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When attempting to change an existing disk drive in the LS421DE NAS, there is no way to Dismount the Disk other than power off the unit.
The only workaround that I have found is to use the disk mfg software to "Write 0's" to the disk and delete existing partitions - then another unit (i.e. LS-WVL/R1 Series can use the drive.
To re-iterate when attempting to "change out" an existing, working hard drive, there is no way to dismount the drive to prepare it for use in another device other than clunky workarounds.
Question is: is this a Bug that will be fixed in future FW updates or is there a procedure that is not apparent in the Manual?

I don't think this unit was designed for the drives to be hot-swappable

No Linkstation is hot-swap capable.

I am NOT trying to Hot-Swap any drives what-so-ever!
Simply trying to "Dismount" the disk so that it will be clean and ready to use by another unit, then power down the unit, replace the drive and power up and format the new drive.
Once again, I'm trying to "Dismount" an existing (small or otherwise working) drive, power down the unit, replace the drive (with Large, or whatever) and proceed.
When you remove a drive from the LS421DE by powering down and then looking at it with any other system such as Windows 7/8 or even Linux, it shows as Multi-Partitions and the older Buffalo units (LS-WVL, LS-WX4) Will not (Cannot) access that drive until it is wiped clean.
BTW, I have even tried Windows 7/8 Pro Disk utilities and there is something in the layout that won't let the Windows system delete all of the partitions, I have to use the WD Disk utilities (for WD disks) to "write zeros" to the drive which deletes the existing partitions, then I can re-use the drive.

You said in your original post "When attempting to change an existing disk drive in the LS421DE NAS, there is no way to Dismount the Disk other than power off the unit."

i.e If you don't want to power off then you would be hot swapping: See link for more info on hot swapping: http://en.wikipedia.org/wiki/Hot_swapping

If you having trouble with reading partitions or modifying/deleting them then use: http://gparted.sourceforge.net/

No LinkStation has a method to 'clean' the drive to remove all partition info for use say in another computer or NAS.

If you want to kill partitions (say after breaking a mirror set because you are feeling lucky :D) You would have to do that in whatever OS you migrate the drive to.

I recall back in my earlier days we used to use the DOS 'debug' command to overwrite the boot sector and wipe partitions.

Once again, I am NOT trying to Hot-Swap anything, simply want to "Dismount" an existing, working drive and replace it with another.
In the LS421DE unit, when going to the Drives section, the "Dismount" button is greyed out and not accessible. The manual for the unit says to "dismount" the drive first, then power off.
I have a couple of LS-WVL-E units as well as a LS-WX2 and when I want to change a drive (for example, replace a small drive with a larger one), I simple save (or backup) the files on that drive, dismount it, power off, replace the drive and power up, format and restore the files. When I look at the old drive just removed (Using Win 7 or 8 Disk utilities) I see a single blank partition that Windows wants to initialize (I bypass that). I can use this drive as is in any of my other units to include the LS421DE.
When I try to do the same in the LS421DE, like I say, the Dismount button is greyed out, so the only option is to power off & change the drive out. As long as the new drive is clean (like one single partition, not initialized by Windows), all is fine. If I try to use this newly removed drive in the LS-WVL-E unit, it WILL NOT complete the initialization - looking at the drive shows multiple partitions which must be cleaned out to the "new, un-initialized" state using 3rd party software before I can use it on the older units.
Main question is: Why is the "Dismount" button disabled in the LS421DE unit when the manual specifically says to "dismount" the drive and why do I need to completely re-initialize the removed drive without any instructions or guidance (believe me I've looked in the manual)?