Simultaneous detection of nine cyanotoxins in drinking water using dual solid-phase extraction and liquid chromatography–mass spectrometry

• Published in: Toxicon (Oxford) 2011-08, Vol.58 (2), p.209-218
• Main Authors: Yen, Hung-Kai, Lin, Tsair-Fuh, Liao, Pao-Chi
• Format: Article
• Language: English
• Subjects: Alkaloids - analysis; Alkaloids - chemistry; Animal poisons toxicology. Antivenoms; Bacterial Proteins - analysis; Bacterial Proteins - chemistry; Bacterial Toxins - analysis; Bacterial Toxins - chemistry; Bacteriology; Biological and medical sciences; Calibration; Cartridges; Chromatography; Chromatography, High Pressure Liquid; Cyanobacteria - metabolism; Cylindrospermopsin; detection limit; Drinking water; Drinking Water - analysis; Extraction; Freshwater; Fundamental and applied biological sciences. Psychology; lakes; Lakes - analysis; LC/MS; Limit of Detection; liquid chromatography; mass spectrometry; Medical sciences; Microbiology; Microcystin; microcystins; Microcystins - analysis; Microcystins - chemistry; monitoring; nodularin; Pathogenicity, virulence, toxins, bacteriocins, pyrogens, host-bacteria relations, miscellaneous strains; Peptides, Cyclic - analysis; Peptides, Cyclic - chemistry; quality control; Solid Phase Extraction; SPE; Spectrometry; Spectrometry, Mass, Electrospray Ionization; Spectroscopy; Surrogate standard; Taiwan; Tap water; Toxicology; Tropanes - analysis; Tropanes - chemistry; Tropanes - isolation & purification; Uracil - analogs & derivatives; Uracil - analysis; Uracil - chemistry; water reservoirs; Water Supply - analysis; water treatment
• ISSN: 0041-0101; 1879-3150
• DOI: 10.1016/j.toxicon.2011.06.003

A solid-phase extraction (SPE)–liquid chromatography (LC)–mass spectrometry (MS) method was developed to concentrate and detect nine cyanotoxins simultaneously, including six microcystins (MCs) congeners, nodularin (NOD), anatoxin-a (ATX) and cylindrospermopsin (CYN), in pure and natural waters. A dual cartridge SPE assembly was tested for the operating parameters of cyanotoxin extraction. A surrogate standard (SS), 1,9-diaminononane, was spiked in all the samples before the SPE extraction, and an internal standard (IS), 2,3,5-trimethylphenyl methyl carbamate, was spiked before LC/MS analysis. The method detection limit (MDL) was 2–100 ng/L for nine cyanotoxins in pure water and was increased by a factor of three to ten in a more complicated water matrix. The recoveries based on SS were between 83 and 104%, while those based on IS were 80–120%. The developed method was successfully employed in analyzing 33 water samples collected from eutrophic lakes, water treatment plants and distribution taps. MCs, NOD, and CYN were detected in the reservoir water, with concentrations as high as 36 μg/L. In addition, for the first time in Taiwan’s tap water, CYN was detected at concentrations as high as 8.6 μg/L. Quality control data for the field samples shows that the analytical scheme developed is appropriate for monitoring cyanotoxins. ► In this study we developed a method for the analysis of nine cyanotoxins. ► We employed a dual cartridge solid-phase extraction and liquid chromatography–mass spectrometry. ► We analyzed 33 water samples from eutrophic lakes, water treatment plants and distribution taps. ► Microcystins, noduralin, and cylindrospermopsin (CYN) were detected in the reservoir water. ► For the first time in Taiwan’s tap water, CYN was detected at concentrations as high as 8.6 μg/L.