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Arsenal explosions have happened through decomposition of old smokeless powder, but this depends on the storage of powder in very large bins or canisters, which allows heat to build up. I don't think there is any chance of this when the powder is stored in one or two pound cans.

The smell test is well worth doing, immediately after a sealed canister is opened. The gases from decomposition have such an acrid smell that you can detect them in very small quantities. Besides, decomposition of the powder usually results in its having less energy, not more.

The key word is sealed. Smokeless powder regularly surprises people by being perfectly good after much more than ten years of hermetically sealed storage. Moisture content doesn't make a great deal of difference, and in fact less for a given percentage than some substances which are deliberate additives. Long-term exposure to either humidity or drying is also an opportunity for other forms of deterioration, but there should be nothing wrong with powder which has been exposed for a week or so to extreme humidity in the distant past, then sealed ever since. But I found strands of artillery powder which had been exposed to extreme sunlight for over two years in Kuwait, and it broke more easily, and burned less brightly, than most plastics.

Black powder is good as long as it continues to look like black powder. If it has been damp enough for the grains to disintegrate, then dried out, the chemical composition is fine. But it may compact too much for free ignition, or it may give the speed, dangerous in some black powder firearms, of much finer-grained powder. If it has been really wet, then dried out, it may be very weak indeed, since the intimate relationship of its constituents (the secret of good black powder) may have been replaced by larger crystals of saltpetre.

Very old primers, such as are found in early cartridges, may decompose enough to become inactive. But modern ones generally don't, and retain their power. If you have a revolver, you have as good a primer tester as any. Just load a case with a primer only, and fire it with a piece of thick copper foil or soft drink can aluminium sandwiched in the cylinder gap. This should be domed and torn, and i think it will look the same as with a primer you have just bought.

I tend to disbelieve in anything causing spontaneous or unduly easy ignition of modern commercial primers. The main thing is to keep them in the original packaging, which is designed to prevent the ignition of one being communicated to the rest, with all the little trays facing the same direction, i.e. not facing one another. If you are fussy, you can lay all the trays side by side in a flat chocolate box. Their action is too momentary to ignite much besides powder, as you can prove by using a piece of paper in the cylinder gap.
 

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In 1993 onwards in Kuwait, I used to find a lot of fired and unfired Iraqi ammunition where their old positions had been. A lot, mostly in 7.62 NATO etc. which they had captured and didn't use, had been dismantled, which I assumed to be for lighting fires. There were also a few sporting rounds, and just one .460 Weatherby Magnum, a bit more powerful than really has much point even for elephant, which they must have looted from some large Kuwaiti houses nearby.
 
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