All outgoing email is being scanned for sensitive information in plain text or attachments. This is standard practice in every corporation and something you are being warned about when being on-boarded as a new-joiner.
And of course this same applies to file uploads. Again, this is standard practice in any company with IT security.
I'm just questioning why she would email to multiple external accounts directly from her corp email instead of saving to 1 personal account and then sharing from there, undetectable, many times. And yes, they would still have detected the 1 email but I'm questioning the accuracy of this explanation; sounds partly made up to make it sound more serious.
Part of my job is administering a system for detecting unauthorized sharing, exporting, or printing. It has thresholds and a rules-based engine for specifying what behavior should trigger alerts. Google's system is probably custom but there are definitely products on the market for this sort of thing.