Determination of cyclic volatile methylsiloxanes in water, sediment, soil, biota, and biosolid using large-volume injection–gas chromatography–mass spectrometry

Abstract Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid–solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection–gas chromatography−mass spectrometry (LVI−GC−MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI–GC–MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS’s associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4 °C were stable within 29 d; however, significant depletion of D6 (60–70%) occurred only after 3 d. Whereas cVMS in sewage influent and effluent were stable at 4 °C within 21 d. cVMS in sediment sealed in amber glass jars at −20 °C and in pentane extracts in vials at −15 °C were stable during 1 month under both storage conditions.