We’ve been using fire to some degree for millions of years. Mercury, tin, and lead ores will release metal in campfires, and once people start to use rocks either to line fire pits or as a heat tool, someone was bound to notice when the rocks at hand were ore. Possibly it was noticed several times without an enduring metallurgic technology taking hold. Once you have the notion that interesting substances can come out of hot rocks, trial and error can take over.
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