Determination and Monitoring of Grayanotoxins in Honey Using LC-MS/MS

This study was performed to establish analysis methods, and evaluated for grayanotoxin in domestic/foreign honey and wild honey. The molecular weight of grayanotoxins I, II and III, excluding grayanotoxin III that has been commercialized, were analyzed by LC-MS/MS. Then, the molecular structure of grayanotoxins I and II were analyzed by NMR. A total 111 samples (25 Korean honey, 21 Korean wild honey, 13 Korean honeycomb honey, 44 foreign honey, 8 foreign wild honey) were examined to determined whether or not each sample contained grayanotoxins I, II, and III. The honey samples were mixed with methanol and loaded into a tC18 cartridge, the filtrate was diluted with water, and the mixture was then analyzed by ESI triple-quadrupole LC-MS/MS. Grayanotoxins were only found in the foreign wild honey and were not detected in Korean honey, Korean honeycomb honey, or Korean wild honey. Three of the samples contained grayanotoxin I, II, and III, and one sample contained only grayanotoxins I and III. The lowest level for grayanotoxin I was 3.13 ± 0.00 mg/ kg, and the highest level was 12.93 ± 0.01 mg/kg. The levels of grayanotoxin II were 0.84 ± 0.01 mg/kg, 0.92 ± 0.00 mg/kg and 1.08 ± 0.01 mg/kg, respectively. The lowest level of grayanotoxin III was 0.25 ± 0.01 mg/kg and the highest level was 3.29 ± 0.74 mg/kg. Through this study, safety management for foreign wild honey has been enabled.