I've hacked about a little and have now changed the 'Limited Email Addresses' option so that it blocks the domains specified as I will find that a much more useful option.
If anyone is interested, replace:
=======
$emaildomain = substr( , 1 + strpos( $user_email, '@' ) );
if( in_array( $emaildomain, $limited_email_domains ) == false ) {
$errors->add('user_email', __("Sorry, that email address is not allowed!"));
}
=======
With
=======
foreach($limited_email_domains as $e => $v) {
if (strpos($user_email, $v)) {
$errors->add('user_email', __("Sorry, that email address is banned."));
}
}
=======
In: wp_includes/wpmu_functions.php
Ideally it would be good to have another option, but as I won't be using the limited email address functionality I'm happy just to do this quick fix for now.