Development of a LC-MS/MS Method for the Analysis of Enniatins and Beauvericin in Whole Fresh and Ensiled Maize

A LC-MS/MS method for the detection of beauvericin and the four enniatins A, A1, B, and B1 in maize and maize silage was developed. The method uses direct injection of maize extracts without any tedious and laborious cleanup procedures. The limit of quantification was determined at 13 ng g−1 for beauvericin and at 17, 34, 24, and 26 ng g−1 for enniatins A, A1, B, and B1, respectively. The method was used in surveys of the compounds in fresh maize samples collected at harvest in 2005 and 2006. All samples had the same distribution of the enniatins: B > B1 > A1 > A. Enniatin B was present in 90% of the samples in 2005 and in 100% in 2006 at levels up to 489 and 2598 ng g−1, respectively. Beauvericin contamination was more frequently detected in 2006 than in 2005 (89 and 10%, respectively) and in higher amounts (988 and 71 ng g−1, respectively). The occurrence of beauvericin and the four enniatins was examined in 3-month-old maize silage stacks from 20 different farms. As observed in fresh maize, enniatin B was the most abundant compound in ensiled maize and was found from 19 stacks at levels up to 218 ng g−1. The stability of enniatin B in maize silage was assessed by analyzing samples from 10 of the silage stacks taken after 3, 7, and 11 months of ensiling. Enniatin B could be detected at all locations after 11 months and appeared to be stable during ensiling.