abstract: United States Environmental Protection Agency (USEPA) had identified and recommended air quality monitoring to take place at 63 schools throughout the country. Unfortunately, tribal schools were not considered during the time USEPA conducted the analysis. The importance of identifying any air toxic pollutants affecting school children needs to be analyzed. Conducting an air monitoring toxic analysis on the Navajo Nation at Church Rock Elementary School, Church Rock, New Mexico (CRNM) was carried out. The current school location posed a concern, in regards to the surrounding stationary, mobile, and natural emissions emitted all types of toxic pollutants. USEPA sponsors various air monitoring program, which Tribal Air Monitoring Support (TAMS) program undertook, and offered tribal programs, organizations or agencies to utilized air monitoring equipment's. The air monitoring setup was conducted with the contract Eastern Research Group, Inc. (ERG) laboratory, where collection of 24-hour ambient air samples for 60 days on a 6-day sampling interval were performed. The analysis for volatile organic compounds (VOCs)were collected from canister samples using USEPA Compendium Method TO-15, polycyclic aromatic hydrocarbons (PAHs) from polyurethane foam (PUF) and XAD-2 resin samples using USEPA Compendium Method TO-13A. Carbonyl compounds were collected by sorbent cartridge samples using USEPA Compendium Method TO-11A, and trace of metals from filters were sampled using USEPA Compendium Method IO-3.5 and FEM EQL-0512-202. A total of 53 VOC concentrations were greater than 1 μg/m3, where dichlorodifluoromethane, trichlorofluoromethane, chloromethane, dichloromethane, propylene, toluene, acrolein and acetylene were detected. A total of 23 carbonyl compound concentrations were greater than 1 μg/m3, where acetone and formaldehyde were measured. Naphthalene average with the highest average for PAHs, where phenanthrene and retene were the second and third highest averages. As for the metals the highest averages resulted from manganese, chromium and lead. Overall, the air toxic pollutants resulted from CRNM surrounding monitoring site were detected. Identifying the potential emitter source or sources cannot be assessed. / Dissertation/Thesis / Masters Thesis Engineering 2015

Benzene, toluene, ethylbenzene, and xylenes (BTEX) are hazardous air pollutants commonly found in outdoor air. Several studies have explored the potential of vegetation to mitigate BTEX in outdoor air, but they are limited to a northern temperate climate and present conflicting results. To investigate this issue in a subtropical climate, we deployed passive air samplers for two weeks in parks and nearby residences at four locations: three in an urban area and one in a rural area in Alabama, USA. All BTEX concentrations were below health-based guidelines and were comparable to those found in several other studies in populated settings. Concentrations of TEX, but not benzene, were 3-39% lower in parks than at nearby residences, and the differences were significant. In and around two of the parks, toluene:benzene ratios fell outside the range expected for vehicular emissions (p<0.01), suggesting that there are additional, industrial sources of benzene near these two locations. The ratio of m-,p-xylene:ethylbenzene was high at all locations except one residential area, indicating that BTEX were freshly emitted. Concentrations of individual BTEX compounds were highly correlated with each other in most cases, except for locations that may be impacted by nearby industrial sources of benzene. Results of this study suggest that parks can help reduce BTEX exposure by a modest amount, but future research is needed to ascertain this potential through more measurements at higher spatial and temporal resolution and analysis of vegetation for evidence of uptake of BTEX. / Master of Science / Benzene, toluene, ethylbenzene, and xylenes (BTEX) compose a significant fraction of anthropogenic non-methane organic gases in the atmosphere. These compounds are harmful to human health and are precursors to secondary organic aerosol and ozone. Several chamber studies have demonstrated that plants can reduce exposure to BTEX in indoor environments, but, to the best of our knowledge, no study has identified this effect in ambient air. To investigate this issue, we sampled for two weeks in parks and nearby residences at four locations; three were in the city of Birmingham, Alabama, and one was in the rural city of Camden, Alabama. All BTEX concentrations were below health-based guidelines and were comparable to those found in several other studies in urban and rural settings. TEX levels were lower in parks compared to residential areas, and the difference was significant. BTEX were attributable to vehicular emissions in the Camden site and one Birmingham site. In the other two Birmingham sites, there were likely additional, industrial sources of benzene. Future research should investigate the effect of different types of vegetation between parks and explore seasonal cycles in vegetation.

Hazardous air pollutants (HAP’s) are assumed to act without threshold meaning any level of exposure can theoretically initiate the carcinogenic process. With approximately 57,000 new cancer diagnoses and 25,900 deaths predicted in Ontario in 2006, the implications of lifetime low dose cumulative exposure to HAP’s in the etiology of cancer is unknown, yet may be significant. As such, this burden of disease (BoD) model was designed to provide a comprehensive assessment of the current and future BoD attributable to long term cumulative exposure to six carcinogenic HAP’s in two highly exposed regions of Ontario, using a summary measure of population health, disability-adjusted life years (DALY’s). Results indicated a total of 32,074 DALY’s were lost in Toronto and Southwestern Ontario (SWO) from six cancer sites in 2001, with the largest burden from cancers of the lung, followed by lymphomas, then leukemia. Approximately 0.58% of the burden (187 DALY’s) was attributable to current HAP exposures, with the largest health impacts associated with exposure to nickel refinery dusts in SWO (8.91 DALY’s) and benzene in Toronto (46.30 DALY’s). The model predicted 0.3% of the exposure attributable BoD (96 DALY’s) could be avoided in the future if ambient exposures were reduced to a feasible distribution. If ambient exposures were further reduced to levels expected if there were no anthropogenic releases, the model predicts 147 DALY’s could be avoided, such that only 0.12% of the total BoD would be attributable to natural sources of HAP’s. Results of the sensitivity analysis support the notion of the DALY as a robust measure to estimate exposure attributable health impacts, as the incorporation of alternative value choices had negligible impact on the relative importance of cancer sites, or exposures to the total BoD. Results of the model can be used by decision makers to inform public health policy regarding abatement priorities of HAP’s in Ontario, on the basis associated health impacts.

Hazardous air pollutants (HAP’s) are assumed to act without threshold meaning any level of exposure can theoretically initiate the carcinogenic process. With approximately 57,000 new cancer diagnoses and 25,900 deaths predicted in Ontario in 2006, the implications of lifetime low dose cumulative exposure to HAP’s in the etiology of cancer is unknown, yet may be significant. As such, this burden of disease (BoD) model was designed to provide a comprehensive assessment of the current and future BoD attributable to long term cumulative exposure to six carcinogenic HAP’s in two highly exposed regions of Ontario, using a summary measure of population health, disability-adjusted life years (DALY’s). Results indicated a total of 32,074 DALY’s were lost in Toronto and Southwestern Ontario (SWO) from six cancer sites in 2001, with the largest burden from cancers of the lung, followed by lymphomas, then leukemia. Approximately 0.58% of the burden (187 DALY’s) was attributable to current HAP exposures, with the largest health impacts associated with exposure to nickel refinery dusts in SWO (8.91 DALY’s) and benzene in Toronto (46.30 DALY’s). The model predicted 0.3% of the exposure attributable BoD (96 DALY’s) could be avoided in the future if ambient exposures were reduced to a feasible distribution. If ambient exposures were further reduced to levels expected if there were no anthropogenic releases, the model predicts 147 DALY’s could be avoided, such that only 0.12% of the total BoD would be attributable to natural sources of HAP’s. Results of the sensitivity analysis support the notion of the DALY as a robust measure to estimate exposure attributable health impacts, as the incorporation of alternative value choices had negligible impact on the relative importance of cancer sites, or exposures to the total BoD. Results of the model can be used by decision makers to inform public health policy regarding abatement priorities of HAP’s in Ontario, on the basis associated health impacts.

Environmental airborne benzene is a ubiquitous hazardous air pollutant whose emissions are generated from multiple sources, including industrial emissions, fuel station emissions, and automobile emissions. Chronic occupational exposures to elevated levels of benzene are known to be associated with leukemic cancers, in particular, acute myeloid leukemia (AML), though epidemiological evidence regarding environmental exposures and subsequent AML development is lacking. This investigation uses historical airborne monitoring data from six counties in the State of Florida to characterize the environmental cancer risk from airborne benzene concentrations using current Federal and State regulatory analysis methodology, and a comparative analysis based on occupational epidemiological evidence. Airborne benzene concentrations were collected from 24 air toxics monitoring stations in Broward, Duval, Orange, Miami-Dade, Hillsborough, and Pinellas counties. From the years 2003 - 2006, 3,794 air samples were collected using 8, 12, and 24 hr samples with sub-ambient pressure canister collectors consistent with EPA benzene methodological protocols 101 and 176. Mean benzene concentrations, by site, ranged from 0.18 - 3.58 ppb. Using risk analysis methodology consistent with the EPA and the Florida Department of Environmental Protection (FLDEP) the resulting cancer risk estimates ranged from 4.37 x 10-6 to 8.56 x 10-5, exceeding the FLDEP's acceptable cancer risk level, 1 x 10-6 for all monitoring sites. The cumulative lifetime exposures were calculated in ppm-years by site, ranging from 0.036 - 0.702 ppmyears. A comparative analysis with available epidemiological literature revealed that associations between benzene exposure and cancer outcomes were related to cumulative lifetime exposures in great excess of 1 ppm-years. The results of this investigation indicate that it is not reasonable to expect additional cancer outcomes in Florida residents as a result of airborne benzene exposures consistent with measured concentrations, despite the fact that all regulatory risk calculations exceed acceptable cancer risk levels in the State of Florida.

No description available.

There is a growing public concern that emissions of mobile source air toxics (MSATs) from motor vehicles may pose a threat to human health. At present, no state or federal agencies require dispersion modeling of these compounds, but many agencies are concerned about potential future requirements. Current air pollution professionals are familiar with Federal Highway Administration (FHWA) and U.S. Environmental Protection Agency (EPA) requirements for dispersion modeling to produce predicted concentrations for comparison with appropriate standards. This research examined a method in which the potential near-road concentrations of MSATs were calculated. It was believed that by assessing MSATs in much the same way that are used for other pollutants, the model and methods developed in this research could become a standard for those quantifying MSAT concentrations near-roadways. This dissertation reports on the results from short-term (1-hour) and long-term (annual average) MSATs dispersion modeling that has been conducted on seven intersections and seven freeway segments in the state of Florida. To accomplish the modeling, the CAL3QHC model was modified to handle individual MSAT emissions input data and to predict the concentrations of several MSATs around these roadway facilities. Additionally, since the CAL3MSAT model is DOS based and not user-friendly, time was invested to develop a Windows® graphical user interface (GUI). Real-world data (traffic volumes and site geometry) were gathered, worst-case meteorology was selected, mobile source emission factors (EFs) were obtained from MOVES2010a, and worst-case modeling was conducted. Based on a literature search, maximum acceptable concentrations (MACs) were proposed for comparison with the modeled results, for both a short-term (1-hour) averaging time and a long-term (1-year) averaging time. iv Results from this CAL3MSAT modeling study indicate that for all of the intersections and freeway segments, the worst-case 1-hour modeled concentrations of the MSATs were several orders of magnitude below the proposed short-term MACs. The worst-case 1-year modeled concentrations were of the same order of magnitude as the proposed long-term MACs. The 1-year concentrations were first developed by applying a persistence factor to the worst-case 1-hour concentrations. In the interest of comparing the predicted concentrations from the CAL3MSAT persistence factor approach to other dispersion models, two EPA regulatory models (CAL3QHCR and AERMOD) with the ability to account for yearly meteorology, traffic, and signal timing were used. Both hourly and annual MSAT concentrations were predicted at one large urban intersection and compared for the three different dispersion models. The shortterm 1-hour results from CAL3MSAT were higher than those predicted by the two other models due to the worst-case assumptions. Similarly, results indicate that the CAL3MSAT persistence factor approach predicted a worst-case annual average concentration on the same order of magnitude as the two other more refined models. This indicated that the CAL3MSAT model might be useful as a worst-case screening approach.

Petroleum refineries emit a variety of airborne substances which may be harmful to human health. HEIDI II (Health Effects Indicators Decision Index II) is a computer-based decision analysis tool which assesses airborne emissions from Canada's oil refineries for reduction, based on ordinal ranking of estimated health impacts. The model was designed by a project team within NERAM (Network for Environmental Risk Assessment and Management) and assembled with significant stakeholder consultation. HEIDI II is publicly available as a deterministic Excel-based tool which ranks 31 air pollutants based on predicted disease incidence or estimated DALYS (disability adjusted life years). The model includes calculations to account for average annual emissions, ambient concentrations, stack height, meteorology/dispersion, photodegradation, and the population distribution around each refinery. Different formulations of continuous dose-response functions were applied to nonthreshold-acting air toxics, threshold-acting air toxics, and nonthreshold-acting CACs (criteria air contaminants). An updated probabilistic version of HEIDI II was developed using Matlab code to account for parameter uncertainty and identify key leverage variables. Sensitivity analyses indicate that parameter uncertainty in the model variables for annual emissions and for concentration-response/toxicological slopes have the greatest leverage on predicted health impacts. Scenario analyses suggest that the geographic distribution of population density around a refinery site is an important predictor of total health impact. Several ranking metrics (predicted case incidence, simple DALY, and complex DALY) and ordinal ranking approaches (deterministic model, average from Monte Carlo simulation, test of stochastic dominance) were used to identify priority substances for reduction; the results were similar in each case. The predicted impacts of primary and secondary particulate matter (PM) consistently outweighed those of the air toxics. Nickel, PAH (polycyclic aromatic hydrocarbons), BTEX (benzene, toluene, ethylbenzene and xylene), sulphuric acid, and vanadium were consistently identified as priority air toxics at refineries where they were reported emissions. For many substances, the difference in rank order is indeterminate when parametric uncertainty and variability are considered.

Formaldehyde and acetaldehyde are listed by the United States Environmental Protection Agency (U.S. EPA) as urban air toxics. Health effects due to significant exposure to these air toxics include increased incidence of nasopharyngeal cancer, myeloid leukemia, and exacerbation of asthma. Determining the spatial variation of air toxics, such as acetaldehyde and formaldehyde, is important for improving health risk assessment and evaluating the effectiveness of source control and reduction programs. Here, a pilot study was designed and performed to investigate small-scale spatial variability in concentrations of aldehydes using passive samplers. A literature review was first completed to select and evaluate current passive sampling and analysis methods. Radiello Aldehyde Samplers and high performance liquid chromatography (HPLC) were selected for sampling and analysis, respectively. An HPLC instrument was then set-up for separation with an Allure AK (aldehyde-ketone) column and for detection of aldehyde-derivatives via ultraviolet-visible (UV-Vis) spectrometer at 365 nm. Samplers were deployed in an (approximately) 0.7 km resolution grid pattern for one week in January 2010. Collected samples and blanks were eluted with acetonitrile and analysis was performed with the HPLC. Aldehyde samples were quantified using calibration standards. Mean aldehyde concentrations were 3.1 and 1.2 =/ mg/m³ for formaldehyde and acetaldehyde, respectively, and mean acetaldehyde/formaldehyde concentration ratios were 0.4. The concentration ratios showed very little variation between sites, and correlation of aldehyde concentrations by site was high (r=0.7). Therefore, it is likely that both aldehydes have similar sources. Spatial variation of aldehyde concentrations was small within the sampling area, as displayed by low coefficients of variation (13 and 23% for formaldehyde and acetaldehyde, respectively) and small concentration differences between sites (average of both aldehydes less than 0.5 mg/m³). Thus, one sampler may be representative of this sampling area and possibly other areas of the same spatial scale. Methods established during this pilot study will be used in a larger field campaign to characterize the spatial distribution of concentrations throughout the county, for analysis of environmental equity and health impacts.

According to the World Health Organization, urban air pollution is a high public health priority due its linkage to cardio-pulmonary disease and association with increased mortality and morbidity (1, 2). Additionally, air pollution impacts climate change, visibility, and ecosystem health. The development of effective strategies for improving air quality requires accurate estimates of air pollutant emissions. In response to the need for new approaches to measuring emissions, we have designed a mobile Flux Lab for the Atmospheric Measurement of Emissions (FLAME) that applies a proven, science-based method known as eddy covariance for the direct quantification of anthropogenic emissions to the atmosphere. The mobile flux lab is a tool with novel, multifaceted abilities to assess air quality and improve the fidelity of emission inventories. Measurements of air pollutant concentrations in multiple locations at the neighborhood scale can provide much greater spatial resolution for population exposure assessments. The lab's mobility allows it to target specific sources, and plumes from these can be analyzed to determine emission factors. Through eddy covariance, the lab provides the new ability to directly measure emissions of a suite of air pollutants. We have deployed the FLAME to three different settings: a rural Appalachian town where coal transport is the dominant industry; schools in the medium-sized city of Roanoke, Virginia; and the large urban areas around Norfolk, Virginia, to measure neighborhood-scale emissions of air pollution. These areas routinely experience high ozone and particulate matter concentrations and include a diverse array of residential neighborhoods and industries. The FLAME is able to capture emissions from all ground-based sources, such as motor vehicles, rail and barge traffic, refuse fires and refueling stations, for which no direct measurement method has been available previously. Experiments focus on carbon dioxide (CO₂), the principal greenhouse gas responsible for climate change; nitrogen oxides (NOx), a key ingredient in ground-level ozone and acid rain; volatile organic compounds (VOCs), a second key ingredient in ozone and many of which are air toxics; and fine particulate matter (PM2.5), a cause of mortality, decreased visibility, and climate change. This research provides some of the first measurements of neighborhood-scale anthropogenic emissions of CO₂, NOx, VOCs and PM2.5 and as a result, the first opportunity to validate official emission inventories directly. The results indicate that a mobile eddy covariance system can be used successfully to measure fluxes of multiple pollutants in a variety of urban settings. With certain pollutants in certain locations, flux measurements confirmed inventories, but in others, they disagreed by factors of up to five, suggesting that parts of the inventory may be severely over- or underestimated. Over the scale of a few kilometers within a city, emissions were highly heterogeneous in both space and time. FLAME-based measurements also confirmed published emission factors from coal barges and showed that idling vehicles are the dominant source of emissions of air toxics around seven schools in southwest Virginia. Measurements from this study corroborate existing emission inventories of CO₂ and NOx and suggest that inventories of PM2.5 may be overestimated. Despite the tremendous spatial and temporal variability in emissions found in dense urban areas, CO₂ fluxes on average are very similar across the areas in this study and other urban areas in the developed world. Nevertheless, the high level of variability in spatial and temporal patterns of emissions presents a challenge to air quality modelers. The finding that emissions from idling vehicles at schools are likely responsible for creating hot spots of air toxics adds to the urgency of implementing no-idling and other rules to reduce the exposure of children to such pollutants. Ultimately, the results of this study can be used in combination with knowledge from existing emission inventories to improve the science and policies surrounding air pollution. / Ph. D.