Improving the On-Line Extraction of Polar Compounds by IT-SPME with Silica Nanoparticles Modified Phases

In the present work the extraction efficiency of in-tube solid-phase microextraction (IT-SPME) for polar herbicides has been evaluated using extractive capillaries coated with different polymeric sorbents. For this purpose, aqueous solutions of herbicides with a wide range of polarities, including some highly polar compounds (log Kow < 1), have been directly processed by IT-SPME coupled on-line to capillary liquid chromatography with UV-diode array detection. For extraction, commercially available capillary columns coated with polydimethylsiloxane (PDMS) and polyetilenglicol (PEG)-based phases have been used, and the results have been compared with those obtained with a synthesized tetraethyl orthosilicate (TEOS)-trimethoxyethylsilane (MTEOS) polymer, as well as the same polymer reinforced with silica nanoparticles (SiO2 NPs). The SiO2 NPs functionalized TEOS-MTEOS coating provided the best results for most herbicides, especially for the most polar compounds. On the basis of the results obtained, conditions for the quantification of the herbicides tested are described using a SiO2 NPs reinforced TEOS-MTEOS coated capillary. The proposed method provided satisfactory linearity up to concentrations of 200 μg/L. The precision was also suitable, with relative standard deviations (RSDs) values ≤9% (n = 3), and the limits of detection (LODs) were within the 0.5–7.5 µg/L range. The method has been applied to different water samples and the extract obtained from an agricultural soil