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your system should have a program called lsof.
As root, run "lsof /mount/point", it should list all resources accessing it (keep in mind.. even being in a samba directory can make it "busy").
If it's still being a pain, you can do "umount -l /mount/point". This makes it unavailable for all future processes, and umounts it quietly in the background when old processes let go of it.
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