Analysis of multiclass cyanotoxins (microcystins, anabaenopeptins, cylindrospermopsin and anatoxins) in lake waters using on-line SPE liquid chromatography high-resolution Orbitrap mass spectrometry

Abstract

An on-line SPE-UHPLC-HRMS method was optimized for filtration, on-line SPE, and HRMS conditions for the rapid screening of 17 cyanotoxins. 8 cyanotoxins were detected with 75% of lakes containing MC-LR and 38% containing anabaenopeptins (A or B).

A Mini-Review on Detection Methods of Microcystins

“…Besides, the developed paper spray ionization method coupled with a time of flight (TOF) MS and a filter-feeder organism coupled with matrix-assisted laser desorption ionization-TOF MS (MALDI-TOF MS) were found to yield effective MCs determination in various water samples [ 83 , 129 ]. It is worth knowing that the high throughput method based on on-line SPE coupled to LC–quadrupole TOF resolution MS (on-line SPE-LC-QToF HRMS) (LOD between 0.004 and 0.01 µg/L), on-line SPE-UHPLC-HRMS (LOD between 8 and 53 ng/L), online SPE-UHPLC-MS/MS (LOD between 0.1 and 0.5 µg/kg) and online concentration LC/MS/MS workflow (LOD between 0.6 and 3.8 ng/L) also successfully detected different variants of MC in water samples [ 34 , 96 , 101 , 102 ]. The matrix solid-phase dispersion (MSPD) followed by HPLC/MS/MS (MSPD-HPLC-MS/MS) (LOD 13.0 μg/kg (dw)) and SPE-UPLC-MS/MS (LOD 0.06–0.42 ng/g f.w) were also used to determine trace levels of MCs in various vegetables [ 142 ].…”

Co-Occurrence of Cyanobacteria and Cyanotoxins with Other Environmental Health Hazards: Impacts and Implications

“…Following wildlife-, domestic animal-, and human-intoxications due to exposure to cyanobacterial mass populations, the volume of research over recent years into the toxicology and toxinology of cyanobacteria and cyanotoxins has increased greatly and such growth continues e.g., [ 1 , 5 , 7 , 8 ]. In recognition of the co-occurrence of multiple variants within individual classes of cyanotoxins, of different cyanotoxin classes, and of cyanotoxins plus phycotoxins, it is encouraging that physico-chemical methods for the co-analysis of these combinations are being developed [ 5 , 19 , 20 , 21 , 140 ]. However, since cyanobacterial mass populations commonly develop in waterbodies which are under intensive anthropogenic use (e.g., for domestic, industrial, and agricultural wastewater discharge, abstraction for drinking water treatment, recreation, crop irrigation, and fisheries) it should be anticipated that toxigenic cyanobacteria can co-occur with a wide range of additional biological and chemical health hazards.…”

“…The further development and application of physico-chemical analytical methods for the detection, identification, and quantification of specific cyanotoxins continues to support and enable the application of policies for the risk management of water resources affected by cyanobacterial mass populations. These include specific methods for individual classes of cyanotoxins [ 5 ] and, increasingly, methods for the multiclass analysis of the toxins in single procedures [ 18 , 19 , 20 , 21 ]. However, whilst such methods alone can provide a partial indication of toxicity presented by axenic strains of cyanobacteria grown in the laboratory, they may not take into full account the toxicological significance of mass populations of cyanobacteria in open environments.…”

Ultra-Trace Analysis of Cyanotoxins by Liquid Chromatography Coupled to High-Resolution Mass Spectrometry

“…PRM mode is normally used for short inclusion lists, as scan speed is not high enough for larger inclusion lists in the same time window. For instance, Roy-Lachapelle et al applied PRM mode to obtain the MS/MS spectra of five cyanotoxins [24]. To have enough scans per peak, ddMS 2 and data-independent acquisitions (DIA) could be applied.…”

“…High and ultra-high performance liquid chromatography coupled with mass spectrometry (HPLC-MS, UHPLC-MS) and tandem mass spectrometry (MS/MS) are the techniques of choice, in particular with triple quadrupole (QqQ) analyzers [11,[15][16][17][18]. However, due to the advances in identification and sensitivity, several HRMS methods have been applied for the determination of cyclic peptides [19][20][21] and multi-class cyanotoxins [22][23][24][25] in freshwater. These methods present limits of detection from 0.3 ng/L to 3900 ng/L, being 0.3-5.6 ng/L the lowest ones reported by Greer et al [18] by UHPLC-MS/MS.…”