There is a major difference between "train air" and "straight air." Subway cars are straight air, wherein air applies the brakes. If there is no air, there are no brakes. Subway cars do employ a "brake pipe" referred to as train line pressure, but it does not function like a railroad brake pipe. Train line pressure simply holds valves closed to keep the train out of an emergency application. This way, if the train comes apart it allows the emergency valve to open resulting in an emergency application. Train air fills every car with air pressure and then controls that air with the brake pipe pressure.
While I don't know the specifics of the incident, we do know that it involved a disabled train. The most likely scenario I can come up with is a dead pair of cars were brought into the yard and uncoupled. After the uncoupling the cars began to roll and, because there was no air in the system as the cars were dead, there was nothing other than wrapping a probably fairly weak handbrake that the employee on board could do.
Moderator: Massachusetts Bay Transportation Authority, Brightline Trains
Avatar:3679A (since wrecked)/3623B (now in service as 3636B).