Cannot unmount external volume

I have an external Firewire La Cie HD containing 4 partitions, 2 of which are back ups.
When I switch on the La Cie. I see 4 icons on my desktop. I work with one of the partitions and when I am finished, I press CMD E to eject it (and normally all 4 disappear together), but sometimes only 3 of them unmount. The 4th (one of the b/u volumes) just stays there and I cannot eject it. I tried to close all the open processes by pressing CMD Tab and quitting everything visible except Finder. but I still cannot eject my b/u volume. I am obliged to shut down the Mac to expel the stubborn partition.
An side effect of this is that while that b/u volume is mounted, I cannot mount again the other partitions. To do that I would have to switch off La Cie and switch it on again, but switching off the external HD before ejecting a mounted volume is not recommanded.
Is there a way to force-eject this volume?
PPC Mac mini, OS 10.4.8

The inability to unmount a volume that's not the boot volume usually indicates that there's some kind of link between it an the boot volume (an open file, symbolic link, etc.).
Try these:
i) launch Terminal, enter this command, and see which files are busy on which volumes are busy:
lsof | grep Volumes
That should give a clue as to which application is running what. Ignore everything dealing with .Trashes and look explicitly for stuff on that recalcitrant volume.
ii) launch Disk Utility, select the internal drive, select unmount.

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