DNS 1 & DNS 2 - how does my router decide?

I had an old nettop sitting about (a Packard Bell Imax Mini) doing nothing so I decided to deploy it as a backup pihole and put its IP it as DNS 2 in my router. I didn't think it'd see much activity but it gets a surprising amount of traffic, particularly from one device (an Amazon Fire OS tablet, which fair spams both DNSs) I assumed the primary PiHole would handle pretty much everything, so I'm wondering by what process traffic is finding its way to the secondary DNS.

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