Determination of Cyanotoxins and Phycotoxins in Seawater and Algae-Based Food Supplements Using Ionic Liquids and Liquid Chromatography with Time-Of-Flight Mass Spectrometry.

Claudia Giménez-Campillo,Marta Pastor-Belda,Natalia Arroyo-Manzanares,Natalia Campillo,Pilar Viñas,Manuel Hernández-Córdoba

doi:10.3390/toxins11100610

Claudia Giménez-Campillo, Marta Pastor-Belda + Show 4 more

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https://doi.org/10.3390/toxins11100610

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Journal: Toxins	Publication Date: Oct 22, 2019
Citations: 16	License type: CC BY 4.0

Affiliation: University of Murcia

Abstract

An analytical procedure is proposed for determining three cyanotoxins (microcystin RR, microcystin LR, and nodularin) and two phycotoxins (domoic and okadaic acids) in seawater and algae-based food supplements. The toxins were first isolated by a salting out liquid extraction procedure. Since the concentration expected in the samples was very low, a dispersive liquid–liquid microextraction procedure was included for preconcentration. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate (80 mg) was used as green extractant solvent and acetonitrile as disperser solvent (0.5 mL) for a 10 mL sample volume at pH 1.5, following the principles of green analytical chemistry. Liquid chromatography with electrospray ionization and quadrupole time of flight-mass spectrometry (LC-Q-TOF-MS) was used. The selectivity of the detection system, based on accurate mass measurements, allowed the toxins to be unequivocally identified. Mass spectra for quadrupole time of flight-mass spectrometry (Q-TOF-MS) and Q-TOF-MS/MS were recorded in the positive ion mode and quantification was based on the protonated molecule. Retention times ranged between 6.2 and 18.3 min using a mobile phase composed by a mixture of methanol and formic acid (0.1%). None of the target toxins were detected in any of the seawater samples analyzed, above their corresponding detection limits. However, microcystin LR was detected in the blue green alga sample.

Highlights

Cyanotoxins and phycotoxins are secondary metabolites produced by harmful algal blooms of toxic phytoplankton species or photosynthetic microorganisms such as cyanobacteria, which are found in both freshwater habitats and marine environments [1]
Five seawater samples from south-eastern Spain were analyzed in duplicate experiments using the Combination of the salting-out assisted liquid-liquid extraction (SALLE) extraction technique optimized Ionic liquids (IL)-Dispersive liquid–liquid microextraction (DLLME) procedure prior to injection into the LC-Q-TOF-MS
Elution profiles demonstrated with a miniaturized procedure (DLLME with LC-TOF-MS) provided low detection limits for marine the absence of interfering compounds eluting at the retention times of the different toxins

Summary

Introduction

Cyanotoxins and phycotoxins are secondary metabolites produced by harmful algal blooms of toxic phytoplankton species or photosynthetic microorganisms such as cyanobacteria (green–blue algae), which are found in both freshwater habitats and marine environments [1]. The toxins are bioaccumulated by marine organisms, meaning that they may enter the human food chain. In humans, they can cause acute symptoms as gastroenteritis, fever, irritation and liver damage. They can cause acute symptoms as gastroenteritis, fever, irritation and liver damage Their chronic effects include neurotoxicity and carcinogenesis [2]. Phycotoxins are found in molluscs such as oysters, mussels, clams and, to a lesser extent, in fish, crabs, turtles and algae [4], and their presence can produce toxic episodes in human health. Domoic acid (DA) and okadaic acid (OA) are the phycotoxins studied in this work

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