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When you copIed the saved Calibre library back to the hard disk did you then remember to remove the Read Only attribute (property) from all files and folders in the restored Calibre library? Writing files to DVD normally sets this attribute, and having that attribute set interferes with normal Calibre operation.
It is also worth checking that the root of the restored library folder contains the Calibre metadata.db file (it should if it is a full copy of the Calibre library).
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