No, it is never accessed in such a way, nor will ever be, but yes the existing key would suffice, because even though it is composite, one part can be used:
Code:
SELECT userID
FROM `access_master`
WHERE dataID = 62
LIMIT 0 , 30
// Showing rows 0 - 29 (2,917 total, Query took 0.0141 sec)
Clearly no table scan there
The concern, and reason for delete, was the amount of disk space required for the extraneous key. While watching my browser tick over waiting for that to complete, I became concerned since I am not familiar with how phpmyadmin goes about the task, plus knowing that it can fail with as simple a task as producing a dump from a large table. Thankfully it did not fail on this and corrupt the table.