You say: seasoned web developer ... so:
So you should know as much as any respectable sys admin. This allows you to pick the right technologies for the business case/constraints.
You should also know about:
- Database servers / DBA
- Network architecture, bottleneck prevention, resource allocation
- Network and system security
- Protocols, firewalls, routing
- Various application stack configurations (beyond LAMP or .NET)
- Distributed systems, scalability
- Technology evaluation (MoEs, MoPs and all that)
And tons of other stuff. Being a web developer is a specialization of 'developer' for a given environment ... as such you should know everything about that environment and everything that emerges out of, develops from or impacts on it.