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At the risk of being overly pedantic, topologists would typically classify this as venom.

Venom is inert if digested; it's only a problem if it gets in your blood stream. So arrows that were laced with venom and thereby contaminated meat were actually perfectly safe to eat.

Poison is different. If ingested, inhaled, or absorbed it will kill you.

It's humbling to think about all the things people have gone through over the past couple hundred thousand years. Somewhere around 117 billion humans have ever lived...? It makes it seem kind of small when we think only 50 or 100 years out when thinking of what the future would be.

The poisions?

Buphanidrine : https://pubchem.ncbi.nlm.nih.gov/compound/Buphanidrine

and

Epibuphanisine https://pubchem.ncbi.nlm.nih.gov/substance/349793761

which are nearly identical compounds (it seems) except for one having an additional -OMe (Methylether) group. Looks like they are https://en.wikipedia.org/wiki/Crinine (s)

From the https://en.wikipedia.org/wiki/Boophone_disticha plant.

How was it determined that these are arrowheads, as opposed to atlatl darts?

The oldest known/discovered/documented bows only go back to ~7,000 BC (Holmegaard bows from Northern Europe).

The linked study (the summary is both more concise and informative): https://www.science.org/doi/10.1126/sciadv.adz3281

For context, this is towards the end of prehistoric human time period Middle Paleolithic [0] and in the middle of geological time period Late Pleistocene [1].

0. https://en.wikipedia.org/wiki/Middle_Paleolithic

1. https://en.wikipedia.org/wiki/Late_Pleistocene

Man has a rather unkind history.

The even worse thing is that in 2026 this hasn't quite improved significantly. What is the main poison used today? I guess that may depend on the definition, probably particles being taken in by the lung in general. But specific poison it may be antifreeze? Or perhaps that is just more famous. Food poisoning probably is among the highest, but it would not be deliberate usually, so it should be counted in another category.