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Best practice is for the ESD mat to be connected to equipment ground (typically ground of an AC electrical outlet) using snaps and a ground cord. The electrostatic charges will follow the path of least resistance. There is no need to place an insulative mat under the ESD mat.
“Concrete” is mentioned in ESD Handbook ESD TR20.20 but as a “Typical Static Electricity Sources” in Table 1 under floors. You are quite correct that during periods of high relative humidity that the moisture will provide a path to ground and for a while measure < 1 x 10E9 ohms, the required limit per ANSI/ESD S20.20-2007 Table 3. Concrete is hygroscopic (readily absorbing moisture), and it would be the moisture, not the concrete that would be providing the resistance path. This certainly would not be a best practice.Statguard® Static Dissipative Floor Finish is used to dissipate static charges as well as prevent triboelectric (static charge generation) charges while providing a clear, high gloss finish that resists wear. Statguard® Static Dissipative Floor Finish is a cross linked polymer free flowing liquid emulsion, which can be applied on any hard surface such as your linoleum tiles.