Try putting a chlorine puck on the stain and seeing if it lifts it? If that doesn't do it go get some cheap chewable Vit C tablets in a sock and bash it a bit to break them up in the sock. Then hold the sock on it a few minutes to see if that is the magic that lifts it.
Chlorine puck works= organic stain
Vitamin C works = metal stain
You haven't added any cheap algaecides that contain copper, have you?
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