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Planta Med 2021; 87(12/13): 1069-1079
DOI: 10.1055/a-1517-5828
Natural Product Chemistry and Analytical Studies
Original Papers

Multi-Class UHPLC-MS/MS Method for Plant Toxins and Cyanotoxins in Food Supplements and Application for Belgian Market Samples[ # ]

Els Van Pamel
1   Flanders Research Institute for Agriculture, Fisheries and Food (ILVO), Technology and Food Science Unit, Melle, Belgium
,
Jean Henrottin
2   CER Groupe, Marloie, Belgium
,
Christof Van Poucke
1   Flanders Research Institute for Agriculture, Fisheries and Food (ILVO), Technology and Food Science Unit, Melle, Belgium
,
Nathalie Gillard
2   CER Groupe, Marloie, Belgium
,
Els Daeseleire
1   Flanders Research Institute for Agriculture, Fisheries and Food (ILVO), Technology and Food Science Unit, Melle, Belgium
› Author AffiliationsSupported by: Belgian Federal Public Service of Health, Food Chain Safety and Environment RT 16/5
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Abstract

The presence of plant toxins and/or cyanotoxins in food supplements implies consumer health risks. Therefore, a targeted ultra-high performance liquid chromatographic-tandem mass spectrometric method to detect/quantify 25 toxins simultaneously in food supplement formulations was developed and validated. Full validation for tablets/powders and secondary validation for a liquid and soft gel capsule indicated that most compounds were efficiently extracted (≥ 75%), while others were only partly extracted (18 – 61%). Trueness was fulfilled (70 – 120%), with some exceptions (mostly at the lowest validation level). Intralaboratory repeatability, intra- and interlaboratory reproducibility values of ≤ 20%, ≤ 25%, and ≤ 25% were obtained for most, respectively. Matrix effects were found to be significant for most compounds. Good sensitivity (µg/kg level) was observed for galegin(e), lycopsamine, lycorine, rubiadin, skimmiamine, and vascin(e), in contrast to helveticoside, lucidin, lucidin-3-primveroside, plumbagin(e), and thujone, which were detected at the mg/kg level. The other compounds were characterized by a sensitivity between 10 to 1000 µg/kg. The validated methodology was applied for 52 food supplements (tablets, capsules, liquids/syrup, etc.) purchased from the Belgian market. In more than 25% of the samples, one or more toxins were detected (concentrations determined using standard addition). Lycopsamine, microcystin LR, solamargine, thujone, and vasicin(e) were the most frequently detected toxins. A clear link between the toxins detected and the plant species on the food supplement ingredient list could not always be established. This generic “dilute-and-shoot” procedure can be used for further research on toxins in food supplements and by extension other plant/algae-based food/feed commodities (herbs, edible flowers, etc.).

Key words

alkaloids - microcystin LR - thujone - Artemisia - Asteraceae - Borago - Boraginaceae - Aphanizomenon flos-aquae - Aphanizomenonaceae

# Dedicated to Professor Arnold Vlietinck on the occasion of his 80th birthday.


Supporting Information

    Table 1S: Formula, retention time, and mass spectrometric characteristics (electrospray ionization type, cone voltage [V], and collision energy [eV]) obtained for the precursor and corresponding product ions for the toxins considered. Table 2S: Overview of the intralaboratory validation parameter results obtained by lab 1 for the UHPLC-MS/MS methodology (retention time [Rt; min], curve type, matrix effects [ME] or signal suppression/enhancement [SSE], extraction efficiency [EE], apparent recovery [RA], repeatability [RSDr], intralaboratory [RSDR] reproducibility, detection limit [LOD], quantification limit [LOQ], and expanded measurement uncertainty [MU]). An elaborative validation (full validation; 3 different concentrations each with 4 replicates) was performed for 1 matrix (3 powdered tablets, on 3 days); secondary validation was performed for the liquid content of an ampule and the content of a softgel capsule. Table 3S: Overview of the intralaboratory validation parameter results obtained by lab 2 for the UHPLC-MS/MS methodology (retention time [Rt; min], curve type, matrix effects [ME] or signal suppression/enhancement [SSE], extraction efficiency [EE], apparent recovery [RA], repeatability [RSDr], intralaboratory [RSDR] reproducibility, detection limit [LOD], quantification limit [LOQ], and expanded measurement uncertainty [MU]). An elaborative validation (full validation; 3 different concentrations each with 4 replicates) was performed for 1 matrix (3 powdered tablets, on 3 days); secondary validation was performed for the liquid content of an ampule.Table 4S: Overview of the interlaboratory reproducibility (RSDR) performed for powdered tablets. Fig. 1S: Chromatogram of plant/algae toxins obtained for an artificially spiked dietary food supplement sample (* targeted compound).

  • Supporting Information


Publication History

Received: 02 December 2020

Accepted after revision: 25 May 2021

Article published online:
09 July 2021

© 2021. Thieme. All rights reserved.

Georg Thieme Verlag KG
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