Batch equilibrium experiments and modeling reveal weak temperature dependence of cyclic volatile methylsiloxane sorption in soil/sediment organic carbon-water systems.

The organic carbon normalized partition coefficient, KOC, describes the equilibrium distribution of a chemical between water and organic carbon in soil or sediment. It is a key parameter in evaluating chemical persistence, mass distribution, and transport using multimedia fate and transport models. Considerable uncertainty remains about the KOC values of cyclic volatile methylsiloxane (cVMS) compounds, and in particular the dependence of KOC on temperature. In this study, we used a batch equilibrium (BE) method to measure KOC values and their temperature dependence between ∼5 and 25 °C for octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) with soil and sediments. Approximate log KOC values at 25 °C were 4.5-5.0 for D4 and 5.5-6.1 for D5 with different sorbents, and decreased by 0.3 log units or less at 4-5 °C. Enthalpies of sorption, ΔHOC, obtained for the different sorbents ranged from +7.2 to +16 kJ mol-1, with average values of +7.9 and +13 kJ mol-1 for D4 and D5, respectively. These values differ in magnitude and direction from those reported elsewhere based on KOC values determined by a novel dynamic purge-and-trap (PnT) method, but are consistent with predictions based on their solvation properties. A new fugacity-based multimedia model incorporating sorption/desorption kinetics was developed and used to predict concentrations in the phases of BE and PnT systems during desorption of cVMS under different experimental and ideal conditions. Model simulations suggested that KOC values for cVMS compounds derived from the PnT systems could be influenced by sorption disequilibrium between water and solids controlled by desorption rates from the particle phase to water, and subsequent losses due to volatilization and degradation. This has the potential to result in overestimation of KOC values when fitting the experimental data of cVMS mass remaining in a PnT system over time, which could explain the observed differences between the methods.

Basic considerations to minimize bias in collection and analysis of volatile methyl siloxanes in environmental samples.

Monitoring studies that aim to quantify volatile methyl siloxanes (VMS) in environmental matrices may encounter a multitude of issues, most of which relate to the unique combination of physical-chemical characteristics of VMS that distinguish them from other classes of organic compounds. These properties, which are critical to their function in various applications, also control their fate and distribution in the environment, as well as the analytical chemistry of their measurement. Polycondensation and rearrangement reactions of VMS oligomers are possible during sample storage and analysis. Thus, care should be exercised to suppress these types of reactions by avoiding any catalytic substances or surfaces in sample collection and analysis equipment. Another factor complicating sample integrity in the analysis of trace levels of VMS, is their ubiquitous presence in many common products and components of instrumentation in the laboratory. For example, some gas chromatography columns and inlet septa have been identified as sources of VMS due to surface-catalyzed transformation of silicones to VMS promoted by moisture under high temperature in some silicone-based GC columns. Possible chemical transformation of the analytes, contamination from other sources, and potential loss of analytes need to be assessed throughout all aspects of the study, from sample collection through analysis, by establishing a rigorous quality assurance and quality control program. The implementation of such a robust QA/QC program facilitates the identification and minimization of potential analytical biases and ensures the validity and usability of data generated from environmental monitoring campaigns for VMS. The objective of this paper is to focus on aspects of collection, processing, and analysis of environmental samples that may influence the quality of the VMS analytical results. This information should then be employed in the design and implementation of future monitoring studies and can used to assess the validity of analytical results from VMS monitoring studies.

Decamethylcyclopentasiloxane (D5) environmental sources, fate, transport, and routes of exposure.

The environmental sources, fate, transport, and routes of exposure of decamethylcyclopentasiloxane (D5; CAS no. 541-02-6) are reviewed in the present study, with the objective of contributing to effective risk evaluation and assessment of this and related substances. The present review, which is part of a series of studies discussing aspects of an effective risk evaluation and assessment, was prompted in part by the findings of a Board of Review undertaken to comment on a decision by Environment Canada made in 2008 to subject D5 to regulation as a toxic substance. The present review focuses on the early stages of the assessment process and how information on D5's physical-chemical properties, uses, and fate in the environment can be integrated to give a quantitative description of fate and exposure that is consistent with available monitoring data. Emphasis is placed on long-range atmospheric transport and fate in water bodies receiving effluents from wastewater treatment plants (along with associated sediments) and soils receiving biosolids. The resulting exposure estimates form the basis for assessments of the resulting risk presented in other studies in this series. Recommendations are made for developing an improved process by which D5 and related substances can be evaluated effectively for risk to humans and the environment.

Determination of soil-water sorption coefficients of volatile methylsiloxanes.

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 using(13)C-enriched sorbates. Sorption and desorption kinetics and isotherms were determined for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), octamethyltrisiloxane (L3), and decamethyltetrasiloxane (L4). Concentrations of [(13)C]-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 (logK(OC)) 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 K(OC) values were systematically greater by 0.1 log units to 0.3 log units. The linear isotherms and low variation in K(OC) values across soils suggested partitioning-dominated sorption of the VMS. Compared with traditional hydrophobic organic compounds, K(OC) 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.

Determination of descriptors for organosilicon compounds by gas chromatography and non-aqueous liquid-liquid partitioning.

Measurements of retention factors by gas chromatography on up to 10 complementary stationary phases at up to 5 temperatures for each stationary phase and liquid-liquid partition coefficients in three biphasic organic solvent systems (n-hexane-acetonitrile, n-heptane-N,N-dimethylformamide and n-heptane-2,2,2-trifluoroethanol) were used to estimate solute descriptors for 54 organosilicon compounds for use in the solvation parameter model. Many of the E descriptor values (electron lone pair interactions) are negative for simple siloxanes and silanes indicating that these compound bind electron lone pairs more tightly than n-alkanes. Silanes and siloxanes with alkyl groups have near zero dipolarity/polarizability (S descriptor). The S descriptor is only modest for simple phenylsilanes, silazanes, silanols, orthosilicates, and alkoxides. All organosilicon compounds with silicon-oxygen bonds are reasonably strong hydrogen-bond bases (B descriptor) but only the silanol group is a reasonably strong hydrogen-bond acid (A descriptor). Silanes (SiH) and silazanes (SiNHSi) are weak hydrogen-bond acids. Cavity formation and dispersion interactions (V or L descriptor) are often the main component of solvation models for siloxanes and silanes that have simple alkyl and aromatic substituents. A number of physicochemical properties (vapor pressure, aqueous solubility, biphasic partition coefficients, sorption coefficients, etc.) for linear and cyclic dimethylsiloxanes can be reliably predicted from their descriptors in established models for organic compounds.