The surrounding area is being evacuated and the head of Ukraine's armed forces has gone to the site, the statement said. There was no mention of any casualties.
Around 10,000 people were evacuated after a fire and explosions hit the defence ministry ammunition depot. It was not immediately clear whether the explosions were an accident or sabotage.
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The airspace in a 20 km radius has been closed and road and rail transport suspended. Hundreds of people have been deployed to the site, a statement by the emergency services said, and the head of Ukraine's armed forces has gone there.
There have been several large fires at ammunition and weapons depots in recent years, an additional drain on Ukraine's military, which has been fighting Russian-backed separatists in eastern regions since 2014.
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"About 10 thousand people were evacuated," the statement by the emergency services said. "From 04:22 am (0122 GMT) the airspace within a radius of 20 km has been closed. The movement of rail and road transport is suspended."
Last year massive explosions at a military depot in the Vynnytsya region, 270 km west of Kiev, forced the authorities to evacuate 24,000 people.
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