Analytical methodologies based on LC–MS/MS for monitoring selected emerging compounds in liquid and solid phases of the sewage sludge

Abstract

In this work, two analytical methodologies based on liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS) were developed for quantification of emerging pollutants identified in sewage sludge after a previous wide-scope screening. The target list included 13 emerging contaminants (EC): thiabendazole, acesulfame, fenofibric acid, valsartan, irbesartan, salicylic acid, diclofenac, carbamazepine, 4-aminoantipyrine (4- AA), 4-acetyl aminoantipyrine (4-AAA), 4-formyl aminoantipyrine (4-FAA), venlafaxine and benzoylecgonine. The aqueous and solid phases of the sewage sludge were analyzed making use of Solid-Phase Extraction (SPE) and UltraSonic Extraction (USE) for sample treatment, respectively. The methods were validated at three concentration levels: 0.2, 2 and 20mg L 1 for the aqueous phase, and 50, 500 and 2000mg kg 1 for the solid phase of the sludge. In general, the method was satisfactorily validated, showing good recoveries (70–120%) and precision (RSD < 20%). Regarding the limit of quantification (LOQ), it was below 0.1mg L 1 in the aqueous phase and below 50mg kg 1 in the solid phase for the majority of the analytes. The method applicability was tested by analysis of samples from a wider study on degradation of emerging pollutants in sewage sludge under anaerobic digestion. The key benefits of these methodologies are: SPE and USE are appropriate sample procedures to extract selected emerging contaminants from the aqueous phase of the sewage sludge and the solid residue. LC–MS/MS is highly suitable for determining emerging contaminants in both sludge phases. Up to our knowledge, the main metabolites of dipyrone had not been studied before in sewage sludge. ã