Determination of Patulin in Apple and Hawthorn Beverages by Solid-Phase Filtration Column and Liquid Chromatography

Abstract

The use of solid-phase filtration column (MycoSep 228®) and liquid chromatography for determination of patulin in apple and hawthorn beverages was investigated. The method passed a series of validation tests, including separation efficiency, sensitivity, repeatability, validation within a collaborative trial, recoveries, and applicability. Accuracy and precision were very good for determination of patulin in both spiked and naturally contaminated apple/hawthorn beverage samples at levels of 10 μg/L and above, with limits of detection and quantification at 8 and 23 μg/L, respectively. The applicability of the method was tested by analyzing commercially available domestic apple and hawthorn beverages. Patulin was found in 3 of 52 (5.77%) apple beverages at concentrations ranging from 63.45 to 88.44 μg/L, and in 6 of 43 (13.95%) hawthorn beverages ranging from 19.8 to 206.88 μg/L. Among these were 3 apple and 4 hawthorn beverage samples with toxin levels that exceeded the Chinese legislative requirement of 50 μg/L in apple- and hawthorn-based products intended for human consumption. Comparable tests revealed that the results obtained by both the new MycoSep-based method and the official AOAC method are not significantly different (t value 0.003268 < t0.05, P > 0.05).

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

“…Compared to the work of Li et al [25] on determination of PAT in the hawberry products with the Xterra C18 column and isocratic elution using tetrahydrofuran-water (0.8 : 92.2, v/v) as the mobile phase, the retention time of PAT in the gradient UHPLC conditions was practically the same (i.e., 5.80 vs. 6.17 min); however, the LOD for the PAT achieved in the former method, operating with UV detection at 276 nm, was only 8.0 µ g/kg compared to 1.0 µ g/kg offered by our method. Similarly, compared to the retention time of PAT observed in the isocratic HPLC method used to analyze hawberry products reported by Zhou et al [26] with a Venusil C18 column and acetonitrile-water (5 : 95, v/v) as the mobile phase, we found in our gradient HPLC conditions a nearly sevenfold shorter retention time for PAT, and moreover, the LOD for PAT reported in the former method with diode array detection was 3.99 µ g/kg compared to 1.0 µ g/kg found using our procedure.…”

“…Replacement of the acetonitrile used in the cleanup/filtration step with a MycoSep®228 AflaPat multifunctional column by Li et al [25] and Zhou et al [26] and with a ProboFast®228 multifunctional column applied by Ji et al [28] with acetonitrile-water (80 : 20, v/v) in our procedure resulted in an improved average recovery of PAT up to 112.7% at a spiked level of 50.0 µ g/kg, and the extraction method accuracy and precision of PAT determination in hawberry products was quite comparable to these three mentioned earlier reports. The satisfactory average extraction recovery of PAT observed in our study (112.7%) was highly improved compared to the rather low average recovery of PAT (i.e., 64.0%) from hawberry products as reported by Xiang et al [27] after use of the ultrasonically supported water-ethyl acetate liquid-liquid extraction.…”

“…In previous years, the number of studies describing the occurrence of PAT in products containing hawberry is still limited. However, some recent data on PAT determination in hawberry-derived beverages [25], hawberry juice [26], hawberry slices, including dried, baked, and charred [27], and dried hawberry products in circular flakes, rolls, strips, and dessert forms [28], have been reported from China. To our best knowledge, for Europe, there are still no papers describing the content of PAT in freshly harvested or stored hawberry or in dietary and medicinal products containing dried or frozen hawberry.…”

A new solid‐phase extraction and HPLC method for determination of patulin in apple products and hawthorn juice in China

“…Although patulin can occur in many moldy fruits, grains, and other foods, the major sources of patulin contamination are apple and related products. Natural contamination of apple and hawthorn products with patulin has been reported in several countries []. Because of toxicity of patulin, the European Commission has stipulated for this toxin a maximum level of 50 μg/kg in fruit (apple) juices and for apple juice ingredients in other beverages, 25 μg/kg in solid apple products such as apple compote and apple puree, and 10 μg/kg in apple products intended for infants and young children [].…”

“…Both liquid–liquid extraction and solid‐phase extraction (SPE) are the typical methods for sample preparation. SPE techniques using C 18 , hydrophilic–lipophilic balance (HLB), or MycoSep®228 AflaPat are commonly used because of their superior precision and recovery []. However, complex procedures are required when using C 18 and HLB, and MycoSep®228 AflaPat is very expensive.…”