A validated UPLC–MS/MS method for the surveillance of ten aquatic biotoxins in European brackish and freshwater systems

Brett Greer, Sara E. McNamee, Bas Boots, Lucia Cimarelli, Delphine Guillebault, Karim Helmi, Stefania Marcheggiani, Stefan Panaiotov, Ulrich Breitenbach, Reyhan Akcaalan, Linda K. Medlin, Katrin Kittler, Christopher T. Elliott, Katrina Campbell

Research output: Contribution to journalArticle

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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 9 min and dual SPE was incorporated providing detection limits of between 0.3 and 5.6 ng/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 1.51 mg/L, with two samples showing combined levels above the guideline set by the WHO of 1 mg/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.
Original languageEnglish
Pages (from-to)31-40
Number of pages10
JournalHarmful Algae
Volume55
DOIs
Publication statusPublished - May 2016

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microcystins
cylindrospermopsin
toxin
nodularin
microcystin-LR
monitoring
hepatotoxins
cyanobacterial toxins
toxins
recreational activity
secondary metabolite
anatoxins
liquid chromatography
incentive
algal bloom
domoic acid
diatom
sampling
mass spectrometry
ultra-performance liquid chromatography

Cite this

Greer, Brett ; McNamee, Sara E. ; Boots, Bas ; Cimarelli, Lucia ; Guillebault, Delphine ; Helmi, Karim ; Marcheggiani, Stefania ; Panaiotov, Stefan ; Breitenbach, Ulrich ; Akcaalan, Reyhan ; Medlin, Linda K. ; Kittler, Katrin ; Elliott, Christopher T. ; Campbell, Katrina. / A validated UPLC–MS/MS method for the surveillance of ten aquatic biotoxins in European brackish and freshwater systems. In: Harmful Algae. 2016 ; Vol. 55. pp. 31-40.
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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 9 min and dual SPE was incorporated providing detection limits of between 0.3 and 5.6 ng/L of original sample. Intra- and inter-day precision analysis showed relativestandard 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 1.51 mg/L, with two samples showing combined levels above the guideline set by the WHO of 1 mg/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.",
author = "Brett Greer and McNamee, {Sara E.} and Bas Boots and Lucia Cimarelli and Delphine Guillebault and Karim Helmi and Stefania Marcheggiani and Stefan Panaiotov and Ulrich Breitenbach and Reyhan Akcaalan and Medlin, {Linda K.} and Katrin Kittler and Elliott, {Christopher T.} and Katrina Campbell",
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Greer, B, McNamee, SE, Boots, B, Cimarelli, L, Guillebault, D, Helmi, K, Marcheggiani, S, Panaiotov, S, Breitenbach, U, Akcaalan, R, Medlin, LK, Kittler, K, Elliott, CT & Campbell, K 2016, 'A validated UPLC–MS/MS method for the surveillance of ten aquatic biotoxins in European brackish and freshwater systems', Harmful Algae, vol. 55, pp. 31-40. https://doi.org/10.1016/j.hal.2016.01.006

A validated UPLC–MS/MS method for the surveillance of ten aquatic biotoxins in European brackish and freshwater systems. / Greer, Brett; McNamee, Sara E.; Boots, Bas ; Cimarelli, Lucia; Guillebault, Delphine; Helmi, Karim; Marcheggiani, Stefania; Panaiotov, Stefan; Breitenbach, Ulrich; Akcaalan, Reyhan; Medlin, Linda K.; Kittler, Katrin; Elliott, Christopher T.; Campbell, Katrina.

In: Harmful Algae, Vol. 55, 05.2016, p. 31-40.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A validated UPLC–MS/MS method for the surveillance of ten aquatic biotoxins in European brackish and freshwater systems

AU - Greer, Brett

AU - McNamee, Sara E.

AU - Boots, Bas

AU - Cimarelli, Lucia

AU - Guillebault, Delphine

AU - Helmi, Karim

AU - Marcheggiani, Stefania

AU - Panaiotov, Stefan

AU - Breitenbach, Ulrich

AU - Akcaalan, Reyhan

AU - Medlin, Linda K.

AU - Kittler, Katrin

AU - Elliott, Christopher T.

AU - Campbell, Katrina

PY - 2016/5

Y1 - 2016/5

N2 - 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 9 min and dual SPE was incorporated providing detection limits of between 0.3 and 5.6 ng/L of original sample. Intra- and inter-day precision analysis showed relativestandard 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 1.51 mg/L, with two samples showing combined levels above the guideline set by the WHO of 1 mg/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.

AB - 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 9 min and dual SPE was incorporated providing detection limits of between 0.3 and 5.6 ng/L of original sample. Intra- and inter-day precision analysis showed relativestandard 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 1.51 mg/L, with two samples showing combined levels above the guideline set by the WHO of 1 mg/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.

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DO - 10.1016/j.hal.2016.01.006

M3 - Article

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JO - Harmful Algae

JF - Harmful Algae

SN - 1568-9883

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