A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography - mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of 04, 05, and D6 in influents to the 11 WWTPs were in the range 0.282-6.69 mu g L-1, 7.75-135 mu g(-1), and 1.53-26.9 mu g L-1, respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009-0.045 mu g L-1, <0.027-1.56 mu g L-1, and <0.022-0.093 mu g L-1, respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009-0.023 mu g L-1, <0.027-1.48 mu g L-1, and <0.022-0.151 mu g L-1 for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003-0.049 mu g g(-1) dw, and 0.011-5.84 mu g g(-1) dw, and 0.004-0.371 mu g g(-1) dw for 04, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008-0.017 mu g g(-1) dw, <0.007-0.221 mu g g(-1) dw, and <0.009-0.711 mu g g(-1) dw for 04, D5, and 06, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.