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This document is intended to provide the newcomer to headspace sampling with a concise summary of the theory and principles of this exciting technique. Enough information is included here for the user to understand the basic concepts and relationships in HS sampling to apply during method development and interpretation of data. Although emphasis is given to the PerkinElmer TurboMatrix HS systems, the document also covers alternative systems so that it should be useful to all potential users of HS systems.