There is no supported way to do so. You can use https://marketplace.atlassian.com/plugins/com.javahollic.confluence.confluencesu to switch into the user and then change it. You can also hack it via the DB, but that is high risk.
Here is an open source utility I created for changing a user's profile photo. It uses Confluences API's so it is safe to use ... as opposed to hacking the database.
https://bitbucket.org/fredclown/confluence-profile-photo-uploader
I just released v1.1.0.0 of the profile photo uploader. It does better face detection and cropping, has a version checker, and a test harness to see how the system will crop and resize your photos.
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