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History of Vermilion:

Used in China since Ancient times (II millenium BC) the pigment was known to the Greeks and Romans and was mentioned by Pliny who called it 'minium'. It was not known to the Egyptians. According to Pliny the whole supply of vermilion came from Sisapo in Spain. The pigment was used up until the discovery of cadmium red, when its use dramatically reduced due to its known blackening upon reaction to hydrogen sulphides in the air.

When was Vermilion used?

Discovery Used until
Antiquity (Greeks), artificial 8th century (vermilion) 19th century

Use of Vermilion among paintings in the SchackGallery, Munich:

Source: Kühn