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The evolution of the sample treatment step towards the incorporation of the principles of Green Chemistry inevitably involves the use of materials that are sustainable from an environmental point of view. One of the most important advances in recent years is the use of natural materials as sorbent phases in microextraction processes. Among the most relevant characteristics of these substrates as regards Green Chemistry is the reusability of resources, which is a rising value to achieve a circular production model. This chapter covers natural materials that have proven their outstanding properties as extractants in sample preparation. Depending on their application, some of them can be used with minimal adjustments, while others require chemical modifications.

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