Green extraction techniques (GreETs) emerged in the last decade as greener and sustainable alternatives to classical sample preparation procedures aiming to improve the selectivity and sensitivity of analytical methods, simultaneously reducing the deleterious side effects of classical extraction techniques (CETs) for both the operator and the environment. The implementation of improved processes that overcome the main constraints of classical methods in terms of efficiency and ability to minimize or eliminate the use and generation of harmful substances will promote more efficient use of energy and resources in close association with the principles supporting the concept of green chemistry. The current review aims to update the state of the art of some cutting-edge GreETs developed and implemented in recent years focusing on the improvement of the main analytical features, practical aspects, and relevant applications in the biological, food, and environmental fields. Approaches to improve and accelerate the extraction efficiency and to lower solvent consumption, including sorbent-based techniques, such as solid-phase microextraction (SPME) and fabric-phase sorbent extraction (FPSE), and solvent-based techniques (μQuEChERS; micro quick, easy, cheap, effective, rugged, and safe), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE), in addition to supercritical fluid extraction (SFE) and pressurized solvent extraction (PSE), are highlighted.

Sample preparation has been recognized as a major step in the chemical analysis workflow. As such, substantial efforts have been made in recent years to simplify the overall sample preparation process. Major focusses of these efforts have included miniaturization of the extraction device; minimizing/eliminating toxic and hazardous organic solvent consumption; eliminating sample pre-treatment and post-treatment steps; reducing the sample volume requirement; reducing extraction equilibrium time, maximizing extraction efficiency etc. All these improved attributes are congruent with the Green Analytical Chemistry (GAC) principles. Classical sample preparation techniques such as solid phase extraction (SPE) and liquid-liquid extraction (LLE) are being rapidly replaced with emerging miniaturized and environmentally friendly techniques such as Solid Phase Micro Extraction (SPME), Stir bar Sorptive Extraction (SBSE), Micro Extraction by Packed Sorbent (MEPS), Fabric Phase Sorptive Extraction (FPSE), and Dispersive Liquid-Liquid Micro Extraction (DLLME). In addition to the development of many new generic extraction sorbents in recent years, a large number of molecularly imprinted polymers (MIPs) created using different template molecules have also enriched the large cache of microextraction sorbents. Application of nanoparticles as high-performance extraction sorbents has undoubtedly elevated the extraction efficiency and method sensitivity of modern chromatographic analyses to a new level. Combining magnetic nanoparticles with many microextraction sorbents has opened up new possibilities to extract target analytes from sample matrices containing high volumes of matrix interferents. The aim of the current review is to critically audit the progress of microextraction techniques in recent years, which has indisputably transformed the analytical chemistry practices, from biological and therapeutic drug monitoring to the environmental field; from foods to phyto-pharmaceutical applications.

The theory and working principle of fabric phase sorptive extraction (FPSE) is presented. FPSE innovatively integrates the benefits of sol–gel coating technology and the rich surface chemistry of cellulose/polyester/fiberglass fabrics, resulting in a microextraction device with very high sorbent loading in the form of an ultra-thin coating. This porous sorbent coating and the permeable substrate synergistically facilitate fast extraction equilibrium. The flexibility of the FPSE device allows its direct insertion into original, unmodified samples of different origin. Strong chemical bonding between the sol–gel sorbent and the fabric substrate permits the exposure of FPSE devices to any organic solvent for analyte back-extraction/elution. As a representative sorbent, sol–gel poly(ethylene glycol) coating was generated on cellulose substrates. Five (cm²) segments of these coated fabrics were used as the FPSE devices for sample preparation using direct immersion mode. An important class of environmental pollutants—substituted phenols—was used as model compounds to evaluate the extraction performance of FPSE. The high primary contact surface area (PCSA) of the FPSE device and porous structure of the sol–gel coatings resulted in very high sample capacities and incredible extraction sensitivities in a relatively short period of time. Different extraction parameters were evaluated and optimized. The new extraction devices demonstrated part per trillion level detection limits for substitute phenols, a wide range of detection linearity, and good performance reproducibility.