Volatile methylsiloxanes (VMS) have been identified as contaminants of emerging concern in aquatic systems. Here, we report on the presence of VMS in sediment and wastewater from Arctic regions in 2014 to 2016 and model their persistence in Adventfjorden in Longyearbyen, Svalbard. Total concentrations of VMS in sediment were dominated by D₄ and D₅ and ranged from 0.0024 to 1.7 ng g⁻¹ at Svalbard (Longyearbyen), from 4.0 to 43 ng g⁻¹ in Greenland (Nuuk) and from 0.19 to 21 ng g⁻¹ in the Canadian Archipelago. Concentrations in wastewater samples from Svalbard ranged from 12 to 156 ng L⁻¹. Large variability in reported values of the partition ratio between organic carbon and water (K_OC) and enthalpy of sorption (ΔH_OC; often estimated from enthalpy of phase change between octanol and water, ΔH_OW) of VMS has resulted in high uncertainty in evaluating persistence in aquatic systems. We evaluated previously reported K_OC and ΔH_OC values from the literature in predicting measured VMS concentrations in sediment and wastewater in scenarios using a fugacity-based multimedia model for VMS concentrations in Svalbard. We tested two different model scenarios: (1) K_OC and ΔH_OW measurements for three cyclic VMS previously reported by Kozerski et al. (Environ. Toxicol. Chem., 2014, 33, 1937–1945) and Xu and Kropscott (Environ. Chem., 2014, 33, 2702–2710) and (2) the K_OC and ΔH_OC measurements from Panagopoulos et al. (Environ. Sci. Technol., 2015, 49, 12161–12168 and Environ. Sci. Technol. Lett., 2017, 4(6), 240–245). Concentrations of VMS in sediment predicted from concentrations in wastewater in scenario 2 were in good agreement with measured concentrations, whereas in scenario 1, predicted concentrations were 2 to 4 orders of magnitude lower. Such large discrepancies indicate that the differences in the predicted concentrations are more likely to be attributed to K_OC and ΔH_OC than to uncertainty in environmental parameters or emission rates.