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You will struggle to entirely remove the stain, but you can try remove the mark if you carefully soak the whole shoe. You risk affecting the shape if you aren't careful with packing the inside (not too tight not too loose).
You can use isopropyl alcohol to soak and dry the entire upper, but otherwise use water and saddle soap if there is dirt too. The shoes may darken after you're done.
You must try to remove all the wax or other coating on the leather (saddle soap/ipa), and then soak it so that it dries consistently across the upper. Using saddle soap will soak in and you can scrub the upper too to get a good finish.
Trick is not to use heat when drying as it will shrink or cause more marks. A little above room temp, or the airing cupboard, not a radiator.
Hope that makes sense. Water marks are a bitch.
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pdlouche
@Olly398
@pdlouche can I pick your brain? My OH has some cheapish brown leather chelsea boots she wore through some rain/puddles without treatment. Best way to remove the water stain / tidemark before I polish. Will post some pics later.