Adsorption of Phthalates on Impervious Indoor Surfaces.

Sorption of semivolatile organic compounds (SVOCs) onto interior surfaces, often referred to as the "sink effect", and their subsequent re-emission significantly affect the fate and transport of indoor SVOCs and the resulting human exposure. Unfortunately, experimental challenges and the large number of SVOC/surface combinations have impeded progress in understanding sorption of SVOCs on indoor surfaces. An experimental approach based on a diffusion model was thus developed to determine the surface/air partition coefficient K of di-2-ethylhexyl phthalate (DEHP) on typical impervious surfaces including aluminum, steel, glass, and acrylic. The results indicate that surface roughness plays an important role in the adsorption process. Although larger data sets are needed, the ability to predict K could be greatly improved by establishing the nature of the relationship between surface roughness and K for clean indoor surfaces. Furthermore, different surfaces exhibit nearly identical K values after being exposed to kitchen grime with values that are close to those reported for the octanol/air partition coefficient. This strongly supports the idea that interactions between gas-phase DEHP and soiled surfaces have been reduced to interactions with an organic film. Collectively, the results provide an improved understanding of equilibrium partitioning of SVOCs on impervious surfaces.

Transformation of Cerium Oxide Nanoparticles from a Diesel Fuel Additive during Combustion in a Diesel Engine.

Nanoscale cerium oxide is used as a diesel fuel additive to reduce particulate matter emissions and increase fuel economy, but its fate in the environment has not been established. Cerium oxide released as a result of the combustion of diesel fuel containing the additive Envirox, which utilizes suspended nanoscale cerium oxide to reduce particulate matter emissions and increase fuel economy, was captured from the exhaust stream of a diesel engine and was characterized using a combination of bulk analytical techniques and high resolution transmission electron microscopy. The combustion process induced significant changes in the size and morphology of the particles; ∼15 nm aggregates consisting of 5-7 nm faceted crystals in the fuel additive became 50-300 nm, near-spherical, single crystals in the exhaust. Electron diffraction identified the original cerium oxide particles as cerium(IV) oxide (CeO2, standard FCC structure) with no detectable quantities of Ce(III), whereas in the exhaust the ceria particles had additional electron diffraction reflections indicative of a CeO2 superstructure containing ordered oxygen vacancies. The surfactant coating present on the cerium oxide particles in the additive was lost during combustion, but in roughly 30% of the observed particles in the exhaust, a new surface coating formed, approximately 2-5 nm thick. The results of this study suggest that pristine, laboratory-produced, nanoscale cerium oxide is not a good substitute for the cerium oxide released from fuel-borne catalyst applications and that future toxicity experiments and modeling will require the use/consideration of more realistic materials.

Developing a reference material for diffusion-controlled formaldehyde emissions testing.

Formaldehyde, a known human carcinogen and mucous membrane irritant, is emitted from a variety of building materials and indoor furnishings. The drive to improve building energy efficiency by decreasing ventilation rates increases the need to better understand emissions from indoor products and to identify and develop lower emitting materials. To help meet this need, formaldehyde emissions from indoor materials are typically measured using environmental chambers. However, chamber testing results are frequently inconsistent and provide little insight into the mechanisms governing emissions. This research addresses these problems by (1) developing a reference formaldehyde emissions source that can be used to validate chamber testing methods for characterization of dynamic sources of formaldehyde emissions and (2) demonstrating that emissions from finite formaldehyde sources can be predicted using a fundamental mass-transfer model. Formaldehyde mass-transfer mechanisms are elucidated, providing practical approaches for developing diffusion-controlled reference materials that mimic actual sources. The fundamental understanding of emissions mechanisms can be used to improve emissions testing and guide future risk reduction actions.

Predicting the emission rate of volatile organic compounds from vinyl flooring.

A model for predicting the rate at which a volatile organic compound (VOC) is emitted from a diffusion-controlled material is validated for three contaminants (n-pentadecane, n-tetradecane, and phenol) found in vinyl flooring (VF). Model parameters are the initial VOC concentration in the material phase (C0), the material/air partition coefficient (K), and the material-phase diffusion coefficient (D). The model was verified by comparing predicted gas-phase concentrations to data obtained during small-scale chamber tests and by comparing predicted material-phase concentrations to those measured at the conclusion of the chamber tests. Chamber tests were conducted with the VF placed top-side-up and bottom-side-up. With the exception of phenol and within the limits of experimental precision, the mass of VOCs recovered in the gas-phase balances the mass emitted from the material phase. The model parameters (C0, K, and D) were measured using procedures completely independent of the chamber test. Gas- and material-phase predictions compare well to the bottom-side-up chamber data. The lower emission rates for the top-side-up orientation may be explained by the presence of a low-permeability surface layer. The sink effect of the stainless steel chamber surface was shown to be negligible.