Influence of matrix on suitability of four methods for organochlorine pesticide analysis in waters

Abstract

The monitoring of organochlorine pesticides has raised a great concern in the last years due to their toxicity (some of them are carcinogenic and endocrine disruptor compounds) and persistence. European Directive 2008/105/EC establishes very restrictive levels for organochlorine pesticides in surface waters. Therefore, simple, fast, highly sensitive and low cost analytical methods are required to detect and quantify these pollutants in water. In the present work, four procedures for extraction and determination are proposed and compared for the analysis of 28 organochlorine pesticides in tap, surface and sea waters. The suitability of each method of analysis was evaluated for each kind of water. The extraction methods proposed were: two solid-phase extraction methods using C₁₈ laminar disk and Oasis HLB cartridges, a solid-phase microextraction procedure using a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre, and a micro liquid–liquid extraction procedure using ethyl acetate as solvent. Determination of pesticides was performed by large volume on-column injector-gas chromatography-electron capture detection (LVOCI-GC-ECD), splitless-GC-ECD and GC-MS (mass spectrometry). All methods present a good sensitivity with method detection limits lower than 10 ng L⁻¹, good accuracy with recoveries between 75 and 120% (with some exceptions) and good precision (relative standard deviations <15%), according to the Commission Decision 2002/657/EC criteria. The advantages and disadvantages of each method are discussed in terms of the green chemistry principles, the figures of merit and the matrix effect. This work tries to be a useful guidance for routine and control analysis laboratories.

Keywords:

• POPs
• solid-phase extraction
• solid-phase microextraction
• micro liquid–liquid extraction
• Green Chemistry

Acknowledgements

This work was financially supported by Xunta de Galicia: project (09MDS038103PR) and ‘Program of Consolidation and structuring of competitive research groups in the Universitary system of Galicia’.