Development and validation of an ultra-high performance liquid chromatographic high resolution Q-Orbitrap mass spectrometric method for the simultaneous determination of steroidal endocrine disrupting compounds in aquatic matrices

- Optimised and validated UHPLC-HR-Q-Orbitrap-MS method.
- Simultaneous quantitative measurement of 70 steroidal EDCs.
- Very low empirical method detection and quantification limits.
- Applicability of method: robust EDC profiling of the marine environment.
- High identification potential because of various diagnostic ions.

The lack of adequate strategies for monitoring endocrine disrupting compounds (EDCs) in the aquatic environment is emphasized in the European Water Framework Directive. In this context, a new UHPLC-HR-Q-Orbirtrap-MS multi-residue method was developed for the simultaneous measurement of 70 steroidal EDCs in two aquatic matrices, i.e. sea and fresh water. First, an instrumental APCI-UHPLC-HR-Q-Orbitrap-MS was devised for separating and detecting the EDC isomers and mass analogues, within 12.5 min per run. Next, an appropriate extraction was statistically optimised using a three-strep workflow (95% confidence interval, p > 0.05); including fractional factorial resolution IV, simplex lattice, and response surface methodological designs. The fitness-for-purpose of the method was demonstrated through successful validation at relevant environmental concentrations, i.e. the low nano- and picogram range. Method quantification limits ranged for the androgens (n = 33), oestrogens (n = 14), progestins (n = 12), and corticosteroids (n = 11) between, respectively, 0.13 and 5.00 ng L−1, 0.25 and 5.00 ng L−1, 0.13 and 2.50 ng L−1, and 0.50 and 5.00 ng L−1. Good linearity (R2 ≥ 0.99) and no lack of fit was observed (95% confidence interval, p > 0.05) for the 70 steroidal EDCs. In addition, good recovery (95-109%) and satisfactory repeatability (RSD < 8.5%, n = 18) and reproducibility (RSD < 10.5%, n = 12) were obtained. Finally, the applicability of the multi-residue method was demonstrated by measuring steroidal EDC in 28 sea water samples collected from four different locations during fall 2016 and winter 2017. Regarding the sea water samples, all the classes were ubiquitously present and included different metabolites, transformation product and or degradation products from the parent EDCs (n = 43).

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