Assessment of Human Exposure to Deoxynivalenol, Ochratoxin A, Zearalenone and Their Metabolites Biomarker in Urine Samples Using LC-ESI-qTOF.

Human are exposed to a wide range of mycotoxins through dietary food intake, including processed food. Even most of the mycotoxin exposure assessment studies are based on analysis of foodstuffs, and evaluation of dietary intake through food consumption patterns and human biomonitoring methods are rising as a reliable alternative to approach the individual exposures, overcoming the limitations of the indirect dietary assessment. In this study, human urine samples were analyzed, seeking the presence of deoxynivalenol (DON), ochratoxin A (OTA), zearalenone (ZEA), and their metabolites. For this purpose, 40 urine samples from female and male adult residents in the city of Valencia (Spain) were evaluated by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-ESI-qTOF) after salting-out liquid-liquid extraction. Analytical data showed that 72.5% of analyzed samples were contaminated by at least one mycotoxin at variable levels. The most prevalent mycotoxins were de-epoxy DON (DOM-1) (53%), ZEA (40%), and α-zearalenol (αZOL) (43%), while OTA was only detected in one sample. The mean concentrations in positive samples were DON (9.07 ng/mL), DOM-1 (20.28 ng/mL), ZEA (6.70 ng/mL), ZEA-14 glucoside (ZEA-14-Glc) (12.43 ng/mL), αZOL (27.44 ng/mL), αZOL-14 glucoside (αZOL-14-Glc) (12.84 ng/mL), and OTA (11.73 ng/mL). Finally, probable daily intakes (PDIs) were calculated and compared with the established tolerable daily intakes (TDIs) to estimate the potential risk of exposure to the studied mycotoxins. The calculated PDI was below the TDI value established for DON in both female and male adults, reaching a percentage up to 30%; however, this percentage increased up to 92% considering total DON (DON + DOM-1). On the other hand, the PDI obtained for ZEA and its metabolites were higher than the TDI value fixed, but the low urine excretion rate (10%) considered should be highlighted. Finally, the PDI calculated in the detected positive sample for OTA exceeded the TDI value. The findings of the present study confirm the presence of the studied mycotoxins and their metabolites as some of the most prevalent in urine.

Dietary Exposure to Mycotoxins through Alcoholic and Non-Alcoholic Beverages in Valencia, Spain.

The present study investigated the presence of 30 mycotoxins in 110 beverage samples of beer, wine, cava, and cider purchased in Valencia (Spain). A validated method based on dispersive liquid-liquid microextraction and chromatographic methods coupled with tandem mass spectrometry was applied. The method showed satisfactory recoveries ranging from 61 to 116% for the different beverages studied. The detection and quantification limits ranged from 0.03 to 2.34 µg/L and 0.1 to 7.81 µg/L, respectively. The results showed that beer samples were the most contaminated, even with concentrations ranging from 0.24 to 54.76 µg/L. A significant presence of alternariol was found in wine, which reached concentrations up to 26.86 µg/L. Patulin and ochratoxin A were the most frequently detected mycotoxins in cava and cider samples, with incidences of 40% and 26%, respectively. Ochratoxin A exceeded the maximum level set by the EU in one wine sample. The results obtained were statistically validated. The combined exposure was assessed by the sum of mycotoxin concentrations contaminating the same samples to provide information on the extent of dietary exposure to mycotoxins. No significant health risk to consumers was associated with the mycotoxin levels detected in the beverages tested.