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I understand you dont have to finish the story to unlock SOME of the PA's, but a few aren't available till after mission 10 is complete. Absolute Dance, Cross Hurricane and a couple more

well, for one thing, they can drop those pa's early on, so you could get the new ult pa's before they are available for sale. To unlock all the new pa's you have to complete story mode. Some of them...

In terms of PA's, I know that the NPC's can drop the new PA's. Lou gave me Absolute dance when i completed the last story mission, Illuminus Ambition. I would assume that the NPC's can drop the other...

train rescue s is a 13* handgun. Forgot the name, im in the process of beating all the s ranks looking for mats for the Tiga De ragan