While I don't have any information on this, I'd suspect they'd be using ESU 4, CW EMS, or one of the NIFOG med channels. Those are what I'd keep an eye on, on top of whatever Fire Dispatch they will be responding to.
Speaking with one of their new employees, it sounds like they are responding on an as-needed basis, for now, after their local resources are not available or beyond their level of care. Knowing how things go, I see that being short-lived. and they get added to the initial call run cards quickly. I heard the initial target areas for coverage were Colden and Eden, so they'd be strategically placed to provide coverage in Southern Erie County, where ALS is often distant and relies on volunteers or distant commercial services.
I also read something about constructing a County EMS crew station on Olean Rd near the end of Rt 400, but I could be wrong about its purpose. Last I heard (last week), fly cars were still being upfitted, but they will be in service in the coming weeks.