Modified vermiculite as a sorbent phase for stir-bar sorptive extraction

The presence of emerging contaminants (ECs) is a cause of great concern nowadays, and they are present at very low concentrations in surface waters, requiring a preconcentration process for their reliable quantification. The technique of Stir-Bar Sorptive Extraction (SBSE) is a valuable tool for achieving this purpose, and different sorbents have been developed to produce the bars. In this sense, we propose the use of the clay mineral vermiculite (Vt), modified with alkylammonium salts, aiming the determination of the ECs: bisphenol A, diclofenac, ibuprofen and triclosan in surface water samples.

The best conditions for sorption and desorption were: 50.0 mL of sample at pH 4.0, under stirring at 600 rpm (120 min), being the desorption carried out under sonication for 20 min using 500 μL of methanol, and the analytes were determined using LC-DAD. A linear range from 0.50 to 2.50 μg L^-1 or from 0.50 to 5.00 μg L^-1 and R² higher than 0.9480 were observed, and attractive real enrichment factors between 116 and 177 times, affording a LOD between 0.11 and 0.33 μg L^-1. The method was applied to determine the four ECs in samples of tap, river, and lake waters, presenting recovery results between 42.0 and 128.0 %, and RSD from 0.4 to 19.6 %. The bars prepared using Vt presented good chemical and mechanical resistance, even modified using the alkylammonium salts, permitting them to be employed at least 30 times, without memory effects.

The modified Vt, afforded a simple, low-cost, and attractive alternative to work as a sorbent phase for SBSE technique, presenting very appropriate analytical parameters, even employing LC-DAD. Although the sorbent was applied to a limited number of contaminants, it is probable that other analytes could be successfully determined. It is important to notice that this is the first study reported, employing modified Vt for SBSE application.