Well it was running on 16gb, and fine for weeks. Its only just recently that its gone down the drain.
That's *exactly* what happens when you starve the system too much. Everything is fine.. then it jumps of a cliff and commits seppuku.
You almost certainly will need more than 32GB of RAM with a zpool of that size. I've got a 60TB zpool (10x6TB in RAIDZ2) and I'm walking a very fine line as the sole user of the server.
I'm very skeptical about your experience claiming it is the disks. I've done some pretty nasty tests to those disks, and unless you are going to tell me you are writing 20GB per disk x however many disks in your zpool, and doing it nonstop for a long period of time (20+ minutes, which is more than your Windows LAN performance charts are showing) then I'm not really buying it.
Since your problem is with reading, that's just negated the whole discussion that it is the disks...
I will definitely put more faith on the RAM being a problem. If you don't have enough RAM, your metadata can't fit, and performance hits the floor. On my system I was getting over 1GB/sec (yes, 1 Gigabyte/sec) and the next morning I couldn't do 10MB/sec. Had to add more RAM to get over the performance problems.