Knowledge of distributions of aerosols is critical to human health, Earth's radiative budget, and air quality. However, the lack of sufficient direct measurements of aerosol type, number, mass concentrations and current limitations of satellite retrievals make it challenging to accurately model the aerosol variability. Such measurement gaps also hinder evaluation of aerosol source budget from emission inventories, modeling of aerosol chemistry, and sinks. In this context, the first study characterizes the potential of multivariate relationships between Aerosol Optical Depth (AOD), a quantity that represents light extinction by aerosols in the atmospheric column and a suite of surface and atmospheric parameters (e.g., vegetation, precipitation, fire characteristics) in order to assess trends in AOD anomalies for the U.S Southwest. This study covers the area that experiences North American Monsoon (NAM) and examines trends in AOD across different aerosol sources in this region such as dust storms, biomass burning, and anthropogenic emissions. We find that aerosols from anthropogenic processes and biomass burning exhibited a strong declining trend in AOD whereas trends along the NAM alley were obfuscated by the monsoon precipitation (sink) and convective dust storms (sources). In the second study, we develop constraints to improve characterization of anthropogenic apparent Elemental Carbon (ECa) using coemitted combustion products such as Carbon Monoxide (CO) and Nitrogen Oxides (NOx). We compare observational ratios of ECa vs CO and ECa vs NOx against those from emission inventories. We find that the observational ratios have increased at sites in the Urban-West due to increase in ECa from 2000-2007 to 2008-2015. Further, emission ratios do not match with observational ratios. We recommend that rigorous efforts are needed to better quantify and monitor the changes in these species in the Urban-West particularly for non-road and residential combustion sectors. The final study of this dissertation discusses a technique to produce forecasts of AOD by combining satellite retrievals and a chemical transport model in an analog based framework. We use model forecasts of AOD, particulate matter (PM) concentrations, and meteorological parameters from Weather Research and Forecasting model with Chemistry (WRF-Chem) to train the framework for choosing analogs (past forecasts similar to current simulations). MODIS Terra and Aqua satellite retrievals of AOD for analog days are then used in a Kalman Filter (KF) framework to determine the forecast error and referred to as KFAN. The analog based estimates better forecasts of AOD for the Western US compared to the East and the mean bias in AOD forecasts are reduced to the range of 0.001-0.1. The reduction in positive bias in AOD is drastic and the method captures the decrease in AOD from morning to afternoon. We find that higher root mean square error (RMSE) values in the East are due to the inability of KFAN to capture the AOD peaks during biomass burning episodes and AOD lows during days of high precipitation rates. A systematic statistical analysis using step-wise linear regression models also show that in the East, there is a stronger dependence of aerosol loading on meteorological factors such as air temperature, precipitation, and relative humidity. As a consequence, overall quality of the analogs in the East is impacted when uncertainties in the simulated meteorological fields are higher. Overall, this study shows that the correlative information from multi-satellite remote sensing retrievals and models provide additional constraints on aerosols using composition/source identification (e.g., aerosol type, landcover, emission sources, fuel consumption), coemitted gas phase species (e.g., CO and NOx), and meteorological parameters (e.g., wind speed, TPW). The synergy of information from these datasets can be beneficial for design of future remote sensing missions, deployment of ground networks, and studies related to feedbacks between meteorology and aerosols.

Measurements by OSIRIS, an infrared imaging system that measures emission from excited-state molecular oxygen, are used to retrieve mesospheric ozone through a photochemical model. The design of the model and the spectral data used in the calculation of pho- tochemical production coe±cients are presented. The model has been run in a variety of modes to provide comparisons with measurements of excited-state molec- ular oxygen; it has been found that the model results are in excellent agreement with measurements. The model is used in conjunction with a retrieval scheme to estimate the con- centrations of mesospheric ozone from measurements made on a satellite platform. An analysis of the sensitivity of retrieved ozone to key model parameters is done, and it is shown that uncertainty in several kinetic reaction rates can signi¯cantly change the retrieved results. Comparisons are made for the ozone retrieved in this work and that from several other instruments that make similar measurements. The retrieved concentrations are shown to be in excellent agreement with results from other instruments. The present work provides a climatological database of mesospheric ozone and will provide useful comparisons with concurrent measurements of mesospheric ozone. The new data obtained in this work are in good agreement with expected results, and it is shown that the unprecedented high-spatial resolution of OSIRIS reveals interesting features that should be further investigated.

Measurements by OSIRIS, an infrared imaging system that measures emission from excited-state molecular oxygen, are used to retrieve mesospheric ozone through a photochemical model. The design of the model and the spectral data used in the calculation of pho- tochemical production coe±cients are presented. The model has been run in a variety of modes to provide comparisons with measurements of excited-state molec- ular oxygen; it has been found that the model results are in excellent agreement with measurements. The model is used in conjunction with a retrieval scheme to estimate the con- centrations of mesospheric ozone from measurements made on a satellite platform. An analysis of the sensitivity of retrieved ozone to key model parameters is done, and it is shown that uncertainty in several kinetic reaction rates can signi¯cantly change the retrieved results. Comparisons are made for the ozone retrieved in this work and that from several other instruments that make similar measurements. The retrieved concentrations are shown to be in excellent agreement with results from other instruments. The present work provides a climatological database of mesospheric ozone and will provide useful comparisons with concurrent measurements of mesospheric ozone. The new data obtained in this work are in good agreement with expected results, and it is shown that the unprecedented high-spatial resolution of OSIRIS reveals interesting features that should be further investigated.

Marine stratocumulus cloud regimes exert a strong climatic influence through their high solar reflectivity. Human-induced changes in stratocumulus clouds, attributed to an increase of the aerosol burden (indirect effects), can be significant given the cloud decks proximity to the continents; nevertheless, the magnitude and the final climatic consequences of these changes are uncertain. This thesis investigates further the interactions between aerosols, cloud microphysics, regional circulation, and radiative response in the Southeast Pacific stratocumulus cloud deck, one of the largest and most persistent cloud regimes in the planet. Specifically, three different aspects are addressed by this thesis: The importance of the synoptic atmospheric variability in controlling cloud microphysical and radiative changes, a validation analysis of satellite retrievals of cloud microphysics from MOderate Resolution Imaging Spectroradiometer (MODIS), and the quantitative assessments of cloud aerosol interactions along with their associated radiative forcing using primarily aircraft remote sensing data. Synoptic and satellite-derived cloud property variations for the Southeast Pacific region associated with changes in coastal satellite-derived cloud droplet number concentration (Nd) are analyzed through a composite technique. MAX and MIN Nd composites are defined by the top and bottom terciles of daily area-mean Nd values over the Arica Bight, the region with the largest mean oceanic Nd, for the five October months of 2001, 2005, 2006, 2007, and 2008. The MAX-Nd composite is characterized by a weaker subtropical anticyclone and weaker winds than the MIN-Nd composite. Additionally, the MAX-Nd composite clouds over the Arica Bight are thinner than the MIN-Nd composite clouds, have lower cloud tops, lower near-coastal cloud albedos, and occur below warmer and drier free tropospheres. At 85˚W, the top-of-atmosphere shortwave fluxes are significantly higher (50%) for the MAX-Nd, with thicker, lower clouds and higher cloud fractions than for the MIN-Nd. The change in Nd at this location is small, suggesting that the MAX-MIN Nd composite differences in radiative properties primarily reflects synoptic changes. The ability of MODIS level 2 retrievals to represent the cloud microphysics is assessed with in-situ measurements of droplet size distributions, collected during the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx). The MODIS cloud optical thickness (t) correlates well with the in-situ values with a positive bias (1.42). In contrast, the standard 2.1 micron-derived MODIS cloud effective radius (r_e) is found to systematically exceed the in-situ cloud-top r_e, with a mean bias of 2.08 um. Three sources of errors that could contribute to the MODIS r_e positive bias are investigated further: the spread of the cloud droplet size distribution, the presence of a separate drizzle mode, and the sensor viewing angles. The sensor zenith viewing angles were found to have little impact, while the algorithm assumption about the cloud droplet spectra and presence of a precipitation mode could affect the retrievals but not by enough to fully explain the positive MODIS r_e bias. The droplet spectra effects account for r_e offsets smaller than 0.6 um, 0.9 um, and 1.6 um for non-drizzling, light-drizzling, and heavy-drizzling clouds respectively. An explanation for the observed MODIS bias is lacking although three-dimensional radiative effects were not considered. This investigation supports earlier studies documenting a similar bias, this time using data from newer probes. MODIS r_e and t were also combined to estimate a liquid water path (LWP) and Nd. A positive bias was also apparent in LWP, and attributed to r_e. However, when selected appropriate parameters a priori, the MODIS Nd estimate was found to agree the best with the insitu aircraft observations of the four MODIS variables. Lastly, the first aerosol indirect effect (Twomey effect) is explicitly investigated with VOCALS-REx observations, collected during three daytime research flights (Nov 9, 11, and 13), utilizing an aerosol-cloud interactions metric, and defined as ACI=dln(t)/dln(Na), with Na corresponding to the accumulation mode aerosol concentration, t derived from a broadband pyranometer, and ACI binned by cloud LWP derived from a millimeter-wavelength radiometer. Aircraft remote sensing estimates of the ACI, during sub-cloud transects, show that the cloud aerosol-interactions are strong and close to the maximum theoretical value for thin clouds, with a decrease of ACI with LWP. Although an explanation for the dependence of ACI on LWP is lacking, we found that a decrease in ACI with LWP is associated with decreases in both surface meridional winds and Nd. Similar to ACI, albedo fractional changes due to Nd fractional changes also tended to be smaller for higher LWPs, but with an overall radiative forcing larger than conservative global estimates obtained in global circulation models. The findings of this thesis emphasize the strong stratocumulus albedo response to an aerosol perturbation and its dependence on the regional scale atmospheric configuration. The results presented here can be used as a benchmark for testing regional and climate models, as well as helping to improve the current parameterizations of the first aerosol indirect effect.

Remote sensing of atmospheric gases improves our understanding of the state and evolution of the Earth’s environment. At the beginning of the thesis, the basic principles for the retrieval of concentrations of atmospheric gases from spectra are presented with a focus on ground-based observations. An overview of the characteristic features of different platforms, viewing geometries, measurement sites, and Fourier Transform Spectrometers (FTSs) used in the measurements are provided. The thesis covers four main projects. The first study of the global distribution of atmospheric phosgene was carried out using a total of 5614 measured profiles from the satellite-borne Atmospheric Chemistry Experiment FTS (ACE-FTS) spanning the period February 2004 through May 2006. The phosgene concentrations display a zonally symmetric pattern with the maximum concentration located approximately over the equator, at about 25 km in altitude, and the concentrations decrease towards the poles. A layer of enhanced concentration of phosgene spans the lower stratosphere at all latitudes, with volume mixing ratios of 20-60 pptv. The reasons for the formation of the phosgene distribution pattern are explained by the insolation, lifetime of phosgene and the Brewer-Dobson circulation. The ACE observations show lower phosgene concentrations in the stratosphere than were obtained from previous observations in the 1980s and 1990s due to a significant decrease in source species. The Portable Atmospheric Research Interferometric Spectrometer for the Infrared (PARIS-IR) is a copy of the ACE-FTS that was designed for ground-based and balloon-borne measurements. The first balloon flight was part of the Middle Atmosphere Nitrogen TRend Assessment (MANTRA) 2004 balloon payload. Some useful engineering information was obtained on the thermal performance of the instrument during the flight. As part of the MANTRA program, a ground-based inter-instrument comparison campaign was conducted with the objective of assessing instrument performance, and evaluating data processing routines and retrieval codes. PARIS-IR provides similar quality results for stratospheric species as does the University of Toronto FTS. An advanced study was carried out for the Carbon Cycle science by Fourier Transform Spectroscopy (CC-FTS) mission, which is a proposed future satellite mission to obtain a better understanding of the sources and sinks of greenhouse gases in the Earth’s atmosphere by monitoring total and partial columns of CO2, CH4, N2O, and CO in the near infrared together with the molecular O2 column. To evaluate the spectral regions, resolution, optical components, and spectroscopic parameters required for the mission, ground-based Fourier transform spectra, recorded at Kiruna, Kitt Peak, and Waterloo, were used. Dry air volume mixing ratios of CO2 and CH4 were retrieved from the ground-based observations. A FTS with a spectral resolution of 0.1 cm-1, operating between 2000 and 15000 cm-1, is suggested as the primary instrument for the mission. Further progress in improving the atmospheric retrievals for CO2, CH4 and O2 requires new laboratory measurements to improve the spectroscopic line parameters. Atmospheric observations were made with three FTSs at the Polar Environment Atmospheric Research Laboratory (PEARL) during spring 2006. The vertical column densities of O3, HCl, HNO3, HF, NO2, ClONO2 and NO from PARIS-IR, the Eureka DA8 FTS, and the ACE-FTS show good agreement. Chorine activation and denitrification in the Arctic atmosphere were observed in the extremely cold stratosphere near Eureka, Nunavut, Canada. The observed ozone depletion during the 2006 campaign was attributed to chemical removal.

Remote sensing of atmospheric gases improves our understanding of the state and evolution of the Earth’s environment. At the beginning of the thesis, the basic principles for the retrieval of concentrations of atmospheric gases from spectra are presented with a focus on ground-based observations. An overview of the characteristic features of different platforms, viewing geometries, measurement sites, and Fourier Transform Spectrometers (FTSs) used in the measurements are provided. The thesis covers four main projects. The first study of the global distribution of atmospheric phosgene was carried out using a total of 5614 measured profiles from the satellite-borne Atmospheric Chemistry Experiment FTS (ACE-FTS) spanning the period February 2004 through May 2006. The phosgene concentrations display a zonally symmetric pattern with the maximum concentration located approximately over the equator, at about 25 km in altitude, and the concentrations decrease towards the poles. A layer of enhanced concentration of phosgene spans the lower stratosphere at all latitudes, with volume mixing ratios of 20-60 pptv. The reasons for the formation of the phosgene distribution pattern are explained by the insolation, lifetime of phosgene and the Brewer-Dobson circulation. The ACE observations show lower phosgene concentrations in the stratosphere than were obtained from previous observations in the 1980s and 1990s due to a significant decrease in source species. The Portable Atmospheric Research Interferometric Spectrometer for the Infrared (PARIS-IR) is a copy of the ACE-FTS that was designed for ground-based and balloon-borne measurements. The first balloon flight was part of the Middle Atmosphere Nitrogen TRend Assessment (MANTRA) 2004 balloon payload. Some useful engineering information was obtained on the thermal performance of the instrument during the flight. As part of the MANTRA program, a ground-based inter-instrument comparison campaign was conducted with the objective of assessing instrument performance, and evaluating data processing routines and retrieval codes. PARIS-IR provides similar quality results for stratospheric species as does the University of Toronto FTS. An advanced study was carried out for the Carbon Cycle science by Fourier Transform Spectroscopy (CC-FTS) mission, which is a proposed future satellite mission to obtain a better understanding of the sources and sinks of greenhouse gases in the Earth’s atmosphere by monitoring total and partial columns of CO2, CH4, N2O, and CO in the near infrared together with the molecular O2 column. To evaluate the spectral regions, resolution, optical components, and spectroscopic parameters required for the mission, ground-based Fourier transform spectra, recorded at Kiruna, Kitt Peak, and Waterloo, were used. Dry air volume mixing ratios of CO2 and CH4 were retrieved from the ground-based observations. A FTS with a spectral resolution of 0.1 cm-1, operating between 2000 and 15000 cm-1, is suggested as the primary instrument for the mission. Further progress in improving the atmospheric retrievals for CO2, CH4 and O2 requires new laboratory measurements to improve the spectroscopic line parameters. Atmospheric observations were made with three FTSs at the Polar Environment Atmospheric Research Laboratory (PEARL) during spring 2006. The vertical column densities of O3, HCl, HNO3, HF, NO2, ClONO2 and NO from PARIS-IR, the Eureka DA8 FTS, and the ACE-FTS show good agreement. Chorine activation and denitrification in the Arctic atmosphere were observed in the extremely cold stratosphere near Eureka, Nunavut, Canada. The observed ozone depletion during the 2006 campaign was attributed to chemical removal.

The objective of this thesis is to evaluate the sources of the differences between the NO2 satellite retrieval products provided by the Royal Dutch Meteorological Institute (KNMI) and the National Aeronautics and Space Administration (NASA). Ground studies have shown that although both products use the same satellite, these products yield different observations for NO2 tropospheric columns concentrations. This study does not validate either retrieval product, but rather indentifies the main sources for the discrepancy. There are several parameters which allow successful retrieval of NO2 vertical columns. For this study, only the difference between the radiative models and the a priori NO2 chemical transport models were considered relevant. All other parameters, such as cloud properties, slant columns, stratospheric serration and their assumptions, were held constant. Here, the models are referred to by their proprietor's acronym: "TOMRAD" refers to the radiative model used by NASA, "DAK" refers to the radiative model used by KNMI, "TM4" refers to the a priori chemical transport model used by KNMI, and "REAM" refers to the a priori chemical transport model maintained by the School of Earth and Atmospheric Sciences at the Georgia Institute of Technology. Mixing these parameters creates four retrievals for comparison. Many significant differences were identified after comparing these four retrievals. First, there are viewing geometry biases between the port side and the starboard side of the satellite retrieval for each swath. These viewing geometry biases lead to artificial periodicities in the retrievals of NO2 tropospheric vertical columns over a specific coordinate or site, such as a city. Furthermore, there were significant differences found after using different a priori NO2 chemical transport models. The low horizontal resolution of TM4 and the satellite retrieval/TM4 coupling effect compared to REAM leads to considerable questioning of the near real time application of the KNMI NO2 retrieval product. Though the TM4 model performs poorly, TM4 retrievals do perform nearly as well as REAM retrievals at capturing day-to-day variability and the spatial variability of the cities used as examples here. The retrievals using TOMRAD outperformed the retrievals using DAK when compared to the high resolution, hourly REAM a priori chemical transport model. In sum, these findings should lead to better optimizations of both the KNMI and NASA retrievals, and thus make their publicly available data products more reliable and accurate for general use.

The Infrared Atmospheric Sounding Interferometer (IASI) provides atmospheric observations with high spectral resolution and its data have been shown to have a significant positive impact on global Numerical Weather Prediction (NWP) and trace gas retrievals. A fundamental component of the retrieval of atmospheric composition is the radiative transfer model used to simulate the observations. An accurate representation of the expected emission spectrum measured by the satellite is essential given that differences in the reproduced atmospheric spectra propagate through a retrieval procedure and produce an altered estimate of the atmospheric state. The importance of the assumptions within the forward model are discussed and it is established that in the simulation of spectra from satellite-borne instruments the choice of the model parameters can have a large impact upon the resulting output. These assumptions are explored in the context of the Reference Forward Model (RFM), which is further configured to optimise its output for simulating the IASI spectrum in the troposphere. In order to ascertain the consistency of different radiative transfer models, comparisons are carried out between the RFM and the Radiative Transfer model for TOVS (RTTOV) in order to quantify any discrepancies in the reproduction of IASI measurements. Good agreement is shown across the majority of the spectrum, with exceptions caused by CO₂ line mixing effects and the H₂O continuum. Alongside model comparisons, the RFM is validated against real IASI measurements. Being a Fourier Transform Spectrometer, there are a large number of channels available from the IASI instrument, which leads to a very large quantity of data. However, this can lead to problems within retrievals and data assimilation. Choosing an optimal subset of the channels is an established method to reduce the amount of data; maintaining the information contained within it whilst eliminating spectral regions with large uncertainties. The method currently used at the UK Met Office to select their spectral channels is re-assessed and a modified method is presented that improves upon the modelling of spectrally correlated errors.

This thesis presents the development and validation of the Hurricane Imaging Retrieval Algorithm (HIRA) for the measurement of oceanic surface wind speed and rain rate in hurricanes. The HIRA is designed to process airborne microwave brightness temperatures from the NOAA, Stepped Frequency Microwave Radiometer (SFMR), which routinely collects data during NOAA hurricane hunter aircraft flights. SFMR measures wind speeds and rain rates at nadir only, but HIRA will soon be integrated with an improved surface wind speed model for expanded utilization with next generation microwave hurricane imagers, such as the Hurricane Imaging Radiometer (HIRad). HIRad will expand the nadir only measurements of SFMR to allow the measurement of hurricane surface winds and rain over a wide swath Results for the validation of HIRA retrievals are presented using SFMR brightness temperature data for 22 aircraft flights in 5 hurricanes during 2003-2005. Direct comparisons with the standard NOAA SFMR empirical algorithm provided excellent results for wind speeds up to 70 m/s. and rain rates up to 50 mm/hr.

First devised over half a century ago, metal-on-polyethylene (MoP) hip prostheses have become the gold standard for total hip arthroplasty (THA), a surgical intervention for degenerative hip joint conditions. The accumulation of polyethylene wear debris after long-term, in vivo articulations, can induce adverse cellular reactions, osteolysis and aseptic loosening of the implant – ultimately resulting in the failure of the THA. Despite the distinct differences between the biotribology of MoP and MoM prostheses, there is a lack of congruent high resolution research investigating the biotribological interactions and surface structures of MoP hip prosthesis components. This study characterized the surface and subsurface microstructural changes in failed MoP hip prosthesis retrievals using advanced electron microscopy techniques. The samples were comprised of retrieved metallic cobalt-chromium-molybdenum (CoCrMo) alloy femoral head components, one ultra-high molecular weight polyethylene (UHMWPE) acetabular cup component, and unused CoCrMo reference samples. The surface of the reference samples contained linear, parallel, uniform scratches as a result of the manufacturing process; whereas the surface of the retrieval samples were covered in an abundance of scratches and a layer of residual deposits, attributable to in vivo articulation of the implant. Characteristic hard phases were observed and examined on the surface and from the cross-sectional preparation of the cast CoCrMo samples. The multiphasic hard phases on the cast samples can strengthen the material but also be sites of crack propagation and material detachment, contributing to the generation of wear particles. Lastly, a nanocrystalline layer, 20 to 400 nm in thickness was observed in the subsurface microstructure of all samples (including references). Previous MoM studies suggest that the nanocrystalline layer is a result of dynamic crystallization in response to multidirectional, chronic loading in vivo, however, the presence of the layer in the unimplanted references suggest that the nanocrystalline layer can be formed during the production of the prosthesis component and therefore, pre-exists implantation. The imperfections on new, unused implants can have protective effects (e.g. troughs from scratches can be a reservoir for wear debris) but may influence in vivo wear processes after implantation (e.g. scratches may be a source of wear debris). Higher resolution analyses on more retrieval and reference samples are required to pinpoint the exact mechanism of failure in MoP hip prostheses and extend the longevity and efficacy of THA. / Thesis / Master of Applied Science (MASc)