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Thats usually mineral deposits from hard water. One solution is to install a water softener--usually on the water to your hot water heater.

It can usually be cleaned with an acid. Vinegar should work. An acid toilet bowl cleaner such as The Works from Walmart should work better. It contains hydrogen chloride (ie hydrochloric acid). Keep it away from metals and rinse thoroughly.

There are also toilet bowl cleaners that contain sulfamic acid. That should work too.

Do not mix acid cleaners with bleach. They are not compatible
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