Influence of pre-treatment process on matrix effect for the determination of musk fragrances in fish and mussel

•For the first time a QuEChERS method was developed for the analysis of fish samples.•PLE and QuEChERS methods were compared for the analysis of musk fragrances in fish samples.•Different clean-up strategies to reduce the matrix effect in fish extracts were assayed.•Developed methods provide limits of detection and quantification at low ng g−1 (d.w.).•Galaxolide and tonalide were found at ng g−1 levels in all the fish samples analysed.

Musk compounds are widely used as fragrances in personal care products. On account of their widespread use and their low biodegradation, they can be found in environmental samples. In our study two extraction methodologies were compared and different clean-up strategies were also studied in order to develop a reliable analytical method, with minimum matrix effect and good detection limits, to determine synthetic musk fragrances- six polycyclic musks, three nitro musks and the degradation product of one polycyclic musk- in fish and mussel samples. The first extraction technique involves a QuEChERS extraction, a consolidate extraction methodology in the field of food analysis of growing interest over recent years, followed by a dispersive solid-phase extraction (dSPE) as clean-up strategy. The second extraction technique consists of a conventional pressurised liquid extraction (PLE) with dichloromethane and an in-cell clean-up to decrease the matrix effect and remove the undesired components⁎present in PLE extracts. Large volume injection (LVI) followed by gas chromatography-ion trap-tandem mass spectrometry (GC-IT-MS/MS) was chosen as the separation and detection technique. Validation parameters, such as method detection limits and method quantification limits were found at ng g−1 levels for both fish and mussel matrices. Good levels of intra-day and inter-day repeatabilities were obtained analysing fish and mussel samples spiked at 50 ng g−1 (d.w.) (n=5, RSDs<17%). The developed PLE/GC-IT-MS/MS method was successfully applied to determine the target musk fragrances present in fish and mussel samples from the local market in Tarragona and fish samples from the Ebro River. The results showed the presence of galaxolide (2.97–18.04 ng g−1 (d.w.)) and tonalide (1.17–8.42 ng g−1 (d.w.)) in all the samples analysed, while the remaining polycyclic musks such as cashmeran, celestolide and phantolide, were only detected in some of the fish samples analysed. None of the samples analysed contained detectable traces of the nitro musks studied.

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