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Basically, enzymes are substances that speed up chemical reactions. In the case of enzyme based cleaners, they are designed to speed up the process of breaking down oils, proteins, etc. that may be in your pool.
Enzymes will break up very large particles into smaller ones that can be handled more easily by your sanitizer. Regular use of an enzyme will help reduce scum line buildup and free up your sanitizer for the work it was intended to do-sanitizing.

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