II.6.2 Mushroom Toxins by Kunio Gonmori and Naofumi Yoshioka
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6.2 II.6.2 Mushroom toxins by Kunio Gonmori and Naofumi Yoshioka Introduction As many as 5,000–6,000 mushroom species are growing in the world. Among them, only about 1,000 species are named; the majority of them are unnamed. Th e number of species of edible mushrooms in Japan is about 300; that of toxic mushrooms is said to be about 30. Various types of toxic mushrooms exist; some show high toxicity, while others show hallucinogenic actions. Morphological and chemical analyses for mushrooms are occasionally required in forensic sci- ence practice. In this chapter, the characteristics of the representative toxic mushrooms and some chemical methods for their toxins are presented. Current situation of mushroom poisonings in Japan According to “National Record of Food Poisoning Incidents” [1], the number of mushroom poisoning incidents taking place in Japan in 1974–1997 was 1,068; it was 431 in 1988–1997 (10 years) with 1,842 poisoned people, including 20 fatal victimsa. Among the 431 incidents, the numbers of incidents according to causative mushrooms are: Rhodophyllus rhodopolius plus Rhodophyllus sinuatus, 133; Lampteromyces japonicus, 127; Tricholoma ustale, 42; Amanita virosa plus Amanita verna, 16; Amanita pantherina, 15; Clitocybe acromelalga, 15; Psilocybe argentipes (a species of magic mushrooms), 12; other mushrooms, 36; not specifi ed, 35 (> Figure 2.1)b. Toxic mushrooms can be classifi ed into 6 groups according to their actions as follows. • Th ose which destroy cells, injure the liver and kidney and thus may cause death (latent period, 6–10 h; Amanita virosa, Amanita verna and Amanita phalloides). • Th ose which act on the autonomic nervous system and provoke symptoms, such as sweat- ing, lacrimation, vomiting and diarrhea (latent period, 20 min–2 h; Clitocybe gibba, Inocybe species and others). • Th ose which inhibit the metabolism of acetaldehyde in blood (disulfi ram-like eff ect), caus- ing a fl ushing phenomenon and palpitation upon drinking alcohol concomitantly (latent period, 20 min–2 h; Clitocybe clavipes, Coprinus atramentarius and others). • Th ose which act on the central nervous system and provoke abnormal excitement and hallucinations (latent period, 20 min–2 h; Amanita pantherina, Psilocybe argentipes and others). • Th ose which irritate the gastrointestinal tract and provoke symptoms, such as abdominal pain, vomiting and diarrhea (latent period, 30 min–3 h; Rhodophyllus rhodopolius, Lamptero- myces japonicus and others). • Others which cause swelling or necrosis of tips of extremities or sharp pain due to distur- bances of the peripheral nerves (Clitocybe acromelalga and others). © Springer-Verlag Berlin Heidelberg 2005 470 Mushroom toxins ⊡ Figure 2.1 Incidence ratio of mushroom poisonings according to species in Japan. It is calculated from the data of “National Record of Food Poisoning Incidents”. The number of the mushroom poisoning incidents was 431; the poisoned subjects involved were 1,842 people. > Table 2.1 shows the outline of the mushroom poisoning analyses, which the authors had undertaken in recent 9 years. As shown in this table, the number of the poisoning cases, in which Amanita virosa had been (suspected to be) causative, was as many as 10. Amanita virosa is highly toxic and sometimes causes fatalities. Th e highest incidence of the Amanita virosa in our laboratories is interpreted to mean that such fatal poisoning cases are selectively brought to our Department for analysis. Two cases were suspected of poisoning by Rhodophyllus rhodopolius (> Table 2.1). Representative mushrooms causing poisoning cases Rhodophyllus rhodopolius ( > Figure 2.2) Th is mushroom shows the highest incidence of poisoning in Japan, because a very similar edible species Rhodophyllus crassipes is available and grows at similar locations. Th e poisoning symptoms are vomiting, diarrhea and abdominal pain appearing 30 min–3 h aft er ingestion. Th e stem of Rhodophyllus rhodopolius is easily crushed by pressure with the fi nger, but that of the edible Rhodophyllus crassipes is not. Th e toxic compound being contained in the mush- room is reported to be muscarine or choline. ⊡ Table 2.1 Outline of mushroom poisoning analyses undertaken by Department of Legal Medicine, Akita University School of Medicine No. Year Requesting institution Causative mushroom The patient Outcome Specimen and detectability of the toxin number 1 1993 H Univ. Dept. Legal Med. Amanita virosa 1 dead detected from the liver and the mushroom 2 1996 T Kyodo Hosp. Dept. Anaesth. Amanita virosa? 1 dead not detected from blood, the liver or kidney (mushroom not available) 3 1996 Y Univ. Dept. Intern. Med Amanita virosa? 1 dead not detected from blood (mushroom not available) 4 1997 D Univ. Emerg. Units Amanita virosa? 1 alive not detected from blood or the mushroom (mushroom available) 5 1997 F Univ. Emerg. Units Amanita virosa? 1 alive not detected from blood stomach contents or (mushroom available) the mushroom 6 1998 A Pref. Hosp. Dept. Intern. Med. Agaricus blazei 2 alive not detected from blood or the mushroom (mushroom available) 7 1998 O Pref. Hosp. Emerg. Units Amanita virosa 1 alive not detected from blood urine or the (mushroom available) mushroom 8 1998 J Med. Univ. Emerg. Units Amanita virosa 7 1 dead detected from blood of one patient causingpoisoningcases mushrooms Representative and Dept. Nephrol 9 1998 J Med. Univ. Emerg. Units Amanita virosa 5 alive not detected from blood or urine and Dept. Nephrol. 10 1998 I Pref. Hosp. Emerg. Units Amanita virosa 1 alive not detected from blood or urine 11 1999 O Munic. Hosp. Dept. Urol. Amanita neoovoidea 1 alive not detected from blood 12 1999 J Med. Univ. Emerg. Units not clear (Rhodophyllus 3 alive not detected from blood, urine or the and Dept. Nephrol. rhodopolius?) mushroom- mushroom containing wheat-flour noodles 13 1999 J Med. Univ. Emerg. Units Lampteromyces japonicus 2 alive not detected from blood, urine or the and Dept. Nephrol. (mushroom available) mushroom 14 1999 A Munic. Gen. Hosp. Dept. Intern. not clear 1 alive not detected from blood Med. (Rhodophyllus rhodopolius ?) 15 2000 Y Publ. Health Center Amanita neoovoidea 0 – not detected from the mushroom (only mushroom available) 16 2000 K Med. Univ. Emerg. Unit Amanita virosa 2 alive not detected from blood or urine, but and Dept. Pediat. (mushroom available) detected from the mushroom 17 2001 A Police H. Q. a magic mushroom (cultivated 1 dead detected from blood, urine and the 471 with a culture medium) mushroom 472 Mushroom toxins ⊡ Figure 2.2 Rhodophyllus rhodopolius. ⊡ Figure 2.3 Amanita virosa. Representative mushrooms causing poisoning cases 473 Amanita virosa (> Figure 2.3) It is a very beautiful white mushroom growing in mountain areas; it is thus being called “ de- stroying”. Only with one mushroom of Amanita virosa, 2 or 3 adult subjects can be killed. Th e Amanita genus mushrooms should be watched most carefully also in the forensic toxicological point of view. Th e main toxin of this genus is considered to be amanitin (> Figure 2.4) or phalloidin (> Figure 2.5). Th e amanitin is subdivided into α-, β- and γ-amanitins. In Japan, Amanita virosa and Amanita verna glow generally, while in Europe and America, Amanita phalloides is responsible for poisoning. Th ere is a report insisting that phalloidin does not exert toxic eff ect upon oral intake [2]. When chemical analysis was performed for 45 patients of ⊡ Figure 2.4 Structure of amanitin. ⊡ Figure 2.5 Structure of phalloidin. 474 Mushroom toxins Amanita verna poisoning in France, amanitin could be detected from plasma in only 11 of 43 patients, from urine in 23 of 35 patients, from the contents of the stomach and duodenum in 4 of 12 patients and from feces in 10 of 12 patients [3]. Th e blood concentrations of amanitin are highly dependent on the intervals aft er ingestion; the concentrations in urine and the con- tents of the stomach and duodenum are much higher than those in blood, and these specimens are more suitable for analysis of amanitin [3]. Lampteromyces japonicus Th is is one of the most common toxic mushrooms with the highest incidence of poisoning, like Rhodophyllus rhodopolius, in Japan. It is usually mistaken for the edible Lentinula edodes, Pleurotus ostreatus, Panellus serotinus or others. Th e shape of Lampteromyces Japonicus is semicircular or kidney-like; the size is as large as 10–25 cm. When it matures, the color of its cap part becomes purplish brown or dark brown. Th e stem is as short as 1.5–2.5 cm and located at a side part of the cap; there is a crater like protrusion in the reverse side of the cap just around the stem. When this part of the cap including the stem is cut, dark coloration can be observed there for the matured mushroom (> Figure 2.6), and the folds and hyphae lumi- nesce in a light yellow color in the dark; these are very useful for its discrimination. However, it should be cautioned that the above dark coloration is absent or obscure in the immature mushrooms. According to the growing circumstances, the Lampteromyces japonicus may show a round cap like Lentinula edodes, and thus is confusing (> Figure 2.7). Since the Lamptero- myces mushrooms can grow in colonies on the dead beech or maple trees, a great number of the mushrooms may be harvested at a single location. Th e harvester distributes them to neighbors and relatives, resulting in simultaneous occurrence of many poisoned patients. Its toxin is lampterol ( illudin S), which causes vomiting and diarrea. Th e fatality by the toxin is very rare. ⊡ Figure 2.6 How to discriminate Lampteromyces japonicus. Representative mushrooms causing poisoning cases 475 ⊡ Figure 2.7 Lampteromyces japonicus mushrooms having circular umbrellas, which tend to be mistaken for edible Lentinula edodes mushrooms.