Monitoring and modelling of siloxanes in a sewage treatment plant in the UK

Monitoring of cyclic volatile methylsiloxanes (cVMS) carried out at Anglian Water’s Broadholme sewage treatment plant (STP) is described. The method deployed used headspace gas chromatography/mass spectrometry (HS-GC/MS) and the addition of isotopically labelled cVMS to correct for partitioning in samples containing high levels of particulate and dissolved organic carbon. The method was capable of measuring cVMS in raw sewage samples, with recoveries of 80%, 85% and 71% respectively, for D₄, D₅ and D₆. The limit of quantification was 0.2 μg L⁻¹ for all three substances. Recoveries close to 100% were observed for all cVMS spiked into treated effluent (LOQ = 0.01 μg L⁻¹). Despite the volatile nature of cVMS and its ubiquitous presence in the ambient atmosphere, the methods deployed showed excellent recoveries, reproducibility and quantification limits. A distinct diurnal variation in cVMS concentration, probably linked with the use of personal care products was observed for raw sewage but not in treated sewage effluent. The estimated per capita consumption of D₅ (∼2.7 mg cap⁻¹ d⁻¹) derived for the population served by this plant was significantly lower than that derived in the Environment Agency (UK) risk assessment (11.6 mg cap⁻¹ d⁻¹). The cVMS were highly removed during sewage treatment with efficiencies greater than 98%. The methods and findings of this pilot study can be used as the basis for future studies on the fate of cVMS substances in STPs.