Determination of endocrine-disrupting compounds in environmental samples using gas and liquid chromatography with mass spectrometry

Abstract

This paper describes certain applications for endocrine-disrupting compounds determination. LC–MS was applied using an electrospray ionization (ESI) technique in positive mode for alcohol polyethoxylates and nonylphenol and octylphenol polyethoxylates (NPEO n and OPEO n ), and in negative mode for 4-nonylphenol (4-NP) and 4-octylphenol (4-OP) to determine targeted compounds in wastewater and sludge. GC–MS and GC–MS–MS were used to determine 4-NP, 4- tert.-octylphenol (4- t-OP), bisphenol A, estradiol-17β, estriol, estrone, testosterone, 17α-ethynylestradiol, cholesterol, coprostan-3-ol, coprostan and coprostan-3-one in both surface water and wastewater after derivatization with N, O-bis(trimethyl-silyl)trifluoroacetamide (BSTFA). Extraction from the water samples was by an SPE technique, using either a copolymeric (Oasis HLB) or C 18 silica sorbents, depending on the target contaminants. Extraction from the sludge samples was by a Soxtec system using methanol. Percentage recoveries for most of the selected compounds, using either a copolymeric (Oasis HLB) or C 18 silica sorbents, were satisfactory (>60%). Quantification limits for the target compounds were at ppb levels in both water and sludge samples when using LC–ESI–MS in both positive and negative modes. They reached ppt levels in water when using GC–MS (in large volume injection mode) and GC–MS–MS. The results revealed 4-NP, NPEO n and AEOs in sludge samples at a concentration range of 1.3–8.5 μg/g, and NPEO n , OPEO n and other compounds, such as coprostan and bisphenol A, in surface water and/or wastewater samples at concentrations ranging from the ppt to ppb levels.