Critical Review and Interpretation of Environmental Data for Volatile Methylsiloxanes: Partition Properties

Volatile methylsiloxanes (VMS) enter the environment through industrial activities and the use of various consumer products. Reliable measurements of environmental partition properties for these compounds are critical for accurate prediction of their environmental fate, distribution, transport, exposure and potential effects. In this study, the measured partition properties including air/water (<i>K</i>_AW), octanol/water (<i>K</i>_OW), and octanol/air partitioning coefficients (<i>K</i>_OA), soil organic carbon/water distribution coefficient (<i>K</i>_OC), and biological medium/fluid partition coefficients, and their temperature dependence were critically reviewed. Based on these results, organosilicon compounds such as methylsiloxanes are expected to behave differently in the environment compared to conventional hydrophobic environmental contaminants, as a result of their inherent characteristics related to molecular size and capacity for different types of molecular interactions that control partitioning. The differences are critical and need to be taken into consideration in environmental exposure and risk analyses of these compounds

Bioconcentration and Aquatic Toxicity of Superhydrophobic Chemicals: A Modeling Case Study of Cyclic Volatile Methyl Siloxanes

Many chemicals in commerce are classified as “superhydrophobic”, having log octanol–water partition coefficients (log <i>K</i>_OW) approaching or exceeding 7. Examples include long-chain alkanes, halogenated aromatics, and cyclic volatile methylsiloxanes (cVMS). We show that superhydrophobic chemicals present unique assessment challenges because of their sparing solubility in water and difficulties in empirical determinations of bioconcentration factors (BCFs) and aquatic toxicity. Using cVMS as an example, BCFs are considerably lower than expected due to biotransformation. Reviewed aquatic toxicity test data for cVMS in a range of aquatic organisms show little or no toxic effects up to solubility limits in water and sediment. Explanations for this apparent lack of toxicity of cVMS, and by extension to other superhydrophobic chemicals, are explored using a conventional one-compartment uptake model to simulate bioconcentration and toxicity tests using an assumed baseline narcotic critical body residue (CBR) and a range of organism sizes. Because of the low aqueous concentrations, equilibration times are very long and BCFs are sensitive to even very slow rates of biotransformation. Most organisms fail to achieve the assumed CBR during feasible test durations even at the solubility limit. Regulatory evaluation of superhydrophobic substances requires specially designed test protocols addressing biotransformation and dietary uptake

Modeling Human Exposure to Indoor Contaminants: External Source to Body Tissues

Information on human indoor exposure is necessary to assess the potential risk to individuals from many chemicals of interest. Dynamic indoor and human physicologically based pharmacokinetic (PBPK) models of the distribution of nonionizing, organic chemical concentrations in indoor environments resulting in delivered tissue doses are developed, described and tested. The Indoor model successfully reproduced independently measured, reported time-dependent air concentrations of chloroform released during showering and of 2-butyoxyethanol following use of a volatile surface cleaner. The Indoor model predictions were also comparable to those from a higher tier consumer model (ConsExpo 4.1) for the surface cleaner scenario. The PBPK model successful reproduced observed chloroform exhaled air concentrations resulting from an inhalation exposure. Fugacity based modeling provided a seamless description of the partitioning, fluxes, accumulation and release of the chemical in indoor media and tissues of the exposed subject. This has the potential to assist in health risk assessments, provided that appropriate physical/chemical property, usage characteristics, and toxicological information are available

Decabrominated Diphenyl Ethers (BDE-209) in Chinese and Global Air: Levels, Gas/Particle Partitioning, and Long-Range Transport: Is Long-Range Transport of BDE-209 Really Governed by the Movement of Particles?

In this paper, we report air concentrations of BDE-209 in both gas- and particle-phases across China. The annual mean concentrations of BDE-209 were from below detection limit (BDL) to 77.0 pg·m^–3 in the gas-phase and 1.06–728 pg·m^–3 in the particle-phase. Among the nine PBDEs measured, BDE-209 is the dominant congener in Chinese atmosphere in both gas and particle phases. We predicted the partitioning behavior of BDE-209 in air using our newly developed steady state equation, and the results matched the monitoring data worldwide very well. It was found that the logarithm of the partition quotient of BDE-209 is a constant, and equal to −1.53 under the global ambient temperature range (from −50 to +50 °C). The gaseous fractions of BDE-209 in air depends on the concentration of total suspended particle (TSP). The most important conclusion derived from this study is that, BDE-209, like other semivolatile organic compounds (SVOCs), cannot be sorbed entirely to atmospheric particles; and there is a significant amount of gaseous BDE-209 in global atmosphere, which is subject to long-range atmospheric transport (LRAT). Therefore, it is not surprising that BDE-209 can enter the Arctic through LRAT mainly by air transport rather than by particle movement. This is a significant advancement in understanding the global transport process and the pathways entering the Arctic for chemicals with low volatility and high octanol–air partition coefficients, such as BDE-209

Assessing the Fate of an Aromatic Hydrocarbon Fluid in Agricultural Spray Applications Using the Three-Stage ADVOCATE Model Framework

Components of emulsifiable concentrates (ECs) used in pesticide formulations may be emitted to air following application in agricultural use and contribute to ozone formation. A key consideration is the fraction of the ECs that is volatilized. This study is designed to provide a mechanistic model framework for estimating emissions of an aromatic hydrocarbon fluid used in ECs based on the results of spray chamber experiments that simulate fate as the fluids become subject to volatilization, sorption to soil, and biodegradation. The results indicate the need to treat the volatilization losses in three stages: (i) losses during spraying, (ii) losses up to 12 h after spraying in which the soil is coated with the ECs, and (iii) subsequent longer term losses in which the ECs become increasingly sorbed and subject to biodegradation. A mass balance model, the agrochemical derived volatile organic compound air transfer evaluation (ADVOCATE) tool, is developed, treating the ECs as seven hydrocarbon component groups, to estimate the volatilization and biodegradation losses using parameters fitted to empirical data. This enables losses to be estimated for each hydrocarbon component under field conditions, thereby providing a basis for improved estimation of ozone formation potential and for designing ECs that have lower emissions