Rapid determination of chromium species in environmental waters using a diol-bonded polymer-stationary column under water-rich conditions coupled with ICPMS

Chromium speciation analysis in environmental water is of great significance for the monitoring of water pollution and assessing its influences on human health. This study proposes a rapid analytical approach for the simultaneous determination of Cr(VI) and Cr(III) in environmental waters by hydrophilic interaction chromatography (HILIC) coupled with ICPMS under a water-rich condition. 2,6-Pyridinedicarboxylic acid (PDCA) was used to unify Cr(III) species in various chemical forms into a stable Cr(III)–PDCA anion complex and then separated from Cr(VI) oxyanion on a diol-bonded polymer-based HILIC column. An aqueous mobile phase containing 50 mmol L⁻¹ ammonium acetate (pH 7.0), 2 mmol L⁻¹ PDCA, and 4% acetonitrile successfully separates chromium species as well as chloride ions. In addition, our method elutes Cr(VI) preferentially over Cr(III)–PDCA, enabling rapid determination of Cr(VI), and both chromium species were analyzed within 6.2 min. The detection limits of 0.19 μg L⁻¹ for Cr(VI) and 0.35 μg L⁻¹ for Cr(III) at m/z 52 under He collision mode are comparable to or better than the conventional ion exchange chromatography–ICPMS methods, and quantitative recovery was obtained from spike-recovery tests on river water samples containing various levels of matrix. Optimization experiments of the HPLC conditions indicate that the retentions of Cr(VI) and Cr(III)–PDCA are characterized by electrostatic and nonpolar interactions, respectively. The retention behavior of inorganic anions and cations in water-rich conditions observed in this study will provide new insights into the separation mechanism in polymer-based HILIC columns, which has been poorly understood. Graphical abstract: (Figure presented.)