Bibiki Bay, Uleguerand Range, Bearclaw Penninsula, Pso'Jxa, Newton/Oldton Molvopolis, Mine Shaft # (can't remember #), Shadow's Maw (or something like that), Attohwa Chasm, Manaclipper, Carpenter's Landing, Phaneut Channel, Promyvion-Mea, Promyvion-Dem, Promyvion-Holla, Promyvion-Vahzl (and their respective BCNM areas), a few new Dynamis areas, a new area that looks similar to Tu'Lia, but doesn't seem to be on the world map, and all the areas in the Tavnazian Archipelago (Lufaise MEadows, Miseraux Coast, Tavnazian Safehold, Phomiuna Acqueducts, Riverne Site #A01, and B01. There might be a couple I'm forgetting, but that's most of it.
Edit: available from the get-go? Hmm....Molvopolis, Attowha Chasm, Bibiki Bay, Uleguerand Range, Bearclaw Pinnacle, Pso'Jxa, Manaclipper, Phaneut Channel, Promyvion (after a few quick cutscenes accessible to anyone who can get to Delkfutt's Tower), Carpenter's Landing, and I think that's about it.