Abstract

The increasing frequency of episodes of harmful algal blooms of cyanobacterial origin is a risk to ecosystems and human health. The main human hazard may arise from drinking water supply and recreational water use. For this reason, efficient multiclass analytical methods are needed to assess the level of cyanotoxins in water reservoirs and tackle these problems. This work describes the development of a fast, sensitive, and robust analytical method for multiclass cyanotoxins determination based on dual solid-phase extraction (SPE) procedure using a polymeric cartridge, Oasis HLB (Waters Corporation, Milford, MA, USA), and a graphitized non-porous carbon cartridge, SupelcleanTM ENVI-CarbTM (Sigma-Aldrich, St. Louis, MO, USA), followed by ultra-high-performance liquid chromatography high-resolution mass spectrometry (SPE-UHPLC-HRMS). This method enabled the analysis of cylindrospermopsin, anatoxin-a, nodularin, and seven microcystins (MC-LR, MC-RR, MC-YR, MC-LA, MC-LY, MC-LW, MC-LF). The method limits of detection (MLOD) of the validated approach were between 4 and 150 pg/L. The analytical method was applied to assess the presence of the selected toxins in 21 samples collected in three natural water reservoirs in the Ter River in Catalonia (NE of Spain) used to produce drinking water for Barcelona city (Spain).

Highlights

  • Cyanobacteria are a group of prokaryotic and photosynthetic organisms that are widespread in freshwater and marine environments

  • MO, USA), followed by ultra-high-performance liquid chromatography high-resolution mass spectrometry (SPE-UHPLC-HRMS). This method enabled the analysis of cylindrospermopsin, anatoxin-a, nodularin, and seven microcystins (MC-LR, MC-RR, MC-YR, MC-LA, MC-LY, MC-LW, MC-LF)

  • Concentrations for three MCs (MC-LY, -LW, and -LF) are different due to prime concentration of each standard provided by the producer, which was 7.5 μg/mL for these three cyanotoxins

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Summary

Introduction

Cyanobacteria are a group of prokaryotic and photosynthetic organisms that are widespread in freshwater and marine environments. About 40 different genera [1] can produce secondary metabolites called cyanotoxins to (apparently) defend their living space against other organisms. Cyanotoxins vary in structure and toxicity, and they may be found within bacterial cells or released into the water. Microcystins (MCs) and nodularins (NODs) are cyclic peptides with hepatotoxic activity containing β-amino acid. The common structure of MCs is cyclo(D-Ala-L-X-D-erythro methylAsp(iso-linkage)-L-Z-Adda-D-Glu(isolinkage)-N-methyldehydro-Ala). The prime structural difference lies within the L-amino-acid residues

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