In short: no. The idea of a LAN is that each machine can communicate directly with any other on the local network, without contacting a router. pfSense can't even see that local traffic (because you have a switch), let alone control it. There are some messy workarounds to this, but it's not worth the effort or confusion.
The solution is that you need to create a separate LAN for each PC. To do this reasonably, you need to either have a separate interface for each PC, or use a VLAN-capable switch to accomplish the segregation. Then all traffic must flow through pfSense to reach the other LANs and you will have full control.
You should, however, be able to control access to the pfSense WebUI or any other service running on pfSense, however you need to disable the 'anti lockout' rule in Advanced Settings.