Solid-phase extraction, quantification, and selective determination of microcystins in water with a gold-polypyrrole nanocomposite sorbent material

Abstract

A novel sorbent material, gold-polypyrrole (Au-PPy) nanocomposite-coated silica, is described for the efficient solid-phase extraction (SPE) of six common microcystins (MCs) well below the recommended United States EPA and World Health Organization (WHO) guidelines. With the optimized SPE protocol, samples spiked with MCs were determined at ng/L concentrations by liquid chromatography-mass spectrometry (LC-MS) in different aqueous sample matrices, including HPLC-grade, tap, and lake water. The average recoveries for all MCs tested in the three water matrices ranged from 94.1-103.2% with relative standard deviations (RSDs) of 1.6-5.4%, which indicated excellent extraction efficiency and reproducibility. Limits of detection (LODs) and limits of quantification (LOQs) for all MCs in both tap and lake water samples were determined to be ≤1.5 ng/L and 5.0 ng/L, respectively. The Au-PPy nanocomposite-coated sorbent material was reusable for at least three independent MC extractions with a single SPE cartridge in the concentration range of 10-500 ng/L. Importantly, off-column selective separation at the sample preparation and preconcentration stage between more hydrophilic and more hydrophobic MCs was achieved by sequential elution through changes in the solvent composition and SPE bed size. Therefore, the Au-PPy nanocomposite-coated silica sorbent is a promising new material for the quantification of MC variants in water samples.

Keywords: Chemical polymerization; Gold-polypyrrole nanocomposite; LC–MS; Microcystins; Selective separation; Solid-phase extraction.