A student has changed something while using an iPad so that the iCloud is using her personal imail account for the other 90 iPads. I've tried to change the preference in iCloud to no avail please help

While in Apple ID, the primary address is correct which is our college.  The iCloud however is using the icloud email address of the student who formerly borrowed the iPad.  I have gone to preferences in an attempt to change the email address, thinking she may have used this as an alias, but it is not posted as an alias. I am stumped on how to fix this. Each time she does something via her personal account, it affects the other 90 iPads in the program & whenever any email is involved it lists her as the sender.

What you have described above contradicts to my information. If you did delete icloud account, there is no way you should see her iclud mail account and if it is not icloud - you just need to delete it as well.
Most likely you just receiving her emails right now and after you delete mail account you should be all set.
Go to settings - mail contacts calendars. Find her account and click - you will see delete button below. When done - e-mail that you changed billing info should disappear. Check it.
Other ipads are not affected and you didn't show in anyway that they are. That is the article that will allow you to check if school billing info is still the same in itunes store.
iTunes Store: Changing account information - Apple - Support

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