title: A validated UPLC-MS/MS method for the surveillance of ten aquatic biotoxins in European brackish and freshwater systems.
abstract: Over the past few decades, there has been an increased frequency and duration of cyanobacterial Harmful Algal Blooms (HABs) in freshwater systems globally. These can produce secondary metabolites called cyanotoxins, many of which are hepatotoxins, raising concerns about repeated exposure through ingestion of contaminated drinking water or food or through recreational activities such as bathing/swimming. An ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) multi-toxin method has been developed and validated for freshwater cyanotoxins; microcystins-LR, -YR, -RR, -LA, -LY and -LF, nodularin, cylindrospermopsin, anatoxin-a and the marine diatom toxin domoic acid. Separation was achieved in around 9min and dual SPE was incorporated providing detection limits of between 0.3 and 5.6ng/L of original sample. Intra- and inter-day precision analysis showed relative standard deviations (RSD) of 1.2-9.6% and 1.3-12.0% respectively. The method was applied to the analysis of aquatic samples (n=206) from six European countries. The main class detected were the hepatotoxins; microcystin-YR (n=22), cylindrospermopsin (n=25), microcystin-RR (n=17), microcystin-LR (n=12), microcystin-LY (n=1), microcystin-LF (n=1) and nodularin (n=5). For microcystins, the levels detected ranged from 0.001 to 1.51μg/L, with two samples showing combined levels above the guideline set by the WHO of 1μg/L for microcystin-LR. Several samples presented with multiple toxins indicating the potential for synergistic effects and possibly enhanced toxicity. This is the first published pan European survey of freshwater bodies for multiple biotoxins, including two identified for the first time; cylindrospermopsin in Ireland and nodularin in Germany, presenting further incentives for improved monitoring and development of strategies to mitigate human exposure.
authors.affiliation: Institute for Global Food Security, School of Biological Sciences, Queen's University Belfast, Stranmillis Road, Belfast BT9 5AG, UK.
authors.forename: Brett
authors.initials: B
authors.lastname: Greer
authors.affiliation: Institute for Global Food Security, School of Biological Sciences, Queen's University Belfast, Stranmillis Road, Belfast BT9 5AG, UK.
authors.forename: Sara E
authors.initials: SE
authors.lastname: McNamee
authors.affiliation: University College Dublin, National University of Ireland, Dublin, Ireland.
authors.forename: Bas
authors.initials: B
authors.lastname: Boots
authors.affiliation: Laboratory of Genetics, School of Biosciences and Veterinary Medicine, University of Camerino, Camerino, MC 62032, Italy.
authors.forename: Lucia
authors.initials: L
authors.lastname: Cimarelli
authors.affiliation: Universite Pierre et Marie Curie, Paris 6, France.
authors.forename: Delphine
authors.initials: D
authors.lastname: Guillebault
authors.affiliation: Veolia Environnement Recherche et Innovation SNC, France.
authors.forename: Karim
authors.initials: K
authors.lastname: Helmi
authors.affiliation: Istituto Superiore di Sanita, Rome, Italy.
authors.forename: Stefania
authors.initials: S
authors.lastname: Marcheggiani
authors.affiliation: National Center of Infectious and Parasitic Diseases, Sofia 1504, Bulgaria.
authors.forename: Stefan
authors.initials: S
authors.lastname: Panaiotov
authors.affiliation: Marilim Gesellschaft fur Gewasseruntersuchung mbH, Germany.
authors.forename: Ulrich
authors.initials: U
authors.lastname: Breitenbach
authors.affiliation: Istanbul University, Istanbul, Turkey.
authors.forename: Reyhan
authors.initials: R
authors.lastname: Akçaalan
authors.affiliation: Universite Pierre et Marie Curie, Paris 6, France.
authors.forename: Linda K
authors.initials: LK
authors.lastname: Medlin
authors.affiliation: BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Straße 11, 12489 Berlin, Germany.
authors.forename: Katrin
authors.initials: K
authors.lastname: Kittler
authors.affiliation: Institute for Global Food Security, School of Biological Sciences, Queen's University Belfast, Stranmillis Road, Belfast BT9 5AG, UK.
authors.forename: Christopher T
authors.initials: CT
authors.lastname: Elliott
authors.affiliation: Institute for Global Food Security, School of Biological Sciences, Queen's University Belfast, Stranmillis Road, Belfast BT9 5AG, UK. Electronic address: katrina.campbell@qub.ac.uk.
authors.forename: Katrina
authors.initials: K
authors.lastname: Campbell
mesh_terms: D002851:Chromatography, High Pressure Liquid; D004784:Environmental Monitoring / Q000379:methods*; D005060:Europe; D005618:Fresh Water / Q000382:microbiology*; D006801:Humans; D052998:Microcystins / Q000032:analysis*; D012623:Seawater / Q000737:chemistry*; D053719:Tandem Mass Spectrometry
chemical_list: D052998:Microcystins
keywords: Biotoxins; Harmful Algal Bloom (HAB); Microcystin; Multiplex; UPLC–MS/MS