Second vinegar-based method:
This method is not eco-friendly, but it will remove mineral stains and grime with little effort.
Supplies you’ll need:
Borax
Toilet brush
Vinegar
Instructions:
1. If you choose to use vinegar, add 1/2 to 2/3 cup to the toilet bowl.
2. Allow the vinegar to sit for 10 to 15 minutes. For extra hard water, you can let this sit for an hour or more.
3. Scrub the toilet lightly with the toilet brush trying to scrub off as much loose minerals as possible.
4. Flush the toilet.
5. Pour a 1/2 cup of borax into the toilet. You want to sprinkle this around the toilet bowl gently, allowing it to hit all the stains. (Start here if you are not using vinegar.)
6. Use the toilet brush to do some scrubbing.
7. Allow the borax to sit in the toilet as long as possible. Overnight is best.
8. Give the toilet another good scrub, making sure all the stains are gone.
9. Flush.
Source: cleaninginstructor.com