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Try holding down ALT and typing in 64 on the keypad. You should be able to type in the ASCII code for any character. @ is 64 on mine, might be on yours, if it isn't try other ASCII values
Hmm, as long as XP is setup for UK, you shouldn'e need any drivers. What happens to your @ key when you just open a command prompt?
Within the properties of your shortcut, the Program Tab has an Advanced button. In there it defines the CONFIG.NT and AUTOEXEC.NT files used when running the DOS app.
Check these files to see if there are any keyboard settings defined. The keyboard.sys driver should be in the \windows\system32 folder. I'll need to hunt for the commands as it's been 3yrs since I've used them