Quick update,
I plugged it into my PC and after several times sending the machine into a spin, it showed up unmounted. I then ran Recuva, which saw it and declared there were no deleted files. Back to Explorer and...there it is, fully mounted and available as if nothing had happened!
I'm just copying some stuff off it and later will see if it works on my Macs. If it does, I think I might re-format anyway as it was clearly in trouble of some sort.
@DV was it something in Recuva that brought it back to life?
[Edit] It will mount on my Mac - but it won't mount automatically. I have to go into "NTFS for Mac" and instruct it to. It takes several minutes to come up. However everything is now safely backed up so all is well (not that there was anything important before as I said).
I think I might invest in another 4TB and copy everything on this one before re-formatting and mirroring back. You can't have too any backups and clearly something was wrong here and remains a bit iffy...