I personally think that they are on very dodgy ground. There is a way to do these things correctly, and opening people's personal email (even if they are on work systems) just by catching sight of a title is not it.
The Telecommunications (Lawful Business Practice) (Interception of Communications) Regulations 2000 and the Human Rights Act 1998 (HRA) - Article 8 both come into play and have to be balanced. The monitoring needs to be justified and proportionate.
I personally would not dream of just opening staff emails without their knowledge without having completed a full audit trail including justification of the monitoring, and evidence as to why I thought I had this justification to read their email. There also has to be a policy in place that workers are aware of that inform them that emails can be monitored.
If I had heard on the grapevine that she had lied in her interview and staff then made comments about seeing her using her work PC for personal use etc, I may look at the covert monitoring of her mails, through well documented procedures. But to simply presume there was something dodgy going on by seeing the title of one personal email, when I shouldn't even be looking at her screen... unfair dismissal case coming up I'm afraid, however unfair this seems.
Was she allowed to access the Internet for personal use? If not, then that could have been the way to dismiss her.
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