample matrix and the considered compound. The analysis of river and wastewater samples confirmed the occurrence of several tri- and di-substituted OPs in the aquatic environment, with the highest concentrations corresponding to tris(butoxyethyl) phosphate (TBEP) and tris(chloropropyl) phosphate (TCPP).