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I don't know if this fits the definition of a natural shampoo, but I really like the Lush Fair Trade Honey shampoo. A little goes a very looong way for me. It is not marketed as a clarifying shampoo, but it works as a clarifier for me and it supposedly helps with removing hard water buildup as well.
It is 50% honey and 20% lineseed, but it has sodium laureth sulfate and lauryl betaine as cleansers. I use very little of it concentrated at my roots and it does such a great job and leaves my hair shiny. I only use it monthly.