Copper and Tin ores are very common and importantly they melt at a low temperature.
Not low enough for an average camp fire, but low enough that you could melt them with a very hot wood fire.
We don’t know how and when humans discovered the first metals but the oldest examples of metal tools date back to circa 9000 BC
It’s likely that it was an accident. Krug put shiny rock in fire and it melted.
He then put 2 and 2 together and figured out how to make the first castings.
After that it was a question of finding different kinds of shiny rocks and seeing if those melted too.
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