Multidetection of urinary ochratoxin A, deoxynivalenol and its metabolites: pilot time-course study and risk assessment in Catalonia, Spain

Abstract

The presence of two main mycotoxins, ochratoxin A (OTA) and deoxynivalenol (DON), is widespread in cerealbased foodstuffs marketed in Europe. The objectives of this study were to develop and validate a multi-detection analytical methodology to simultaneously assess the urinary concentrations of OTA, DON and their metabolites, and to apply this methodology in a preliminary follow-up trial in Catalonia (Spain). Hence, an ultra-performance liquid chromatography with tandem mass spectrometry method was developed to simultaneously assess the urinary levels of OTA, DON, deoxynivalenol-3-glucoside (DON-3-glucoside), deoxynivalenol-3-glucuronide (DON-3-glucuronide), 3-acetyldeoxynivalenol (3-ADON) and de-epoxy-deoxynivalenol (DOM-1). Urine mycotoxins levels and food dietary intake were prospectively monitored in a group of volunteers throughout a restriction period followed by a free-diet period. The proposed multi-detection methodology for urinary OTA and DON metabolites was validated, providing suitable recovery, linearity and precision. The results from the pilot trial showed that urinary OTA, DON and its metabolites were detected in most background samples, displaying moderate reductions after the restriction period and subsequently recovering the background levels. Despite the restriction period, some DON metabolites, such as 3-ADON or DOM-1, were still found in urine samples, placing alternative sources of DON exposure other than the ones considered in the study under suspicion. DON and DON-3-glucuronide were significantly associated with consumption of bread, pasta and pastries, while OTA was only associated with consumption of wine and breakfast cereals. The urinary levels of OTA were significantly correlated with plasmatic levels of OTA and ochratoxin α, supporting the results from the multidetection method in urine. The results also showed that the high exposure to DON could be held throughout the time by the same person, exceeding the tolerable daily intake systematically instead of eventually. The estimates of OTA exposure through urine are largely higher than those obtained with the dietary approach. The background levels found in urine revealed that the exposure to DON and OTA could be of concern for the Catalonian population, thus, further studies applying this biomonitoring methodology in a larger sample of Catalonian population are needed to accurately characterise the human health risks at population level.

The authors are grateful to the Spanish government (projects AGL2010-22182-C04-04 and AGL2011-24862) for the financial support. A. Vidal thanks the Spanish Government (Ministry of Education) for the pre-doctoral grant.