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History of Indigo:

Indian indigo was probably used as a painting pigment by ancient Greeks and Romans. Marco Polo (13th century) was the first to report on the preparation of indigo in India. Indigo was quite often used in European easel painting since the Middle Ages. Increasingly, analysis has identified indigo present not only in underpaint, but also in top paint layers.

When was Indigo used?

Discovery Used until
Antiquity (Egyptian) continues in use

Use of Indigo among paintings in the SchackGallery, Munich:

Source: Kühn

Other purples
(intro) - Carmine - Cobalt violet - Indigo