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Normally caused by calcium build up or caclcification. Prevetion and cures can be found on my blog.See the link on this message Permanent brown stains are usually caused by "iron". Rebar attached to the pool exterior and encapsulated in bottom of a concrete deck is the usual suspect. Another cause, which can be reversed, is an older heater. If a heater is involved, have the headers and impellers checked for iron. If they're iron, have them changed-out, then try a sequestering agent following the directions. Permanent stains in fiberglass pools are caused by either iron (brown), chlorophyl (green), or air holes caused by failing gel coat (black).

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Q: What causes permanent brown stains to a fibreglass pool?
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