Optimization and validation of solvent and supercritical-fluid extractions for the trace-determination of polycyclic aromatic hydrocarbons in sewage sludges by liquid chromatography coupled to diode-array and fluorescence detection

Abstract

There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural land. Inorganic pollutants are regularly controlled, but organic pollutants have received little attention up to now. The main problem for trace analysis of organic pollutants comes from the complexity of the various matrices of sludges, which depends on their origins. Therefore, methods described for soils and sediments cannot be directly applied to sludges which contain high amount of lipids. This paper provides a method for trace-determination of polycyclic aromatic hydrocarbons in the range of mg/kg of dried sludge including an extraction step, and an analysis step by liquid chromatography with fluorescence detection for sensitive quantification and UV–diode-array detection for confirmation. The extraction step was optimized by a selection of the solvent used for both Soxhlet and supercritical-fluid extraction and by setting the experimental conditions (temperature, pressure, modifier, etc.) used for SFE. Extraction recoveries were found similar and quantitative for the two procedures. However supercritical-fluid extraction appears to be a good alternative to Soxhlet extraction because of the consumption of less time and solvent. Detection limits were obtained in the range of 0.1–1 mg/kg of dried sludges, with possible confirmation by UV spectra. The whole method (extraction/quantification/confirmation) was validated using sludges which have been certified by the Community Bureau of Reference from Brussels (CRM No. 088). Application to the determination of PAHs in urban sludges is presented.