If I'm reading your request correctly, you may be able to wire the control coils of two normally open relays in parallel to the 24v zone valves of the two respective zones. The normally open contacts of those relays would then be placed in parallel with each other (so either one would complete the circuit) and in series with the aquastat circuit.
That way, the aquastat would only be able to start the boiler if one or both of the normally open contacts were in fact closed. The thermostat in either of the zones would energize the circulator pump and the 24v zone valve AND the 24v relay with the N/O contacts. If either one closes it would bring the temp up because then and only then would the aquastat be in the circuit, and if both zones are satisfied, the aquastat is removed from the circuit and the boiler would no longer maintain the temp at the setpoint of the aquastat.
HOWEVER.... do not do this based on this discussion without consulting an on site repairman...none of us here have the luxury of placing eyes on your system therefore any and all suggestions should be considered bogus. There are many things to consider when changing a proven control scheme and things are easily overlooked without having information "in-hand".
That being said, I really wouldn't suggest doing what you want to do at all...consider and outdoor thermostat that will lock out your boiler until the outdoor temp gets to the point that your alternate heat source begins to struggle. It would go in series with the aquastat and only allow the boiler to come on at that outdoor temp setpoint and below. Then again..... refer to the previous paragraph....lololol
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