The dealer uses their VST scan tool to run it through its diagnostic test mode and by doing that, they can properly determine if the pump's running, not electrically inop or siezed by doing so.
The pump doesn't always come on everytime the engine's started cold, there's a few conditions that need to be met and it's determined by the fuel ECU.
I've never tryed activating the pump by the means that you're listing as I use the VST and it's never let me down, nor have I seen where the air pump circuit was anything more involved that a bad pump and/or relay.
In your case, if you're sure that your relay isn't getting the proper voltages, then your next step is to 1) get a OEM wiring manual from Volvo (800-25-volvo or online at their site) and 2) using that wiring diagram, trace the circuits to/from the relay and determine what's not getting voltage and why. It's remotely "possible" that you have a ECU problem but I doubt it. It's more likely IMHO that you're not knowing when that air pump is suppose to work and trying to fault check something that might not even be a problem. For example, is the check engine light on and if so, are you sure you've got air pump codes?
If the check engine light's off and you're not getting air pump codes, then I wouldn't even worry about it. BTW, I've seen intermittant air pump codes appear too that commonly occurs when temps go below freezing and I speculate that it's because moisture is in the pump and thus freezing the pump. As the temps increase, the pump later works and will test normally but eventually the moisture becomes excessive and the pump motors get noisy and/or just sieze. It's a very bad design, put into the worst possible location where moisture can't escape.
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