Photochemistry and transport of tropospheric ozone and its precursors in urban and remote environments

Tropospheric ozone (O3) adversely affects human health, reduces crop yields, and contributes to climate forcing. To limit these effects, the processes controlling O3 abundance as well as that of its precursor molecules must be fully characterized. Here, I examine three facets of O3 production, both in heavily polluted and remote environments. First, using in situ observations from the DISCOVER-AQ field campaign in the Baltimore/Washington region, I evaluate the emissions of the O3 precursors CO and NOx (NOx = NO + NO2) in the National Emissions Inventory (NEI). I find that CO/NOx emissions ratios derived from observations are 21% higher than those predicted by the NEI. Comparisons to output from the CMAQ model suggest that CO in the NEI is accurate within 15 ± 11%, while NOx emissions are overestimated by 51-70%, likely due to errors in mobile sources. These results imply that ambient ozone concentrations will respond more efficiently to NOx controls than current models suggest. I then investigate the source of high O3 and low H2O structures in the Tropical Western Pacific (TWP). A combination of in situ observations, satellite data, and models show that the high O3 results from photochemical production in biomass burning plumes from fires in tropical Southeast Asia and Central Africa; the low relative humidity results from large-scale descent in the tropics. Because these structures have frequently been attributed to mid-latitude pollution, biomass burning in the tropics likely contributes more to the radiative forcing of climate than previously believed. Finally, I evaluate the processes controlling formaldehyde (HCHO) in the TWP. Convective transport of near surface HCHO leads to a 33% increase in upper tropospheric HCHO mixing ratios; convection also likely increases upper tropospheric CH3OOH to ~230 pptv, enough to maintain background HCHO at ~75 pptv. The long-range transport of polluted air, with NO four times the convectively controlled background, intensifies the conversion of HO2 to OH, increasing OH by a factor of 1.4. Comparisons between the global chemistry model CAM-Chem and observations show that consistent underestimates of HCHO by CAM-Chem throughout the troposphere result from underestimates in both NO and acetaldehyde.

MICROFLUIDIC ASSAY PERFORMANCE ENHANCEMENT USING POROUS VOLUMETRIC DETECTION ELEMENTS FOR IMPEDEMETRIC AND OPTICAL SENSING

Microfluidic technologies have great potential to help create automated, cost-effective, portable devices for rapid point of care (POC) diagnostics in diverse patient settings. Unfortunately commercialization is currently constrained by the materials, reagents, and instrumentation required and detection element performance. While most microfluidic studies utilize planar detection elements, this dissertation demonstrates the utility of porous volumetric detection elements to improve detection sensitivity and reduce assay times. Impedemetric immunoassays were performed utilizing silver enhanced gold nanoparticle immunoconjugates (AuIgGs) and porous polymer monolith or silica bead bed detection elements within a thermoplastic microchannel. For a direct assay with 10 µm spaced electrodes the detection limit was 0.13 fM AuIgG with a 3 log dynamic range. The same assay was performed with electrode spacing of 15, 40, and 100 µm with no significant difference between configurations. For a sandwich assay the detection limit was10 ng/mL with a 4 log dynamic range. While most impedemetric assays rely on expensive high resolution electrodes to enhance planar senor performance, this study demonstrates the employment of porous volumetric detection elements to achieve similar performance using lower resolution electrodes and shorter incubation times. Optical immunoassays were performed using porous volumetric capture elements perfused with refractive index matching solutions to limit light scattering and enhance signal. First, fluorescence signal enhancement was demonstrated with a porous polymer monolith within a silica capillary. Next, transmission enhancement of a direct assay was demonstrated by infusing aqueous sucrose solutions through silica bead beds with captured silver enhanced AuIgGs yielding a detection limit of 0.1 ng/mL and a 5 log dynamic range. Finally, ex situ functionalized porous silica monolith segments were integrated into thermoplastic channels for a reflectance based sandwich assay yielding a detection limit of 1 ng/mL and a 5 log dynamic range. The simple techniques for optical signal enhancement and ex situ element integration enable development of sensitive, multiplexed microfluidic sensors. Collectively the demonstrated experiments validate the use of porous volumetric detection elements to enhance impedemetric and optical microfluidic assays. The techniques rely on commercial reagents, materials compatible with manufacturing, and measurement instrumentation adaptable to POC diagnostics.