Steven S. Cox

Measuring partition and diffusion coefficients for volatile organic compounds in vinyl flooring

Interactions between volatile organic compounds (VOCs) and vinyl flooring (VF), a relatively homogenous, diffusion-controlled building material, were characterized. The sorption/desorption behavior of VF was investigated using single-component and binary systems of seven common VOCs ranging in molecular weight from n-butanol to n-pentadecane. The simultaneous sorption of VOCs and water vapor by VF was also investigated. Rapid determination of the material/air partition coefficient (K) and the material-phase diffusion coefficient (D) for each VOC was achieved by placing thin VF slabs in a dynamic microbalance and subjecting them to controlled sorption/desorption cycles. K and D are shown to be independent of concentration for all of the VOCs and water vapor. For the four alkane VOCs studied, K correlates well with vapor pressure and D correlates well with molecular weight, providing a means to estimate these parameters for other alkane VOCs. While the simultaneous sorption of a binary mixture of VOCs is non-competitive, the presence of water vapor increases the uptake of VOCs by VF. This approach can be applied to other diffusion-controlled materials and should facilitate the prediction of their source/sink behavior using physically-based models.

Measuring Concentrations of Volatile Organic Compounds in Vinyl Flooring

ABSTRACT The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics. To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m2 section of new VF was punched randomly to produce ~200 0.78-cm2 disks. The disks were milled to a powder at -140 °C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatog-raphy/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 |ig/g VF for n-hexadecane to 130 |Jg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix.

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.

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.

Barrier materials to reduce contaminant emissions from structural insulated panels

Publisher Summary The use of Structural Insulated Panels (SIPs) to create very tight building envelopes helps reducing the environmental impact and energy use of new housing. Typically, SIPs are constructed from oriented strand board (OSB) and rigid foam in multilayered sandwich-like structures. Although environmental and energy advantages make panelized systems very attractive, the tighter building envelopes may result in degraded indoor air quality. The potential release of volatile contaminants from SIPs must also be considered to ensure the reduced energy use. A physically based diffusion model that predicts emissions from a single layer of vinyl flooring has recently been developed and successfully validated. A logical extension of this approach is to apply the model to predict emissions from multilayer systems such as SIPs. A double-layer model is developed to predict the rate of mass transfer from double-layered building material to indoor air. It is assumed that the two layers are flat homogeneous slabs, that internal mass transfer is governed by diffusion, and that the indoor air is well mixed. An analytical solution to the double-layer model is presented and used to demonstrate the potential for a thin surface barrier layer to reduce contaminant emission rates from building materials.