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.

Master of Science / Department of Agronomy / Jay M. Ham / The potential environmental impact of animal feeding operations on air quality has created the need for accurate air emissions measurements. Of particular concern are ammonia emissions from cattle feedlots, operations that contribute a large portion of the agricultural ammonia emissions inventory. Micrometeorological methods are ideal for emissions measurements from large, open-source areas like feedlot pens; however, theoretical assumptions about the boundary layer must be made, which may not hold true above the heterogeneous, fetch-limited surface of the feedlot. Thus, the first objective of this work was to characterize the surface boundary layer of an open-air cattle feedlot and provide insight into how micrometeorological techniques might be applied to these non-ideal sites. Eddy covariance was used to measure fluxes of momentum, heat, water, and carbon dioxide from a commercial cattle feedlot in central Kansas. Data supported the use of eddy covariance and similar methods (i.e., relaxed eddy accumulation) for flux measurements from both cattle and pen surfaces. The modeled cumulative source area contributing to eddy covariance measurements at a 6 m sample height was dominated by just a few pens near the tower, making the characteristics of those pens especially important when interpreting results. The second objective was to develop a system for measuring ammonia fluxes from feedlots. A new type of relaxed eddy accumulation system was designed, fabricated, and tested that used honeycomb denuders to independently sample ammonia in up-moving and down-moving eddies. Field testing of the relaxed eddy accumulation system at a feedlot near Manhattan, KS showed fluxes of ammonia ranged between 60 and 130 μg m-2 s-1 during the summer of 2007. Even in the high ammonia environment (e.g., 300-600 μg m-3), the honeycomb denuders had enough capacity for the 4-hour sampling duration and could be used to measure other chemical species that the denuders could be configured to capture. Results provide a foundation for emissions measurements of ammonia and other gases at cattle feedlots and help address some of the challenges that micrometeorologists face with any non-ideal source area.

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from both anthropogenic and biogenic emission sources in the urban surface layer. We describe a new relaxed eddy accumulation system combined with a dual-channel gas chromatography - flame ionization detection used for volatile organic compound (VOC) flux measurements in the urban area, focusing on the results of selected anthropogenic VOCs, including benzene, toluene, ethylbenzene and xylenes (BTEX), and biogenic VOCs including isoprene and its oxidation products, methacrolein (MACR) and methyl vinyl ketone (MVK). We present diurnal variations of concentrations and fluxes of BTEX, and isoprene and its oxidation products during summer time (May 22 - July 22, 2008) and winter time (January 1 - February 28). The measured BTEX values exhibited diurnal cycles with a morning peak during weekdays related to rush-hour traffic and additional workday daytime flux maxima for toluene and xylenes in summer time. However, in winter time there was no additional workday daytime peaks due mainly to the different flux footprints between the two seasons. A comparison with different EPA National Emission Inventories (NEI) with our summer time flux data suggests potential underestimates in the NEI by a factor of 3 to 5. The mixing ratios and fluxes of isoprene, MACR and MVK were measured during the same time period in summer 2008. The presented results show that the isoprene was affected by both tail-pipe emission sources during the morning rush hours and biogenic emission sources in daytime. The observed daytime mixing ratios of isoprene were much lower than over forested areas, caused by a comparatively low density of isoprene emitters in the tower's footprint area. The average daytime isoprene flux agreed well with emission rates predicted by a temperature and light only emission model (Guenther et al., 1993). Our investigation of isoprene's oxidation products MACR and MVK showed that both anthropogenic and biogenic emission sources exist for MACR, while MVK was strongly dominated by a biogenic source, likely the isoprene oxidation between the emission and sampling points.