There's no doubt, cleaning grout can make you pout. Grout is very porous, which means liquid cleaners seep through it like excrement through a goose. So you need a lot of patience. First, spray a 50/50 solution of hydrogen peroxide and water directly on the spot. Make sure you soak it good. Let it set 15 minutes, and repeat. Note: If you are working with colored grout, ignore the preceding instructions. The peroxide, which is a bleach, will remove the color from colored grout. If you still can't get the stain out, soak a heavy-duty paper towel in peroxide and lay it over the stain. Cover the towel with plastic wrap to prevent the peroxide from drying out quickly. The towel holds the peroxide on the surface giving it time to dissolve the stain. If that doesn't work, mix a paste of straight peroxide and baking soda. Allow the bubbling to subside. Apply to the stain and let it set. Re-spray with peroxide as it dries out. Miscellaneous notes: Shaving cream also does a good job removing stains on grout. If your grout is colored test an inconspicuous spot first. Tile stores now carry a cleaner stick that resembles chalk. It is safe to use on colored grout and works wonders. Finally, once you remove the stains from the grout, seal it.
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