PA uses top-down first-match (like most FW's do nowadays) which gives that your "Alerting" rule will never be hit since its shadowed by "Block URL for everyone". Could you paste the output you get from the commit-window when you commits? There should be warnings about the shadowing I mentioned above aswell as lack of dependencies (which what I guess is why your user never hits that allow rule). To test if your userid is correct you could as a test (if possible) set application to "any" to verify that its application related and not userid related. By the way - your service-column should NEVER be set to any (in my opinion) - you should use "application-default" OR set this manually (like TCP80, TCP443 if you only want browsing to occur on these ports).
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