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Some homes with vaulted ceilings still have a pretty good size attic over them (some don't). Either go up in the attic yourself, or have someone go up for you and see if the area over the vaulted ceiling is visible.
If there isn't an attic space over the vaulted ceiling part of the house, then its impossible to know the type or depth of the insulation unless you can find someone that has x-ray vision.....or you open up the ceiling and take a look.
AS far as putting more insulation up there goes.....kind of the same thing as seeing it. If there is room above, its easy to put more in, if theres no access, then its a lot more difficult.
Although barking spider is correct that you can't know the exact depth / type of insulation w/o x-ray vision even an inexpensive thermal imagining camera will give you a pretty good idea as to how effectively insulated a hidden space might be. Very high end thermal cameras can be used to give an accurate "as built" R value for a wall / ceiling and the better insulation contractors will then be able to tell you if it is cost effective to add more.
There are options to non- destructively add insulation. Finished walls / ceilings can have small holes drilled and expanding foam or blown insulation added. Before you commit to doing that you ought to get a detailed energy audit, that spells out expected return on various upgrades.
Good Luck!
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