In 1995 my gun shop burned to the ground.
In it I had 30+ thousand rounds of loaded ammo, thousands of primers, about a dozen cans of gun powder, seven guns, 4 reloading presses and a LOT of other firearms and ammo loading junk.
It was a very exciting morning, and quite an education.
First, off don't believe that all the ammo will just pop and maybe split the case but is no danger. Most unconfined ammo will do this but there always can be the exceptions to the rule. Some ammo may explode with enough force to make the bullet or case deadly.
Second, powder, in the original cans is very safe. It does not explode. The can top or bottom just poops out and the powder burns.
The exception is Black Powder. It explodes.
Cans, like WD40 do explode. They are much more dangerous than gun powder.
After the fire my Wife and I spent two days sorting out what we could to show the insurance adjuster.
These are some of the gun powder cans. The exploded ones are Black Powder or stuff like WD40.
Note the bullet holes in the center cans.
All the loaded ammo was stored in steel GI ammo cans. That means that that those bullets went through, at least, a steel can before going through the powder cans.
This full can of FMJ 9mm reloads was about 15 feet from the fire. The heat caused about 40 rounds to explode.
Two things, the rounds appeared to explode with some force but this did not cause any other rounds in the can to explode.
I eventually shot all the surviving ammo.
The ammo did strange things in the steel cans.
A half can of AK ammo burst, with some force, but not a case or bullet broke through the can. This is it after I opened the lid.
Note the bullet and blast holes in the other cans.
While other cans had multiple holes in the very beat up cans.
It must have been very exciting in this 50 cal GI can for a while.
There were a number of bullet holes in the stuff that couldn't completely burn.
IMO the only way to store ammo is in GI steel cans. Some of the ammo did eventually blow through the cans but not before anyone that is able would have escaped the fire.
As far as fireman getting close to a fire that contains a lot of ammo?
I wouldn't let the fireman near my shop until it was burned out, and that was before I saw the bullet holes.