The sorption behaviors of 4 cyclic and linear volatile methyl siloxane (VMS) compounds between water and organic matter in 3 United Kingdom soils were studied by a batch equilibrium method using13C-enriched sorbates. Sorption and desorption kinetics and isotherms were determined for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), octamethyltrisiloxane (L3), and decamethyltetrasiloxane (L4). Concentrations of [13C]-VMS in the soil and aqueous phases were measured directly by extraction and gas chromatography–mass spectrometry techniques. All VMS compounds were sorbed rapidly, reaching constant distributions in all soils by 24 h. Desorption kinetics were very rapid, with reattainment of equilibrium within 1 h. In the main, linear isotherms were observed for aqueous concentrations at or below 4% of the solubility limits. The average sorption organic carbon partition coefficient (log KOC) values across soils were 4.23 for D4, 5.17 for D5, 4.32 for L3, and 5.13 for L4, with standard deviations of 0.09 to 0.34. Desorption KOC values were systematically greater by 0.1 log units to 0.3 log units. The linear isotherms and low variation in KOC values across soils suggested partitioning-dominated sorption of the VMS. Compared with traditional hydrophobic organic compounds, KOC values for the VMS compounds were significantly lower than expected on the basis of their octanol–water partition coefficients. A linear free energy relationship analysis showed that these differences could be rationalized quantitatively in terms of the inherent characteristics of the VMS compounds, combined with the differences in solvation properties of organic matter and octanol. Environ Toxicol Chem 2014; 33:1937–1945.
The trophic transfer of cyclic methylsiloxanes (cVMS) in aquatic ecosystems is an important criterion for assessing bioaccumulation and ecological risk. Bioaccumulation and trophic transfer of cVMS, specifically octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), were evaluated for the marine food webs of the Inner and Outer Oslofjord, Norway. The sampled food webs included zooplankton, benthic macroinvertebrates, shellfish, and finfish species. Zooplankton, benthic macroinvertebrates, and shellfish occupied the lowest trophic levels (TL ≈2 to 3); northern shrimp (Pandalus borealis) and Atlantic herring (Clupea harengus) occupied the middle trophic levels (TL ≈3 to 4), and Atlantic cod (Gadus morhua) occupied the highest tropic level (TL>4.0). Trophic dynamics in the Oslofjord were best described as a compressed food web defined by demersal and pelagic components that were confounded by a diversity in prey organisms and feeding relationships. Lipid-normalized concentrations of D4, D5, and D6 were greatest in the lowest trophic levels and significantly decreased up the food web, with the lowest concentrations being observed in the highest trophic level species. Trophic magnification factors (TMF) for D4, D5, and D6 were <1.0 (range 0.3 to 0.9) and were consistent between the Inner and Outer Oslofjord, indicating that exposure did not impact TMF across the marine food web. There was no evidence to suggest biomagnification of cVMS in the Oslofjord. Rather, results indicated that trophic dilution of cVMS, not trophic magnification, occurred across the sampled food webs.
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