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It's not entirely understood how or why iontophoresis works, but it's believed that the electric current and mineral particles in the water work together to microscopically thicken the outer layer of the skin, which blocks the flow of sweat to the skin's surface

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Neuschwander-Tetri BA, Loomba R, Sanyal AJ, Lavine JE, Van Natta ML, Abdelmalek MF, et al

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