Oh well, so much for that theory!
Would using mail or PEAR Mail with SMTP make any difference?
The only other thing I can think of is that I know the emails for the domain are running off Google's email servers, rather than the host's own servers.
If these emails get sent directly from the host server would they be using the host server's SMTP settings from the php.ini file, whereas an email sent from a computer using the same address would use Google's SMTP settings.
In which case entering the Google server's SMTP settings in the UE behaviour settings might help?
Or am I barking up the wrong tree again?