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The cause of the fire, which broke out around 2230 GMT, was not yet known, according to local media.
Television footage showed the building engulfed by a raging blaze that firefighters had not brought under control.
The museum was founded in 1818 by King Joao VI and is among Brazil’s most important, with valuable national treasures inside.
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“This is a cultural tragedy,” the director of the National History Museum said on Globo TV.