Try this. Open a Terminal window, the Terminal application is in /Applications/Utilities/
type:
crontab -e (this opens the cron schedule for editing)
i (no Return key, this command puts you in Insert mode)
@reboot cd /Volumes ; umount -f volumename
Substitute the volume's real name for volumename. Remember to be case sensitive if this is under Panther or Tiger. Then type:
Escape key (this exits Insert mode)
:wq (saves the edited crontab and exits the editor)
You can quit Terminal now.
It should unmount the volume on each startup or reboot. Use at your own risk, it will forcibly unmount the volume even if something is writing to it at the time. If something is, you could end up with some disk damage to the volume in question. Check it after a few tries, see if it has any damage.
Edited for clarity