Identification of trichothecene-type mycotoxins in toxic mushroom Podostroma cornu-damae and biological specimens from a fatal case by LC–QTOF/MS

Abstract

In some autopsy cases, there are unknown natural toxins that are suspected to cause serious damage to the person. However, without reference materials, it is almost impossible to identify the suspicious natural toxins by GC–MS or LC–MS. In this case, a man drank mushroom −liquor with a meal at his home. Seven hours later, he was transported to the emergency room, and 12hours later, he died. In the ingested mushroom-infused-liquor, there were pieces of mushroom that were estimated to be Podostroma cornu-damae (Hypocreaceae) based on their morphological characteristics. To identify the species, chemical component analysis was conducted using LC–QTOF–MS/MS. Monoisotopic mass, fragment ions, and isotope distributions were obtained from the LC–QTOF–MS/MS analysis. In addition, fragment ions and structure matching were tested for target compound confirmation. In this analysis, several toxic trichothecene-type mycotoxins were identified including roridin D, roridin E, roridin Q, satratoxin G, satratoxin H, satratoxin H 12′-acetate, satratoxin H 13′-acetate, satratoxin H 12′,13′-diacetate, and verrucarol. At autopsy, heart blood, peripheral blood, and the stomach contents were collected, and only satratoxin H was detected in these samples. This is the first finding of a trichothecene-type mycotoxin in a human biological sample from an expected case of P. cornu-damae intoxication. We demonstrated that LC–QTOF–MS/MS analysis was an effective method for mushroom intoxication cases in the absence of reference materials. Additionally, the experience, knowledge, and analytical methods we obtained in this study will be great assets for solving other cases of possible natural toxin intoxication.