Validation of user- and environmentally friendly extraction and clean-up methods for compound-specific stable carbon isotope analysis of organochlorine pesticides and their metabolites in soils

• Environmentally friendly extraction methods for soils are compatible with CSIA.
• The clean-up procedures and solvent evaporation step do not cause isotope effects.
• Modified Ultrasonic Extraction (MUSE) provided the highest pre-concentration factor.
• The analytical uncertainty of the MUSE procedure is ≤0.4‰.
• The limits of detection for CSIA of chlorinated pesticides in soils are <1 mg/kg.

In order to evaluate the potential of compound-specific stable carbon isotope analysis (CSIA) for tracking organochlorine pesticides in soil systems, sample pre-treatment methods have to be developed, which can provide recoveries sufficient for low detection limits without altering the isotope ratio of the target compounds. In this study we tested the compatibility of CSIA with user- and environmentally friendly extraction methods, including the Quick, Easy, Cheap, Effective, Rugged and Safe procedure (QuEChERS), Ultrasonic Assisted Extraction (USE) and Focused Ultrasonic Extraction (FUSE), as well as clean-up methods, including sulfuric acid clean-up and Florisil® column chromatography for hexachlorocyclohexanes (HCHs), p,pʹ-dichlorodiphenyltrichloroethane (DDT) and their environmental metabolites (chlorinated benzenes, dichlorodiphenyldichloroethylene – DDE and dichlorodiphenyldichloroethane – DDD) in soils. We optimized the extraction methods for maximum recovery and pre-concentration. At optimal conditions, all extraction methods and clean-up procedures, as well as the pre-concentration of the extract by solvent evaporation, led to insignificant changes in carbon isotope ratios of the target compounds. We modified the USE procedure to increase the volume of withdrawn organic extract, resulting in a higher pre-concentration of the target compounds by the subsequent solvent evaporation step. This Modified Ultrasonic Assisted Extraction (MUSE) was the most suitable procedure, and it was validated for the determination of carbon isotope ratios of the target compounds using two different types of soil matrices. The method could be applied to analyze carbon isotope ratios of HCHs, DDT, and their chlorinated metabolites in soil samples with concentrations ranging from 0.3 to 0.8 mg/kg. The analytical uncertainty of MUSE, incorporating both accuracy and precision, was ≤0.4‰.