For more about texture atlases go here
https://developer.apple.com/library/ios/recipes/xcode_help-texture_atlas/AboutTextureAtlases/AboutTextureAtlases.html#//apple_ref/doc/uid/TP40013290-CH2-SW1
PDF does load in Xcode and can be used it seems.
I quickly tried to import one into a project and use it in an animation and it didn't seem to load in an animation. So I'm not sure.
Keep in mind Sprite Kit itself may not be able to use PDF even if Xcode can.
I tried to load a PDF document though. Stick with PNGs.
I'd probably go with using .PNG because they have been pretty reliable for me.
To make a texture atlas you can make a new folder on you computer with the name convention nameofthetextureatlas.atlas .
Put your images in that folder.
Drag it into your Xcode project navigator sidebar
Ensure Add to Targets is checked , Create folder references is checked, & Add to targets is checked.
Then to animate an SKSpriteNode you can do something along the lines of
var textureArray = [SKTexture]()
textureArray.append(SKTextureAtlas(named: "name of atlas").textureNamed("Name of Frame 1"))
textureArray.append(SKTextureAtlas(named: "name of atlas").textureNamed("Name of Frame 2"))
self.runAction(SKAction.animateWithTextures(textureArray, timePerFrame: 1))
Note: filenames do not include .atlas or .PDF at the end and always give files unique names.