Reports from Russia said about 1,500 firefighters were sent to tackle the blaze and residents were evacuated from the nearby village of Nagorny, about 15km from the city of Chapaevsk.
The Emergencies Ministry said about four people needed hospital treatment after five explosions triggered the fire.
The first was reported at about 3pm yesterday and further blasts were still being heard hours later.
It is still not clear what caused the shells to explode.
More than 200 engines were sent to the scene but reports said firefighters initially struggled to get close to the blaze because of the danger of the exploding shells.
Local authorities declared a state of emergency after the explosions, according to RT.com.
The Federal Investigative Committee said it was set off by the ‘involuntary’ explosions of shells.
Videos of the explosions uploaded online show a huge ball of flame being sent hundreds of feet into the air.
Dark plumes of smokes were also pictured rising from the site.
Ministry official Vladimir Stepanov said: ‘Some 6,000 people were evacuated from a nearby village.
‘More than 30 people sought medical help, four of them are hospitalised.’
The Interfax news agency said the shells at the Chapaevsk base have a range of less than 1km.
Russian munitions, which frequently date back to the Soviet era, have exploded several times in recent years and the resulting fires usually rage for days.
In October, a soldier caused a devastating fire at an ammunition depot by dropping a cigarette butt.
More than 4,000 tonnes of ammunition being transported in crates exploded.
In 2009, eight soldiers were killed and two others were injured in a massive blast at an ammunition depot in the central Russian city of Ulyanovsk.
Ten days earlier, 3,000 people had to be evacuated after an explosion at the same site.
In other cases, shells have exploded during munitions disposal.
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