Multivariate calibration-assisted high-performance liquid chromatography with dual UV and fluorimetric detection for the analysis of natural and synthetic sex hormones in environmental waters and sediments

A green method is reported based on non-sophisticated instrumental for the quantification of seven natural and synthetic estrogens, three progestagens and one androgen in the presence of real interferences. The method takes advantage of: (1) chromatography, allowing total or partial resolution of a large number of compounds, (2) dual detection, permitting selection of the most appropriate signal for each analyte and, (3) second-order calibration, enabling mathematical resolution of incompletely resolved chromatographic bands and analyte determination in the presence of interferents. Consumption of organic solvents for cleaning, extraction and separation are markedly decreased because of the coupling with MCR-ALS (multivariate curve resolution/alternating least-squares) which allows the successful resolution in the presence of other co-eluting matrix constituents. Rigorous IUPAC detection limits were obtained: 6–24 ng L⁻¹ in water, and 0.1–0.9 ng g⁻¹ in sediments. Relative prediction errors were 2–10% (water) and 1–8% (sediments). - Highlights: • A green and simple chromatographic method for endocrine disruptors is proposed. • Diode array and fluorescence detectors are simultaneously used. • Eleven sex hormones are determined in water and sediment samples. • Outstanding selectivity is attained with MCR-ALS second-order algorithm. - Liquid chromatography coupled to chemometrics allows one to selectively and sensitively quantitate eleven endocrine disruptors in challenging scenarios using a green analytical approach.