Critical overview on the use of hydrophobic (deep) eutectic solvents for the extraction of organic pollutants in complex matrices.

During the last decades, many efforts have been devoted to the adaptation of sample preparation techniques and methods to the principles of Green Analytical Chemistry. Among them, this article review focusses on those aimed to green the solvents involved in sample treatment. Research in this field started in the late 1990s with the synthesis of room temperature ionic liquids, which were later replaced by the deep eutectic solvents (DESs). During the last years, a subclass of DESs, the so-called hydrophobic deep eutectic solvents (HDESs) have attracted attention. HDESs have contributed to circumventing some of the limitations of early-synthesised hydrophilic DESs regarding the cost of raw materials, the simplicity of synthesis, and the biocompatibility and, apparently, the biodegradability of the mixtures. In addition, these mixtures allowed the treatment of aqueous samples and the extraction of non-polar analytes. This article discusses fundamental aspects regarding the nomenclature used concerning HDESs, summarises the main physicochemical properties of these mixtures, and through discussion of key application studies, describes current progress in the use of these green solvents for the extraction of trace organic contaminants from a variety of matrices. Remaining gaps and possible lines of future development in this emerging, active and attractive research area are also identified and critically discussed.