Date of Award

Fall 2014

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Paul B. Shepson

Committee Chair

Qianlai Zhuang

Committee Member 1

Dor Ben-Amotz

Committee Member 2

Garth J. Simpson

Abstract

Improved quantification of carbon-cycle sources and sinks is an important requirement for determining mitigation strategies and modeling future climate interactions. Analytically robust measurements require high-precision instrumentation and thoughtful experimental design to produce rigorous and reproducible results despite complex and quickly changing meteorological and environmental conditions. Here, an aircraft platform equipped with a high-precision cavity ring-down spectrometer for CO2, CH4 and H2O quantification was used to acquire data from previously un-sampled sources. The aircraft mass-balance technique was used to quantify CH4 emissions from natural gas well pads in the drilling stage, which were 2-3 orders of magnitude higher than previous estimates of emissions from this stage. In addition, the first in-situ flare emission data was collected for natural gas flares in North Dakota, Pennsylvania and Texas. Flare efficiency was high for most flares, higher than assumed efficiency. However, a few flares sampled with lower efficiencies closer to the assumed flare efficiency suggest the need for characterization of operational conditions specific to operators and basins. Finally, eddy-covariance O2 and heat fluxes were measured over three east-coast forests at sites close to and far from surface eddy-covariance towers. Tower data is often used in models to represent a larger heterogeneous region. Aircraft and tower O2 and sensible heat flux agreed well, indicating that for these sites, tower data is a good approximation of the larger region, though significant variability was observed. Aircraft latent heat fluxes were routinely much larger that tower fluxes, most likely due to the influence of advection which is measured by the aircraft eddy-covariance technique, but not by towers.

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