Seemingly no matter what options I choose on the Volunteer Report it throws the error "DB Error: unknown error" and I don't see anything in the Apache error logs.
What's the best way to troubleshoot this and see the actual error? Thanks.
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You are looking in the wrong place.
Check your PHP logs on your webserver.
Check the civicrm logs in /civicrm/ConfigAndLog or wherever you have configured that folder.