Development of pressurized subcritical water extraction combined with stir bar sorptive extraction for the analysis of organochlorine pesticides and chlorobenzenes in soils

An analytical method for the determination of several organochlorine pesticides (OCPs) like hexachlorocyclohexanes (HCHs), cyclodiene derivates (dieldrin, aldrin, endrin, heptachlor, heptachlor epoxide, endrin aldehyde, endosulfan and ensodulfan sulphate) and DDX compounds (p,p′-DDE, p,p′-DDD and p,p′-DDT) as well as chlorobenzenes in soils has been developed. The procedure is based on pressurized subcritical water extraction (PSWE) followed by stir bar sorptive extraction (SBSE) and subsequent thermodesorption–gas chromatography/mass spectrometry analysis. Significant PSWE and SBSE parameters were optimized using spiked soil and water samples. For the PSWE of the organochlorine compounds, water modified with acetonitrile as the extraction solvent, at an extraction temperature of 120 °C, and three cycles of 10 min extraction proved to be optimal. Under optimized conditions, the figures of merit, such as precision, accuracy and detection limits were evaluated. The detection limits obtained for soil samples were in the range 0.002–4.7 ng/g. Recoveries between 4.1 and 85.2% were achieved from samples spiked at a concentration level of 25–155 ng/g. The main advantages of this method are the avoidance of clean-up and concentration procedures as well as the significant reduction of the required volume of organic solvents. The described method was applied to the determination of the pollutants in soil samples collected from a polluted area, the Bitterfeld region (Germany). The results obtained by PSWE–SBSE were in a good agreement with those obtained by a reference method, a conventional pressurized liquid extraction (PLE).