When connected to the internet with a Mobile Broadband service, it will not usually be possible to send mail using your normal ISP's SMTP (outgoing) mail server, unless it supports "SMTP Authentication".
Therefore, the email program's settings need to be changed to use the 3G network's own SMTP server and these should be the current server addresses for the various networks:
Vodafone 3G SMTP Serverssmtp.vodafone.net
send.vodafone.net
smtp.vizzavi.co.uk
Three 3G SMTP Serverssmtp-mbb.three.co.uk
smtp.three.co.uk
T-Mobile 3G SMTP Serverssmtp.t-email.co.uk (May need to use SMTP Auth and tick "Use In mail settings")
Orange 3G SMTP Serverssmtp.orange.net
smtp.orange.co.uk
O2 SMTP Serverssmtp.o2.co.uk - GPRS and 3G
Virgin SMTP Serversmail.virgin.net
smtp.virgin.net
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Mike