Volatile dimethylsiloxanes in market seafood and freshwater fish from the Xúquer River, Spain

Volatile dimethylsiloxanes are a family of synthetic organosilicon-compounds, which have received rising attention because of their widespread use and occurrence in the environment. In the present work, an analytical method based on ultrasound-assisted solid-liquid extraction (USAE) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) has been optimized and applied to assess the presence of eight volatile dimethyl siloxanes (VMS) (hexamethylcyclotrisiloxane (D3), octamethylcyclotetra-siloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), octamethyltrisiloxane (MDM), decamethyltetrasiloxane (MD2M) and dodecamethylpentasiloxane (MD3M) and tetradecamethylhexasiloxane (MD4M)) in fish. The optimized method presented limits of quantification between 0.1 and 1.3 pg/g for linear volatile dimethylsiloxanes (lVMS) and between 13 and 39 pg/g for cyclic volatile dimethylsiloxanes (cVMS) and intraday relative standard deviation (between 1.9 and 7.0%). Recovery yields were between 71 and 92%. 40 fish samples collected in different markets in Barcelona, (Spain), and 16 samples of fish directly collected at the Xúquer River were analysed. cVMS were detected in almost all the river fish samples at concentrations between pg/g and ng/g, with a significant correlation between the fat content and VMS concentrations in fish. In addition, significant higher concentrations were found in market samples, suggesting sources of contamination from their manipulation and storage in indoor environments. Multivariate analyses were applied to the results and the siloxane profiles and analyte correlations are discussed.