Herein we present a simple, rapid and low cost strategy for the preparation of robust stir bar coatings based on the combination of montmorillonite with epoxy resin. The composite stir bar was implemented in a novel automated multisyringe stir bar sorptive extraction system (MS-SBSE), and applied to the extraction of four chlorophenols (4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol) as model compounds, followed by high performance liquid chromatography-diode array detection. The different experimental parameters of the MS-SBSE, such as sample volume, selection of the desorption solvent, desorption volume, desorption time, sample solution pH, salt effect and extraction time were studied. Under the optimum conditions, the detection limits were between 0.02 and 0.34 μg L−1. Relative standard deviations (RSD) of the method for the analytes at 10 μg L−1 concentration level ranged from 3.5% to 4.1% (as intra-day RSD) and from 3.9% to 4.3% (as inter-day RSD at 50 μg L−1 concentration level). Batch-to-batch reproducibility for three different stir bars was 4.6–5.1%. The enrichment factors were between 30 and 49. In order to investigate the capability of the developed technique for real sample analysis, well water, wastewater and leachates from a solid waste treatment plant were satisfactorily analyzed.
