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If they have opened and read it, and by doing so essentially get the information they need, you really can't unring the bell.
If they claim they haven't read it, and you think they did, you'd have to prove it the same way you prove anything in court - by evidence. There would likely be several sources of evidence in this case. Witnesses ("I saw CEO Joe open and read it." or "CEO Joe told me he read it.") Or probably some technical evidence, like a forensic computer expert going into the system and figuring out whose computers have opened the attachment. That would seem to be a legally (lawsuit, lawyers, motions, court orders) and technically (expensive experts) expensive process.
The ex-employee would probably argue he's done nothing wrong and has not violated the non-compete. He got the e-mail, but never showed it to anyone, if the employer went into the system and got it themselves, he didn't know or expect that would or could happen.
In any event, the lawyer who sent that e-mail to the ex-employee to his work e-mail address was not very smart or careful.
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