Ultra-High-Performance Liquid Chromatography Coupled with Quadrupole Orbitrap High-Resolution Mass Spectrometry for Multi-Residue Analysis of Mycotoxins and Pesticides in Botanical Nutraceuticals

Abstract

Cannabidiol (CBD) food supplements made of Cannabis sativa L. extracts have quickly become popular products due to their health-promoting effects. However, potential contaminants, such as mycotoxins and pesticides, can be coextracted during the manufacturing process and placed into the final product. Accordingly, a novel methodology using ultra-high-performance liquid chromatography coupled with quadrupole Orbitrap high-resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS) was developed to quantify 16 mycotoxins produced by major C. sativa fungi, followed by a post-target screening of 283 pesticides based on a comprehensive spectral library. The validated procedure was applied to ten CBD-based products. Up to six different Fusarium mycotoxins were found in seven samples, the most prevalent being zearalenone (60%) and enniatin B1 (30%), both found at a maximum level of 11.6 ng/g. Co-occurrence was observed in four samples, including one with enniatin B1, enniatin A and enniatin A1. On the other hand, 46 different pesticides were detected after retrospective analysis. Ethoxyquin (50%), piperonyl butoxide (40%), simazine (30%) and cyanazine (30%) were the major residues found. These results highlight the necessity of monitoring contaminants in food supplements in order to ensure a safe consumption, even more considering the increase trend in their use. Furthermore, the developed procedure is proposed as a powerful analytical tool to evaluate the potential mycotoxin profile of these particular products.

Target Quantification and Semi-Target Screening of Undesirable Substances in Pear Juices Using Ultra-High-Performance Liquid Chromatography-Quadrupole Orbitrap Mass Spectrometry

“…Up to 65% of the conventional juice samples ( n = 14) showed contamination with only one mycotoxin, whereas four or more mycotoxins co-occurred in the majority of organic samples (71%, n = 7). The most common associations were ZEN alongside its two metabolites, and ZEN, T-2, and ENNB, which seems to be a frequent mixture in several plant-based foodstuffs [ 24 , 25 ]. Furthermore, ENNB1 and ENNA1 co-occurred with ENNB in organic samples, and the combination ENNA and ENNA1 was also observed in one conventional juice sample.…”

Using Cholinesterases and Immobilized Luminescent Photobacteria for the Express-Analysis of Mycotoxins and Estimating the Efficiency of Their Enzymatic Hydrolysis

“…These are currently the most actively pursued areas: (i) elucidating the mechanisms of toxic effects of mycotoxins on living organisms [ 5 ]; (ii) development and testing of effective selective and sensitive analytical methods for the detection of mycotoxins in food, agricultural feed, and raw materials for the pharmaceutical industry [ 9 , 10 ]; (iii) search for sorbents capable of removing mycotoxins from raw materials [ 11 ]; (iv) the search for new methods for the destruction of mycotoxins, especially those involving bio-destructors [ 12 , 13 ]. The last of the above directions is especially important today, since it implies the development of means, including combined action, that eliminate mycotoxins not only due to their sorption, but also due to their catalytic decomposition.…”

“…In fundamental and applied research in the field of mycotoxins, liquid chromatography (LC) and enzyme-linked immunosorbent assay (ELISA) are most widely used today. An LC run is followed by mass spectrometry (MS), sensitive fluorescence detection (FLD), or ultraviolet (UV) detection [ 9 , 10 , 12 ]. High analytical accuracy and selectivity are the main advantages of the abovementioned methods.…”

“…The initial choice of perspective biocatalysts for in-depth study is based on the published data. For example, it is known that enzymes of some classes, including hexa-histidine-tagged organophosphorus hydrolase (His 6 -OPH), exhibit destructive activity towards various mycotoxins [ 3 , 9 , 10 , 13 , 14 , 15 , 16 , 17 ]. Computer design, and, in particular, the molecular docking method [ 18 , 19 ], is yet another technique which has been proved useful for the initial selection of promising potential candidates from a number of enzymes for the decomposition of mycotoxins.…”

Application of LC–MS/MS in the Mycotoxins Studies

“…the quantification of 16 mycotoxins produced by major C. sativa fungi [7]. They report that up to six different Fusarium mycotoxins were found in seven of the ten analyzed samples, the most prevalent being ZEN (60%) and ENN B1 (30%).…”