UC Berkeley

Humans spend most of their time indoors, in residences and commercial buildings. In this thesis, I evaluate exposures to volatile (VOCs) and semivolatile organic compounds (SVOCs) in indoor environments. I use a combination of literature review and evaluation, mechanistic modeling, and skin-wipe collection and analysis to develop an understanding of the role of indoor air as an exposure medium for inhalation and passive dermal uptake of pollutants. This dissertation explores three related research topics on indoor environments and human exposures. In Chapter 2, I conduct a comprehensive review of reported measurements of pollutants found in commercial buildings. I used the literature review to estimate concentration ranges that can be compared to health-based exposure limits as basis for hazard assessment. I use the regulatory exposure limits set by government agencies to calculate hazard indices as the ratio of observed concentrations to regulatory standards. I also compare the odor and pungency thresholds of individual pollutants to observed concentrations to evaluate their potential to exceed odor thresholds. The hazard evaluation identifies the potential for health impacts at concentrations commonly found in commercial buildings. This analysis focuses exclusively on VOCs and SVOCs in commercial buildings and identified a limited set of pollutants that pose health concerns. I also characterize the selected pollutants in terms of the chemical properties that,affect partitioning to various indoor surfaces, and subsequently their fate and transport in indoor environments. Based on chemical properties and indoor fate, I grouped the pollutants into five groups. I use an hierarchical k-means analysis based on octanol-air partitioning coefficient, octanol-water partitioning coefficient, air-water partitioning coefficient, and molecular weight. The pollutants in each group are expected to behave similarly in indoor environments.

In Chapter 3, I evaluate the role of buildings operation parameters such as ventilation and filtration in limiting exposures to pollutants originating from indoor and outdoor sources. I use a simple well-mixed-air model of an indoor space to study the impact of ventilation on concentrations of ozone, nitrogen dioxide, carbon monoxide, and radon. I employ a chemical-thermodynamics-(fugacity)-based mass balance model in conjunction with a particle mass balance to study the fate and transport of particulate matter, VOCs, and SVOCs. The fugacity mass balance model accounts for chemical partitioning among air, air-borne particles, and indoor surfaces. I ran the fugacity model with indoor and outdoor source of VOCs and SVOCs and indoor and outdoor sources of particulate matter. I evaluate the consequent inhalation exposures these sources with two outcome metrics, intake fraction (iF) for indoor sources and indoor/outdoor concentration ratio for outdoor sources. The exposure to particulate matter of indoor and outdoor origin was evaluated using the outcome metrics iF and the indoor proportion of outdoor particles (iPOP). The model evaluation shows that ventilation is most effective at controlling exposures to VOCs that have an indoor source. Filtration is seen to be effective at controlling exposures to particulate matter and SVOCs that partition preferentially onto particulate matter.

In Chapter 4, I explore the role of indoor air in delivering SVOCs to human occupants through passive dermal uptake. I collected wipe samples from thirteen subjects who were randomly chosen. For each subject, I collected three sequential wipe samples from the forehead and one sample from the palm. I analyzed the samples for a suite of SVOCs and skin lipids (squalene and sapienic acid) in an analytical laboratory using gas chromatography and liquid chromatography. All forehead wipe samples contained SVOCs indicating that air to skin transfer of pollutants for passive dermal uptake could be a significant exposure pathway for SVOCs. Because skin lipid concentrations decrease with depth the quantitation of skin lipid concentrations from each wipe allowed me to estimate the depth of sampling by each skin wipe. This is the first study to quantitatively evaluate the depth of sampling by skin wipes. I use the experimental results together with a theoretical model to explore the potential role of skin as a passive sampler for short-term personal exposures, indoors. For this I develop a metric called the equivalent time of exposure (ETE) to study the usefulness of sequential skin wipe samples as a passive sampler. I used partitioning coefficients from air to skin surface, combined with a dynamic skin mass transport model, to study the theoretical transport of pollutant through the stratum corneum. I compare the modeled concentrations to measured concentrations, at comparable depths. The ETE is the amount of time to which the subject would have to be exposed to a constant air concentration to attain the observed skin-wipe concentration depth profile in the stratum corneum. Based on the ETE, I find that skin wipe samples could be indicative of exposures up to 6 hours prior to wipe sampling, depending on the diffusion coefficient of the pollutant.

The overarching goal of this research is to evaluate the role of indoor air in mediating the transfer to human receptors of pollutants released indoors or brought indoors from outdoor sources. The indoor air mass controls the fate and transport of pollutants in indoor spaces, and the rate of delivery of pollutants for inhalation and dermal uptake. The research highlights the important role of air-to-surface and air-to-particle partitioning in facilitating or mitigating source-receptor relationships. The work illustrates future research opportunities for tracking the complex web of indoor/outdoor pathways that bring pollutants into the human environment and into the blood and other viable tissues of the human population.