Online Solid-Phase Extraction LC-MS/MS: A Rapid and Valid Method for the Determination of Perfluorinated Compounds at Sub ng·L⁻¹ Level in Natural Water

Abstract

In this research paper, we report a method able to detect perfluorinated compound at pg·L −1 levels in superficial and underground water samples. An online solid phase extraction HPLC-MS/MS method was developed for the analysis of 12 perfluoroalkyl acids (PFASs). The method is based on injection of 5000 µ L of water sample in SPE online WAX column followed by chromatography separation and mass spectrometry determination. SPE online elution was performed by water + 0.05% NH 4 OH and methanol + 0.05% NH 4 OH, while separation of target compounds was achieved within 10 min by Gemini chromatographic column operating from 1 to 12 pH range and using a mixture of water-methanol + 0.05% NH 4 OH. Sub ng·L −1 method detection limits (from 0.2 to 5 ng·L −1 ), linearity (from 0.2 to 250 ng·L −1 ), accuracy (from 80 to 120%), and precision (RSD less than 15% at LOQs levels) were achieved. The method is capable of measuring PFAS at trace levels, but above all it can reach the limit of 200 pg·L −1 required by European regulation for PFOS determination in surface and underground waters. The method was validated for quantitative analysis of PFASs in real water samples.