Simultaneous analysis of different algal toxins by LC-MS

Hummert, Christian; Rühl, A.; Reinhardt, Katrin; Gerdts, Gunnar; Luckas, Bernd

doi:10.1007/bf02491781

Cited by 30 publications

(18 citation statements)

References 25 publications

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“…We are aware of one previous instance where an LC-MS system was deployed on a scientific cruise for shipboard analysis of phycotoxins [1], but this approach was a compromise between obtaining spectral information in near real-time while sacrificing sensitivity. The instrument was a small single-quadrupole mass spectrometer, operated in the selected-ion-monitoring (SIM) mode.…”

Section: Introductionmentioning

confidence: 99%

LC-MS-MS aboard ship: tandem mass spectrometry in the search for phycotoxins and novel toxigenic plankton from the North Sea

et al. 2008

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Phycotoxins produced by various species of toxigenic microalgae occurring in the plankton are a global threat to the security of seafood resources and the health of humans and coastal marine ecosystems. This has necessitated the development and application of advanced methods in liquid chromatography coupled to mass spectrometry (LC-MS) for monitoring of these compounds, particularly in plankton and shellfish. Most such chemical analyses are conducted in land-based laboratories on stored samples, and thus much information on the near real-time biogeographical distribution and dynamics of phycotoxins in the plankton is unavailable. To resolve this problem, we conducted shipboard analysis of a broad spectrum of phycotoxins collected directly from the water column on an oceanographic cruise along the North Sea coast of Scotland, Norway, and Denmark. We equipped the ship with a triple-quadrupole linear ion-trap hybrid LC-MS-MS system for detection and quantitative analysis of toxins, such as domoic acid, gymnodimine, spirolides, dinophysistoxins, okadaic acid, pectenotoxins, yessotoxins, and azaspiracids (AZAs). We focused particular attention on the detection of AZAs, a group of potent nitrogenous polyether toxins, because the culprit species associated with the occurrence of these toxins in shellfish has been controversial. Marine toxins were analyzed directly from size-fractionated plankton net tows (20 μm mesh size) and Niskin bottle samples from discrete depths, after rapid methanolic extraction but without any further clean-up. Almost all expected phycotoxins were detected in North Sea plankton samples, with domoic acid and 20-methylspirolide G being most abundant. Although AZA was the least abundant of these toxins, the high sensitivity of the LC-MS-MS enabled detailed quantification, indicating that the highest amounts of AZA-1 were present in the southern Skagerrak in the 3-20 μm sizefraction. The direct on-board toxin measurements enabled isolation of plankton from stations with high AZA-1 levels and from the most suspicious size-fraction, i.e. most likely to contain the AZA-producer. A large number (>100) of crude cultures were established by serial dilution and later screened for the presence of AZAs after several weeks growth. From one crude culture containing AZA, a small dinoflagellate was subsequently isolated and brought into pure culture. We have thus proved that even sophisticated mass spectrometers can be operated in ship laboratories without any limitation caused by vibrations of the ship's engine or by wave movement during heavy seas at wind forces up to nine Beaufort. On-board LC-MS-MS is a valuable method for near real-time analysis of phycotoxins in plankton for studies on bloom dynamics and the fate of toxins in the food web, and for characterization and isolation of putatively toxigenic organisms.

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Section: Introductionmentioning

confidence: 99%

LC-MS-MS aboard ship: tandem mass spectrometry in the search for phycotoxins and novel toxigenic plankton from the North Sea

et al. 2008

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“…Unfortunately, NMR spectroscopy is quite insensitive, requiring µg to mg amounts of material for successful identification of such complex molecules [14]. In contrast, mass spectrometry is a very sensitive technique that has been routinely used for the analysis of marine toxins for several years [15,16]. Furthermore, recent developments in other areas, such as proteomics and drug discovery, have led to an entirely new generation of hybrid mass spectrometers, with significantly enhanced capabilities in terms of structural identification of unknown compounds, substantially increased sensitivity and mass accuracy.…”

Section: Introductionmentioning

confidence: 99%

Structural study of spirolide marine toxins by mass spectrometry

Sleno

Chalmers

Volmer

2004

Analytical and Bioanalytical Chemistry

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The spirolides are a family of marine biotoxins derived from the dinoflagellate Alexandrium ostenfeldii, recently isolated from contaminated shellfish and characterized. A crude phytoplankton extract has been extensively studied for mass spectrometric determination and characterization of several known spirolides and previously unreported compounds. The complex sample was initially analyzed by full-scan mass spectrometry in an ion-trap instrument, enabling identification of several components. Subsequent analysis by selected-ion monitoring in a triple-quadrupole instrument resulted in the confirmation of the identities of the compounds detected in the ion trap. Purification of the crude extract was performed using an automated mass-based fractionation system, yielding several fractions with different relative contributions of the spirolide components. Collision-induced dissociation (CID) in the triple-quadrupole instrument produced significant fragment ions for all identified species. Selective enrichment of some minor compounds in certain fractions enabled excellent CID spectra to be generated; this had previously been impossible, because of interferences from the major toxins present. Fourier-transform ion cyclotron resonance (FTICR) mass spectrometry was then performed for accurate determination of the masses of MH+ ions of all the species present in the sample. Additionally, infrared multiphoton dissociation in the FTICR instrument generated elemental formulae for product ions, including those formed in the previous collisional activation experiments. Collection of these results and the fragmentation scheme proposed for the main component of the extract, 13-desmethyl spirolide C, from part I of this study, enabled elucidation of the structures of some uncharacterized spirolides and some biogenetically related compounds present at previously unreported masses.

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“…In some cases, the mixture of multiple congeners with different properties requires very different chromatographic conditions for needed separation, including reverse phase to ion-pair or ion-exchange chromatography. [28]. The method developed by Dahlmann et al [29] enabled simultaneous quantification of 7 toxins with a single chromatographic run within 30 minutes using a single quadrupole MS. Table 2 illustrates a range of physicochemical and toxicological properties for several selected algal toxins, including the most commonly occurring algal toxins such as microcystins (MCs), nodularins (NOD), anatoxins (ANTX), cylindrospermopsin (CYL), and saxitoxins (STX).…”

Section: Monitoring and Analytical Challenges For Measuring Various Tmentioning

confidence: 99%

Current Techniques for Detecting and Monitoring Algal Toxins and Causative Harmful Algal Blooms

2014

J Environ Anal Chem

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The detection and monitoring techniques for algal toxins and the causative harmful algal blooms (HABs) are essential for the protection of aquatic lives, shellfish safety, drinking water quality, and public health. Toward the development of fast, easy, and reliable techniques, much progress has been made during the last decade for the qualitative and quantitative analysis of algal toxins. This review highlights the recent progress and new trends of these analytical and monitoring tools, ranging from in-situ quick screening protocols for the monitoring of algal blooms to mass spectrometric analysis of trace levels of various algal toxins and structural elucidation. Solid-phase adsorption toxin tracking (SPATT) deployed in the field for the passive sampling of algal toxins has been recently validated, and improved ELISA-based methods with lower detection limits for more toxins have become commercially available for both screening and routine monitoring purposes. Liquid chromatography-mass spectrometry with several recent mass spectrometric innovations has expanded our understanding of traditional toxins, their metabolites along with newly discovered toxins of ecological importance. Several established in vivo and in vitro bioassays will continue to be used as benchmark toxicological testing of algal toxins; however, newly emerged molecular probing techniques such as real-time quantitative polymerase chain reaction (qPCR) have extended our ability to trace algal toxins from causative organisms at the molecular level. New chemical and biological sensors, lab-on-chip and remote sensing of blooms being developed will hold promise for early warning and routine monitoring to better manage and protect our freshwater, coastal and marine resources from adverse impact by harmful algal blooms.

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Simultaneous analysis of different algal toxins by LC-MS

Cited by 30 publications

References 25 publications

LC-MS-MS aboard ship: tandem mass spectrometry in the search for phycotoxins and novel toxigenic plankton from the North Sea

LC-MS-MS aboard ship: tandem mass spectrometry in the search for phycotoxins and novel toxigenic plankton from the North Sea

Structural study of spirolide marine toxins by mass spectrometry

Current Techniques for Detecting and Monitoring Algal Toxins and Causative Harmful Algal Blooms

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