Tom Lane is one of the largest contributors to Postgres, this post analyzes some of the Postgres mailing list archives for emails with some fun findings. (An updated post originally from 2013.)
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Autovacuum generally works pretty well and keeps your database healthy and performing quickly, but there are some things that can introduce complications as highlighted here such as long running queries.
Most applications these days use sequences (via serial) without even realizing it. Here’s a great primer on how they work and some of the details about them.