I used to work in a shop where the DBAs, in addition to some of the other replies posted here, would be the owner of the database architecture.
All physical/structural changes are done in coordination with the DBA team, who is the only group allowed to make these changes in any environment other than development. They create the scripts, work with the developers, and serve as a change management control board.
For interfaces (SPs, UDFs, etc), they manage them in the production environment, and check them for consistency and quality (in a larger shop, a lot of different types of programming style can exist from one SP to the next, depending on author). They maintain the library of production interface code (and keep a version control history of production).
Additionally, large clustered databases require management, not just involving replication (this enterprise has databases in different parts of the world, for redundancy and fault tolerance).
Lastly, performance, optomization (indexing) and tweaking grow as an effort as the size of the databases on the server grow (num databases, amount of data, amount of structure, etc). Even a perfectly architected database will have more of these things to manage, if it is successful.
I'm sure Google, for example, has a good number of people employed just to keep the data farm operating efficients and reliably.