(1) Copper Explanation: Copper occurs naturally as native copper and was known to some of the oldest civilizations on record. It has a history of use that is at least 10,000 years old, and estimates of its discovery place it at 9000 BC in the Middle East; a copper pendant was found in northern Iraq that dates to 8700 BC. There is evidence that gold and meteoric iron (but not iron smelting) were the only metals used by humans before copper.