Direct injection analysis of polar micropollutants in natural drinking water sources with biphenyl liquid chromatography coupled to high-resolution time-of-flight mass spectrometry

Abstract

A method for the trace analysis of polar micropollutants (MPs) by direct injection of surface water and groundwater was validated with ultrahigh-performance liquid chromatography using a core-shell biphenyl stationary phase coupled to time-of-flight high-resolution mass spectrometry. The validation was successfully conducted with 33 polar MPs representative for several classes of emerging contaminants. Identification and quantification were achieved by semi-automated processing of full-scan and data-independent acquisition MS/MS spectra. In most cases good linearity (R2 ≥ 0.99), recovery (75% to 125%) and intra-day (RSD < 20%) and inter-day precision (RSD < 10%) values were observed. Detection limits of 9 to 83 ng/L and 9 to 93 ng/L could be achieved in riverbank filtrate and surface water, respectively. A solid-phase extraction was additionally validated to screen samples from full-scale reverse osmosis drinking water treatment at sub-ng/L levels and overall satisfactory analytical performance parameters were observed for RBF and reverse osmosis permeate. Applicability of the direct injection method is shown for surface water and riverbank filtrate samples from an actual drinking water source. Several targets linkable to incomplete removal in wastewater treatment and farming activities were detected and quantified in concentrations between 28 ng/L for saccharine in riverbank filtrate and up to 1 μg/L for acesulfame in surface water. The solid phase extraction method applied to samples from full-scale reverse osmosis drinking water treatment plant led to quantification of 8 targets between 6 and 57 ng/L in the feed water, whereas only diglyme was detected and quantified in reverse osmosis permeate. Our study shows that combining the chromatographic resolution of biphenyl stationary phase with the performance of time-of-flight high-resolution tandem mass spectrometry resulted in a fast, accurate and robust method to monitor polar MPs in source waters by direct injection with high efficiency.