Over the past two decades, greater attention has been paid to the
use of chemical processes in an environmentally and human friendly way to suit
green chemistry approaches. The latter goal consists of designing chemical
processes to either reduce or eliminate hazardous substances, as guided by the
12 Principles of Green Chemistry [1]. In this
context, new analytical procedures have been
developed to protect people’s health and to eliminate, or at least reduce, the
negative impact of chemical products (e.g., organic
solvents) on the environment [1–3]. Much
effort has been made to develop green analytical separation methods, especially
with the advent of ultra-high performance liquid chromatography (UHPLC),
capillary electrophoresis (CE) and supercritical fluid chromatography (SFC),
which use significantly reduced quantities of organic solvents. For complex
matrices or at very low analyte concentrations, the sample preparation step is
considered to be the most polluting step of the analytical process [2,4].
Liquid–liquid extraction (LLE) and solid-phase extraction (SPE) are widely used
for sample clean-up and analyte preconcentration; however, large volumes of
hazardous organic solvents that are harmful to both humans and the environment
are required for these extractions. Therefore, new sample preparation
techniques have been developed over the last few years that (i) replace the toxic
organic solvents used and (ii) reduce solvent consumption [4].
For the former, toxic solvents can be replaced with alternative, nontoxic
extraction agents, such as supercritical fluids (supercritical fluid
extraction, SFE), ionic liquids, superheated water (subcritical water
extraction, SWE) and surfactants (cloud point extraction, CPE). For the latter,
recent investigations have focused on developing miniaturised sample
preparations that drastically reduce solvent consumption (i.e.,
microextraction techniques) [5] or extract
the analyte of interest without a solvent (i.e.,
solventless sample preparation techniques) [6].
This miniaturisation can
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