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Well, I solved the mystery, and I feel slightly idiotic.
A while back, while organizing my fanfiction section, I discovered column icons (thanks BetterRed!). I added icons to the Title column to let me know if a certain fanfic was complete or in progress and loved it.
I then needed another icon, but you can apparently only have one icon per column, so I put this new icon on the Edit column, even though it had nothing to do with editing. So, even though the icon was not in use, I guess the column keeps that space 'reserved', therefore it doesn't show as centered with as small as I keep that column.
Also explains why, when I renamed the new column that *was* centered back to Edit, it changed to what I thought was not centered. While modifying another icon rule, I found the *problem* and felt very silly
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