So, evidently, my new boots are causing blisters on the tips of my toes. I hadn't noticed them until I put the same boots on today, after an interim of 4 days. The blisters on the biggest 3 toes on each foot burst simultaneously (for each foot) as I put the boots on. It felt oddly like my feet were trying to jet-propel themselves out of said feet. It didn't work - I only ended up with dampish socks and huge amounts of loose skin on the tip of each toe. They're not really painful, just disgusting.
I think I will be careful about wearing said boots in the future.