Hydroxyanthracene derivatives (HADs) are plant substances produced by a variety of plant species, including different Aloe, Rheum, and Rhamnus species and Cassia senna. These plants are often used in food supplements to improve bowel function. However, recently, the European Commission prohibited a number of HADs due to toxicological concerns. These HADs included aloin (aloin A and aloin B), aloe-emodin, emodin, and danthron. Most of the currently available analytical methods are restricted to the analysis of only these compounds and do not include other HADs. In this view, a multi-analyte method could be useful for both regulatory analysis and dietary intake studies. To this end, such a method, employing liquid chromatography–tandem mass spectrometry and targeting 16 different HADs, was developed and validated in this study. Limits of quantification were in the range from 0.025 mg kg−1 to 1 mg kg−1. The recovery of the method was within the acceptable range of 80% to 120%, with the exception of physcion. Repeatability varied from 0.5% to 11.6%, and the range for within-laboratory reproducibility was from 3.4% to 16.3%. The expanded measurement uncertainty was below 50% for all HADs. Subsequently, 24 commercial samples of food supplements and herbal infusions sourced in Belgium were analyzed. The results indicated that although the industry put a great effort into minimizing the amount of aloin and danthron present in food supplements, more than half of the products still exceeded the maximum tolerated levels suggested for aloe-emodin and emodin.
Toxic cyanobacterial blooms are prevalent in surface waters. Depending on several conditions, these blooms produce cyanotoxins. Human exposure to these toxins can occur through multiple routes, including contaminated crops through irrigation with contaminated water. Analytical methods have been developed for cyanotoxin quantification to investigate these exposures. Yet, proper comparisons between different labs via proficiency tests or interlaboratory comparison tests, as well as method quality assurance, are impossible. Developing reference materials for cyanotoxins in plants would help resolve these problems. Therefore, a novel liquid hydroculture setup was optimized to grow and contaminate strawberries. During fruit ripening, these plants were exposed to growth medium contaminated with pure microcystin-LR or freeze-dried cyanobacterial biomass containing different microcystin congeners. Afterwards, fruits, greens, and roots were harvested. Validated UHPLC-MS/MS methods were used to quantify the microcystin congeners in the growth medium and the plants. Furthermore, both contamination conditions resulted in the accumulation of toxin(s) in the roots and the greens. Yet in the contamination models, no toxin(s) accumulated in the fruits. Therefore, this contamination approach, combined with strawberries as a berry plant model, is only suitable for reference material production for limited matrices. Our cultivation model to produce reference material could be evaluated for other berry producers.