From target analysis to suspect and non-target screening of endocrine-disrupting compounds in human urine

Abstract

In the present work, a target analysis method for simultaneously determining 24 diverse endocrine-disrupting compounds (EDCs) in urine (benzophenones, bisphenols, parabens, phthalates and antibacterials) was developed. The target analysis approach (including enzymatic hydrolysis, clean-up by solid-phase extraction and analysis by liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS)) was optimized, validated and applied to volunteers’ samples, in which 67% of the target EDCs were quantified. For instance, benzophenone-3 (0.2–13 ng g−1), bisphenol A (7.7–13.7 ng g−1), methyl 3,5-dihydroxybenzoate (8–254 ng g−1), mono butyl phthalate (2–17 ng g−1) and triclosan (0.3–9 ng g−1) were found at the highest concentrations, but the presence of other analogues was detected as well. The developed target method was further extended to suspect and non-target screening (SNTS) by means of LC coupled to high-resolution MS/MS. First, well-defined workflows for SNTS were validated by applying the previously developed method to an extended list of compounds (83), and then, to the same real urine samples. From a list of approximately 4000 suspects, 33 were annotated at levels from 1 to 3, with food additives/ingredients and personal care products being the most abundant ones. In the non-target approach, the search was limited to molecules containing S, Cl and/or Br atoms, annotating 4 pharmaceuticals. The results from this study showed that the combination of the lower limits of detection of MS/MS and the identification power of high-resolution MS/MS is still compulsory for a more accurate definition of human exposome in urine samples. Graphical abstract: [Figure not available: see fulltext.].