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Psychoactive Amanitas
Timeline
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5000 - 3000 BCE
The earliest linguistic evidence of Amanita muscaria use as an intoxicant.   

Based on linguistic analysis of languages from northern Asia. Around 4000 BCE, the Uralic language split into two branches, both of which contain similar root words for "inebriation". In some of these languages the root "pang" signifies both 'intoxicated' and the A. muscaria mushroom. These linguistic similarities suggest (but do not prove) that A. muscaria was known to be intoxicating before the languages split around 4000 BCE.


References
Wasson RG. Soma: Divine Mushroom of Immortality. Harcourt Brace Jovanovich, 1968.


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