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You pretty much have to do it at night. AFAIK, the spray isn't instantly effective, it takes a little time to kill them. Thus if you can get them when they're inactive, you have a better chance of poisoning them fatally. Also, the more of them you kill, the less there are around to sting you. As another consideration, it is easier to approach the nest without being stung if you do it in the dark.
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