I suspect the library was removed from Dropbox external to calibre so calibre is still looking for the library on Dropbox.
The easiest fix (if it works) would be to create a new calibre library on the local hard drive in the root of the user's home directory, copy the contents of the Dropbox folder to that location and then use calibre's Swith/create new library to point to the new location and select Use the previously existing library at the new location.
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