No, not showing a user in GAL is the closest you can come.
Also, none of this matters if the event organiser has ever communicated with such a user, because all such users will also be listed when creating an event.
Basically, you can use Steve Job's quote "You're doing it wrong" to guide you further when communicating with such users. 🙂
People should not have more than one account, and definitely not accounts used for every day work.
If you are a superadmin, you may have one daily and one admin account, which is fine, but then you can set gal off on the admin account, since nobody should ever communicate with it, and also tell people, if they ever make that mistake, to not do so. You can even have an auto-reply telling them of the fact. And then, of course, never yourself email or communicate with users with your admin account.
If people need to be able to receive email to different addresses, both aliases and Groups can be used, and even Recipient Address Mapping works for that.
As much as possible, you/they should always avoid emailing from different addresses, but even there the user can use the SendAs feature, and still do it from their daily account.
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