Since I don't recall a "free shipping" checkbox in shipping settings, my guess is for your international customers, you started to setup shipping bands to those countries but did not enter any rates at the bottom of that screen, thus it defaults to 0.00 (free)...
I think Calibrick is right, if looks like your Royal Mail 2nd class which ships worldwide has a zero price. You have a note on it which says to use 'Request a quote' but that won't stop buyers using that shipping method.
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