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. The history of copper metallurgy is thought to have followed the following sequence: 1) cold working of native copper, 2) annealing, 3) smelting, and 4) the lost wax method. In southeastern Anatolia, all four of these metallurgical techniques appears more or less simultaneously at the beginning of the Neolithic c. 7500 BC. However, just as agriculture was independently invented in several parts of the world, copper smelting was invented locally in several different places. It was probably discovered independently in China before 2800 BC, in Central America perhaps around 600 AD, and in West Africa about the 9th or 10th century AD. Investment casting was invented in 4500–4000 BC in Southeast Asia and carbon dating has established mining at Alderley Edge in Cheshire, UK at 2280 to 1890 BC. Ötzi the Iceman, a male dated from 3300–3200 BC, was found with an axe with a copper head 99.7% pure; high levels of arsenic in his hair suggest his involvement in copper smelting. Experience with copper has assisted the development of other metals; in particular, copper smelting led to the discovery of iron smelting. Production in the Old Copper Complex in Michigan and Wisconsin is dated between 6000 and 3000 BC. Natural bronze, a type of copper made from ores rich in silicon, arsenic, and (rarely) tin, came into general use in the Balkans around 5500 BC.[citation needed]

When was copper first known to have been used?