title: Liquid chromatography-tandem mass spectrometry application, for the determination of extracellular hepatotoxins in Irish lake and drinking waters.
abstract: A novel method for the determination of hepatotoxins; microcystins (MCs), and nodularin (Nod) in lake water and domestic chlorinated tap water has been developed using liquid chromatography hyphenated with electrospray ionization triple quadrupole mass spectrometry (LC-ESI-MS/MS). Optimization of the mass spectrometer parameters and mobile-phase composition was performed to maximize the sensitivity and reproducibility of the method. Detection of the hepatotoxins was carried out using multiple reaction monitoring experiments, thus improving the selectivity of the method. A total ion chromatogram and a precursor ion scan on ion m/z 135 was also applied to all samples to detect unknown microcystins or microcystins for which there are no standards available. A comprehensive validation of the LC-ESI-MS/MS method was completed that took into account matrix effects, specificity, linearity, accuracy, and precision. Good linear calibrations were obtained for MC-LR (1-200 microg/L; R2=0.9994) in spiked lake and tap water samples (1-50 microg/L; R2=0.9974). Acceptable interday repeatability was achieved for MC-LR in lake water with RSD values (n=9) ranging from 9.9 (10 microg/L) to 5.1% (100 microg/L). Excellent limits of detection (LOD) and limits of quantitation (LOQ) were achieved with spiked MCs and Nod samples; LOD=0.27 microg/L and LOQ=0.90 microg/L for MC-LR in the "normal linear range" and LOD=0.08 microg/L and LOQ=0.25 microg/L in the "low linear range" in both lake and chlorinated tap water. Similar results were obtained for a suite of microcystins and nodularin. This sensitive and rapid method does not require any sample preconcentration, including the elimination of solid-phase extraction (SPE) for the effective screening of hepatotoxins in water below the 1 microg/L WHO provisional guideline limit for MC-LR. Furthermore, SPE techniques are time-consuming, nonreproducible at trace levels, and offer poor recoveries with chlorinated water. The application of this LC-ESI-MS/MS method for routine screening of hepatotoxins in lake and chlorinated tap water (average Cl2=0.23 mg/L) is achieved and this study represents the first direct method for the screening of hepatotoxins in chlorinated tap water.
authors.affiliation: PROTEOBIO, Mass Spectrometry Centre for Proteomics and Biotoxin Research, Cork Institute of Technology, Bishopstown, Cork, Ireland.
authors.forename: Orla
authors.initials: O
authors.lastname: Allis
authors.forename: Justine
authors.initials: J
authors.lastname: Dauphard
authors.forename: Brett
authors.initials: B
authors.lastname: Hamilton
authors.forename: Aine Ni
authors.initials: AN
authors.lastname: Shuilleabhain
authors.forename: Mary
authors.initials: M
authors.lastname: Lehane
authors.forename: Kevin J
authors.initials: KJ
authors.lastname: James
authors.forename: Ambrose
authors.initials: A
authors.lastname: Furey
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods; D007494:Ireland; D052998:Microcystins / Q000032:analysis*; D008968:Molecular Conformation; D010456:Peptides, Cyclic / Q000032:analysis*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D053719:Tandem Mass Spectrometry / Q000379:methods*; D013997:Time Factors; D014881:Water Supply / Q000032:analysis*
chemical_list: D052998:Microcystins; D010456:Peptides, Cyclic; C063998:nodularin