Some additional information is worth noting.
We have a dual WAN setup:
WAN1 - 192.168.254.1
WAN2 - 192.168.253.1
Systems in the DMZ use WAN2, systems on the LAN use WAN1, so it is somewhat strange that the firewall log is filling with blocked DNS responses going to the WAN1 interface when the systems that should be actively using DNS in the middle of the night are on the DMZ (i.e. email). Occasionally there is a block on the WAN2 interface, so this is not exactly conclusive of anything, but I still find it worth a mention.
Also, the configuration on pfSense is that DNS should be overridden by DHCP on WAN, and DHCP on WAN provides pfSense with the ISP DNS server addresses. I have tried statically setting the DNS servers in pfSense with the same result. :-\