Analysis of chlorophenols, bisphenol-A, 4-tert-octylphenol and 4-nonylphenols in soil by means of ultrasonic solvent extraction and stir bar sorptive extraction with in situ derivatisation

A novel method based on ultrasonic solvent extraction and stir bar sorptive extraction for the analysis of phenolic organic pollutants including chlorophenols, bisphenol-A, 4-tert-octylphenol and 4-nonylphenol in soil samples was developed. The different parameters that affect both the extraction of analytes from the soil samples, such as solvent selection, extraction time, and the partitioning from the solvent/water mix to poly(dimethylsiloxane) (PDMS) were studied. The final selected conditions consisted of the extraction of I g of soil with 15 mL methanol by sonication for 30 min. The methanol extract was mixed with 85 mL of Milli-Qwater and extracted by means of stir bar sorptive extraction with in situ derivatisation. The stir bars were analyzed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The effects of the matrix on the recovery of the various pollutants under the developed method were studied using two soils with very different physicochemical properties. Method sensitivity, linearity, repeatability, and reproducibility were also studied. Validation and accuracy of the method were conducted by analyzing two commercial certified reference materials and by comparing the analysis of real samples with the proposed method and a classical method using pressurized solvent extraction (PSE)-GC-MS. The main advantage of this method is a substantial solvent reduction. For the extraction of only 1 g of solid sample allowing limits of detection ranging from 0.2 to 1.7 mu g kg(-1) dw. Repeatability and reproducibility variation were lower than 20% for all investigated compounds. Results of the certified reference materials and the real samples verify the high accuracy of this method. (C) 2009 Elsevier B.V. All rights reserved.