Here's a unique historical look at how Tor users have been de-anonymized and caught by Adrian Crenshaw at the DEFCON hacker conference a couple years back.
DROPPING DOCS ON DARKNETS: HOW PEOPLE GOT CAUGHT
Tip o' the hat to /u/SirReal14 for his post in /r/CryptoAnarchy/.
Oh god, I actually cringed at the email address with Ross, had never heard of that leading to his arrest.