Thinking about the report I found at one point of a tribe in south america that would crush up and snort the tips of their poison darts when their preferred psychoactives weren't available (ayahuasca, etc)
I managed to find the compounds they were ingesting in this case, it turns out the frog secretion commonly used in many poison darts binds to the opioid receptors creating a potent but atypical sedative/analgesic effect, likely potent enough to kill an animal but not a human
It's also possible that the tribe did this semi-frequently and had developed a tolerance to the effects, similar to that seen with the practice of rubbing kambo into skin, another frog secretion which contains similar compounds
There was another really incredible report I heard of a tribe where the shaman would discover new useful botanicals by taking brugmansia (deleriant similar to datura) then wandering into the rainforest for days
He would fall asleep under a specific tree that was hewn out by a species of ant that puts off this black secretion all over the base lf the trunk, which was considered to be a portal to an alternate realm, similar to the irish legend of "fairy rings"
The shaman would sleep there for a few days, during which time he would be visited by spirits who would give him a new plant and instruct him on its uses, then when he awakened he would find said plant in his hand and return to his people to pass on the info
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