Advantageous Extraction, Cleanup, and UHPLC-MS/MS Detection of Patulin Mycotoxin in Dietary Supplements and Herbal Blends Containing Hawberry from Crataegus spp.

Abstract

Patulin (PAT) is a highly genotoxic mycotoxin still found as the common contaminant of various kinds of spoiled fruits and related commodities which are often endorsed as the health-enhancing products. Thus, a fast and convenient liquid-solid extraction followed by a solid-phase cleanup with the MycoSep®228 AflaPat multifunctional column was used for the highly efficient isolation of PAT with an average recovery of 112.7% from commercial dietary supplements and herbal blends formulated with dried hawberry. Analysis of the PAT content was carried out using gradient elution with a Synergi Polar C18 column (150 × 2 mm, 4 μm) and UHPLC system equipped with a mass spectrometer. PAT was detected in all (n=14) commercial single-component dietary supplements formulated with dried hawberry belonging to Crataegus monogyna and/or Crataegus laevigata. Similarly, PAT was detected in 67% of the studied multicomponent commercial herbal blends (n=6) that contained—in addition to hawberry—different amounts of apple, chokeberry, elderberry, hibiscus, or mallow. Moreover, the PAT content was determined in the hawberry collected from the mature wild hawthorn trees belonging to three botanical species, Crataegus monogyna Jacq., Crataegus laevigata (Poiret) DC, and Crataegus rhipidophylla Gand, growing in the recreational forest areas and in the law-protected state national forest park in Poland. In conclusion, to prevent PAT accumulation and reduce the health risk of consumers in globalizing markets, the implementation of improved cultivation/processing practices of hawthorn trees and hawberry as well as increased analytical control related to the presence of PAT in dietary supplements and herbal blends formulated with fresh, dried, or frozen hawberry should be urgently recommended.

Determination of patulin in products containing dried fruits by Enzyme‐Linked Immunosorbent Assay technique Patulin in dried fruits

“…The current studies have shown that lower concentration of PAT has been reported for products containing only one dried ingredients (SC) compared with multicomponent products (MC), which is confirmed by previous studies using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) method (Przybylska et al, 2019). In the cited research, it was found a lower average concentration of PAT for dietary supplements (11.4 ± 5.5 µg/kg) formulated with hawthorn fruits from Crataegus monogyna/Crataegus laevigata trees compared with multicomponents products containing mostly dried hawthorn fruits (15.7 ± 31.6 µg/kg).…”

“…In addition, analytical results suggested that only in 26% of the analyzed dried commercial products concentration of PAT was higher than the maximum tolerance limit of 50 µg/kg recommended by WHO (Drusch & Ragab, 2003;Przybylska et al, 2019). See Figure 2.…”

“…There are no directives relating to the presence of patulin in medicinal plant. The Joint Expert Committee on food Additives of the World Health Organization (JECFA) recommended that daily human exposure to PAT should be reduced to 0.4 µg/kg body weight per day (Hussain et al, 2020;Przybylska et al, 2019).…”

Current Strategies for Studying the Natural and Synthetic Bioactive Compounds in Food by Chromatographic Separation Techniques

“…Some studies demonstrate the important role of HPLC with UV, DAD, or FL detector as well as UHPLC-MS/MS in the study of patulin (mycotoxin) and related compounds in fruits e.g., mangoes, apples, grapes, oranges, and fruit products (juices and drinks) for children [52][53][54][55][56][57][58]. In this case C18 column and different usually binary mobile phases consisting, for example, of eluent A: 10 mM ammonium acetate in water and eluent B: 10 mM ammonium acetate in methanol [52] or acetonitrile-water [54] with gradient elution have been successfully applied. These methods allowed determining patulin at different levels given in µg/mL or µg/kg [52][53][54][55][56][57][58].…”

“…In this case C18 column and different usually binary mobile phases consisting, for example, of eluent A: 10 mM ammonium acetate in water and eluent B: 10 mM ammonium acetate in methanol [52] or acetonitrile-water [54] with gradient elution have been successfully applied. These methods allowed determining patulin at different levels given in µg/mL or µg/kg [52][53][54][55][56][57][58].…”