Highly efficient microextraction of chlorophenoxy acid herbicides in natural waters using a decanoic acid-based nanostructured solvent prior to their quantitation by liquid chromatography–mass spectrometry

Solvents used in microextraction require high solubilising capability to efficiently extract the target compounds. In this article, nanostructured solvents made up of alkyl carboxylic acids (ACAs) aggregate are proposed for the efficient microextraction of acidic pesticides from natural waters. The target compounds were chlorophenoxy acid herbicides (CPAHs) widely used in agriculture, forestry and gardening (viz. 2,4-D, MCPA, MCPP, 2,4,5-T and MCPB). The supramolecular solvents (SUPRASs) tested were generated from solutions of reverse micelles of octanoic (OcA), decanoic (DeA) and dodecanoic (DoA) acid in THF by the addition of water, which acted as the coacervating agent. The DeA-based SUPRAS was the most efficient extractant for CPAHs; actual concentration factors (ACFs) of 260 for 2,4-D, 290 for MCPA, and 400 for MCPP, 2,4,5-T and MCPB were obtained. The explanation for so high ACFs can be found in the extremely efficient retention mechanisms that the DeA-based SUPRAS provides for CPAHs (i.e. formation of hydrogen bonds and hydrophobic interactions), and the high number of binding sites that it contains (i.e. the concentration of biosurfactant in the SUPRAS was 0.56 mg μL⁻¹). Both characteristics permitted to effectively extract the target analytes in a low volume of solvent (about 2 μL of solvent per mL of sample). Others assets of the proposed supramolecular solvent-based microextraction (SUSME) approach included recoveries no dependent on matrix composition, rapidity (sample treatment spent about 15 min), use of low volume of sample (63 mL per analysis) and simplicity (no special lab equipments was needed). Combination with liquid chromatography/ion–trap mass spectrometry LC–(IT)MS] afforded method quantitation limits for CPAHs within the interval 22–30 ng L⁻¹. The precision of the method, expressed as relative standard deviation (n = 11, CPAH] = 200 ng L⁻¹), was in the range 2.9–5.8%. The applicability of the method to the analysis of natural waters was assessed by determining the target analytes in fortified river and underground water samples.