Liquid chromatographic–tandem mass spectrometric method for the simultaneous determination of alkylphenols polyethoxylates, alkylphenoxy carboxylates and alkylphenols in wastewater and surface-water

Four different pellicular stationary phases (i.e. octadecylsilane, octasilane, Phenyl-Hexyl and pentafluorophenyl) were investigated for the chromatographic resolution of alkylphenols (APs), alkylphenols polyethoxylates (APnEOs) and alkylphenoxy carboxylates (APECs) using mixtures of water and organic solvents (i.e. methanol, acetonitrile and tetrahydrofuran) as eluents, in order to obtain their determination by a single LC–MS/MS run. In fact, alkylphenols and alkylphenoxy carboxylates must be analysed in negative ion mode, whereas alkylphenols polyethoxylates undergo ionisation only in positive ion mode, and therefore, two distinct LC–MS/MS analysis are commonly adopted. The best resolution among the aforementioned target analytes was achieved on the pentafluorophenyl column, eluting with an acidified water–acetonitrile–tetrahydrofuran mixture and using the post column addition of an ammonia solution in methanol for the detection of positively ionisable compounds. Under these optimized chromatographic conditions the investigated compounds were determined via a single chromatographic run, with only one polarity switch, in 15 min, achieving the following instrumental detection limits: 600 pg for AP1EOs, 0.8–14 pg for AP2EOs, 10.4–150 pg for APs and 4.4–4.8 pg for APECs. The chromatographic method was coupled with solid-phase extraction and clean-up procedures and successfully applied to the analysis of wastewater and surface water samples, highlighting mean concentration ranging from 6 ng/L for 4-t-OP1EC to 1434 ng/L for 4-NP1121EC, depending on the sample analysed.