Analytical pyrolysis of poly(dimethylsiloxane) and poly(oxyethylene) siloxane copolymers. Application to the analysis of sewage sludges

Abstract

Dimethicone (poly(dimethylsiloxane), PDMS) and its copolymers bearing a poly(ethylene glycol) (PEG) side chain (PEG-12 dimethicone and PEG-8 dimethicone) are utilised as ingredients in personal care products. These materials along with bis-PEG-18 methyl ether dimethyl silane were analysed by Py-GC–MS. The pyrolysates of dimethicone was dominated by cyclic dimethyl siloxanes from D3 to over D10. Besides Dn, the pyrolysates of PEG-dimethicone were featured by the presence of linear dimethyl siloxanes Ln. Hydroxylated siloxanes were also tentatively identified. Pyrograms were also characterised by PEG oligomers with different terminal groups (hydroxyl, ethyl, ethenyl). The molecular structure of pyrolysis products from the combined structural units of PDMS and PEG could not be assigned. Internal standard calibration protocols using pyrolysis products of PEG-12 dimethicone (L6, L8, L9, and triethyleneglycol monoethyl ether) exhibited satisfactory linearity (R2 > 0.992) in the 0.75−58 μg range and repeatability (RSD < 15 %). Three samples of dried sewage sludge from a municipal water treatment plant were extracted with tetrahydrofuran and the extracts analysed by Py-GC–MS. The pyrograms were characterised by intense signals due to the lipid matrix (hydrocarbons, fatty acids, steranes, sterenes, sterols). Dn and Ln were identified indicative for the presence of siloxanes at levels around 60−290 μg gdw−1, while pyrolytic markers of PEG were not revealed. The recovery of PEG-12 dimethicone (17 μg) in spiked sample was 76 %. Galaxolide, galaxolide lactone and triclosan were identified in the pyrograms. The results of this study evidenced the potential of Py-GC–MS as a screening tool for the determination of cosmetic ingredients in sewage sludge.