In summer 2012, a landfill liner comprising an estimated 1.3 million shredded tires burned in Iowa City, Iowa. During the fire, continuous monitoring and laboratory measurements were used to characterize the gaseous and particulate emissions and to provide new insights into the qualitative nature of the smoke and the quantity of pollutants emitted. Significant enrichments in ambient concentrations of CO, CO2, SO2, particle number (PN), fine particulate (PM2.5) mass, elemental carbon (EC), and polycyclic aromatic hydrocarbons (PAH) were observed. For the first time, PM2.5 from tire combustion was shown to contain PAH with nitrogen heteroatoms (a.k.a. azaarenes) and picene, a compound previously suggested to be unique to coal-burning. Despite prior laboratory studies’ findings, metals used in manufacturing tires (i.e. Zn, Pb, Fe) were not detected in coarse particulate matter (PM10) at a distance of 4.2 km downwind. Ambient measurements were used to derive the first in situ fuel-based emission factors (EF) for the uncontrolled open burning of tires, revealing substantial emissions of SO2 (7.1 g kg−1), particle number (3.5×1016 kg−1), PM2.5 (5.3 g kg−1), EC (2.37 g kg−1), and 19 individual PAH (totaling 56 mg kg−1). A large degree of variability was observed in day-to-day EF, reflecting a range of flaming and smoldering conditions of the large-scale fire, for which the modified combustion efficiency ranged from 0.85-0.98. Recommendations for future research on this under-characterized source are also provided.

The Iowa City Landfill in eastern Iowa, United States, experienced a fire lasting 18 days in 2012, in which a drainage layer of over 1 million shredded tires burned, generating smoke that impacted the surrounding metropolitan area of 130,000 people. This emergency required air monitoring, risk assessment, dispersion modeling, and public notification. This paper quantifies the impact of the fire on local air quality and proposes a monitoring approach and an Air Quality Index (AQI) for use in future tire fires and other urban fires. Individual fire pollutants are ranked for acute and cancer relative risks using hazard ratios, with the highest acute hazard ratios attributed to SO2, particulate matter, and aldehydes. Using a dispersion model in conjunction with the new AQI, we estimate that smoke concentrations reached unhealthy outdoor levels for sensitive groups out to distances of 3.1 km and 18 km at 24-h and 1-h average times, respectively. Modeled and measured concentrations of PM2.5 from smoke and other compounds such as VOCs and benzo[a]pyrene are presented at a range of distances and averaging times, and the corresponding cancer risks are discussed. Through reflection on the air quality response to the event, consideration of cancer and acute risks, and comparison to other tire fires, we recommend that all landfills with shredded tire liners plan for hazmat fire emergencies. A companion paper presents emission factors and detailed smoke characterization.

This report describes the preparation of a series of 17 novel racemic spirocyclic scaffolds that are intended for the creation of compound libraries by parallel synthesis for biological screening. Each scaffold features two points of orthogonal diversification. The scaffolds are related to each other in four ways: Through stepwise changes in the size of the nitrogen bearing ring.Through the oxidation state of the carbon centered point of diversification.Through the relative stereochemical orientation of the two diversification sites in those members that are stereogenic.Through the provision of both saturated and unsaturated versions of the furan ring in the scaffold series derived from 3-piperidone. The scaffolds provide incremental changes in the relative orientation of the diversity components that would be introduced onto them. The scaffolds feature high sp3 carbon content which is essential for the three dimensional exploration of chemical space. This characteristic is particularly evident in those members of this family that bear two stereocenters, i.e. the two series derived from 3-piperidone and 3-pyrrolidinone. In the series derived from 3-piperidone we were able to “split the difference” between the two diastereomers by preparation of their corresponding unsaturated version.

grant program funded by NIH P30 ES005605, the High Resolution Mass Spectrometry Facility and the Center for Global and Regional Environmental Research. Many thanks to the Stone research group for always providing support and promoting a collaborative scientific environment. Specifically, I am grateful to Thilina Jayarathne and Chathurika Rathnayake for help with sample collection and analysis. Finally I would like to thank my friends and family, especially my future wife Kelly, for all their love and support through my graduate research. At times graduate school was a little rough and I could not have completed this work alone.