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You could try Salactol. I've never had a callus but I know a few people who have used Salactol and found it to be effective. As for why you get them on your big toe, I imagine it's pretty much the same reason as to why you get them anywhere. The general consensus seems to be they're caused ''because of excessive pressure at a specific area of the foot. Some common causes of callus formation are high-heeled dress shoes, shoes that are too small, obesity, abnormalities in the gait cycle (walking motion), flat feet, high arched feet, bony prominences, and the loss of the fat pad on the bottom of the foot.'' http://www.foot.com/info/cond_calluses.jsp
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