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Volatile Rounds apply Volatile on enemies after being shot, and then explode for X damage in the area after receiving X damage while volatile. They don't have to die to cause the explosion. Can only be applied when you have the volatile rounds status.
Destabilising Rounds require the enemy to die to activate the volatile explosion. There's no need to have the volatile rounds status to make this effect occur, so less upkeep worry. There's a 3 second cooldown on it activating again, though.
You can run both at the same time so you've always got Volatile rounds going, but you could just slot something else in to build yourself up stronger in other ways.