This should not be possible , as NextSequenceValue simply queries the database for the next sequence (using .nextval) and databases often handle that really well.
It could be that the app is overwriting the value somehow via an update. Check the creation user/last updated for the duplicate unique id which one is newer is probably the duplicate, also to be safe make the field uneditable.
If you are using branch versioning or archiving you can use the history to investigate how the unique id happened to be.
Do you know what is the database?