A. James Clark School of Engineering
Permanent URI for this communityhttp://hdl.handle.net/1903/1654
The collections in this community comprise faculty research works, as well as graduate theses and dissertations.
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Item ATMOSPHERIC ORGANIC AEROSOLS: THE EFFECT OF PHYSIOCHEMICAL PROPERTIES ON HYGROSCOPICITY(2023) Malek, Kotiba; Asa-Awuku, Akua; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Aerosols, tiny solid or liquid particles, are ubiquitous in the atmosphere yet their impact on climate remains poorly understood. One prominent way aerosols are able to impact the climate is through their ability to uptake water and form clouds. The chemical diversity and aerosol interactions in the atmosphere can greatly complicate the investigation of aerosol-cloud interactions. This complexity is expressed with a large uncertainty associated with aerosols’ role on climate change. This dissertation investigates the aerosol-cloud interaction by measuring the water uptake of atmospherically relevant aerosols. Our results highlight the importance of accounting for various physiochemical properties when exploring the water uptake of atmospheric aerosols. One such property is liquid-liquid phase separation (LLPS) in ternary mixtures. Our work offers new evidence, insight, and a paradigm shift to the contribution of LLPS to supersaturated droplet activation. We complemented this finding with a theoretical model, that incorporates solubility, O:C ratio, and LLPS, for predicting κ-hygroscopicity of ternary mixtures. Another physiochemical property that was shown to play a key role in droplet activation of polymeric aerosols is chemical structure. Our study shows that polycatechol is more hygroscopic than polyguaiacol and the difference in hygroscopicity is attributed to the density of hydroxyl groups in both structures. Polycatechol has a higher density of hydroxyl groups than polyguaiacol, resulting in polycatechol having stronger water uptake affinity than polyguaiacol. When maintaining the same structural makeup by investigating the water uptake of two isomeric compounds, we discovered that solubility was the driving force in water uptake. The more soluble isomer o-aminophenol was more hygroscopic than p-aminophenol. Hence, a small change in the position of functional groups can impact solubility which in turn influence hygroscopicity. Lastly, we explored the presence of gas-phase organics on the water uptake of isomers with a wide range of solubilities. Our work highlights that gas-phase organics, specifically ethanol, can influence the water uptake of aerosols. Ethanol was shown to increase water uptake efficiencies based on solubility, with the least soluble compound showing stronger affinity to water uptake. Overall, this thesis advances our knowledge and understanding of aerosol-cloud interactions and its implications on climate change.Item AEROSOL-CLOUD-CLIMATE INTERACTIONS DUE TO CARBONACEOUS AEROSOLS(2022) Gohil, Kanishk; Asa-Awuku, Akua A; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Aerosols can affect the net radiation budget and global climate of the Earth either “directly” – through their radiative properties, or “indirectly” – through their cloud-forming abilities by acting as Cloud Condensation Nuclei (CCN). The interactions between aerosols and clouds are the most significant sources of uncertainty in the overall radiative forcing from due to a lack of understanding related to the droplet formation mechanism of aerosols. These uncertainties are majorly associated with the carbonaceous aerosols present in the atmosphere, notably due to their compositional diversity, vastly variable physicochemical properties, and unique water uptake characteristics. In this dissertation, new lab-based measurement techniques and computational methods have been developed to resolve the CCN activity and water uptake behavior of pure and mixed carbonaceous aerosol particles.The first part of this dissertation accomplishes two goals: 1. The development and application of a new CCN measurement method, and 2. The formulation of a new computational framework for CCN activity analysis of aerosols. The results in this dissertation demonstrate the significance of size-resolved morphology and dissolution properties of aerosol particles in improving their CCN activity analysis under varying ambient conditions. Furthermore, these results suggest that in the future, more comprehensive CCN analysis frameworks can be developed by explicitly treating other physical and chemical properties of the aerosols to further improve their CCN activity analysis. The second part of this dissertation focuses on large-scale analysis. The CCN analysis framework is implemented into a climate model to quantify the water uptake behavior of carbonaceous aerosols, and then study the subsequent variabilities associated with the physical and radiative properties of ambient aerosols and clouds. Statistical techniques are also developed in this work for chemical characterization of ambient aerosols. The characterization results show large regional compositional variations in ambient aerosol populations. These results also suggest that the knowledge of chemical species is necessary to quantify the water uptake properties of the aerosol population.Item EXPERIMENTAL CHARACTERIZATION OF ATMOSPHERIC TURBULENCE SUPPORTED BY ADVANCED PHASE SCREEN SIMULATIONS(2020) PAULSON, DANIEL A; Davis, Christopher C; Electrical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Characterization of optical propagation through the low turbulent atmosphere has been a topic of scientific investigation for decades, and has important engineering applications in the fields of free space optical communications, remote sensing, and directed energy. Traditional theories, starting with early radio science, have flowed down from the assumption of three dimensional statistical symmetry of so-called fully developed, isotropic turbulence. More recent experimental results have demonstrated that anisotropy and irregular frequency domain characteristics are regularly observed near boundaries of the atmosphere, and similar findings have been reported in computational fluid dynamics literature. We have used a multi-aperture transmissometer in field testing to characterize atmospheric transparency, refractive index structure functions, and turbulence anisotropy near atmospheric boundaries. Additionally, we have fielded arrays of resistive temperature detector probes alongside optical propagation paths to provide direct measurements of temperature and refractive index statistics supporting optical turbulence observations. We are backing up these experimental observations with a modified algorithm for modeling optical propagation through atmospheric turbulence. Our new phase screen approach utilizes a randomized spectral sampling algorithm to emulate the turbulence energy spectrum and improve modeling of low frequency fluctuations and improve convergence with theory. We have used the new algorithm to investigate open theoretical topics, such as the behavior of beam statistics in the strong fluctuation regime as functions of anisotropy parameters, and energy spectrum power law behavior. These results have to be leveraged in order to develop new approaches for characterization of atmospheric optical turbulence.Item REAL-TIME COMPARISON OF PHYSICAL AND CHEMICAL AEROSOL MEASUREMENT METHODS(2019) OYEBANJO, FRANCIS; Asa-Awuku, Akua; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Atmospheric aerosols are major contributors to air pollution. Overexposure to these particles can cause severe respiratory and cardiovascular impairments. Aerosols also affect the planet's climate through radiative forcing. Various techniques exist to monitor the physical and chemical characteristic of aerosols but few allow for real-time analysis. In this thesis, real-time field measurements of aerosol particles were compared with values reported by state regulatory agencies. These values were also compared to mass concentrations of PM2.5 in order to determine if a correlation exists between the two. Lastly, the relationship between particle mobility-size and chemical characterization using Raman spectroscopy is explored in an effort to obtain quantitative semi-continuous spectral data. This study found no variation between local and regional particulate matter measurements and no discernable correlation between PM2.5 mass and particle number concentration. The relationship between particle size and Raman intensity remains unknown due to the non-uniformity of mobility-size selected particles.Item Forward Scattering Meter for Visibility Measurements(2019) Ferlic, Nathaniel A.; Davis, Christopher C; Van Iersel, Miranda; Electrical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Atmospheric aerosols, containing water, constitute most of the air during non-ideal weather conditions including fog, haze, and mist. These aerosols cause light to be attenuated while propagating through the atmosphere causing the effective visibility to decrease. The visibility is dependent on the extinction coefficient of the aerosol distribution that can be found using Mie scattering theory. In the case of a real environment a distribution of particle sizes must be considered where the particles present are described by a weighted value relative to the number density. In this thesis a forward scattering meter is devised that measures the amount of scattered light at a specific forward scattering angle under the assumption that the scattered light is linearly related to the extinction coefficient of different weather conditions. To validate the design, it will be compared against a commercial visibility meter along with using a fog chamber to simulate various weather conditions.Item DATA-DRIVEN STUDIES OF TRANSIENT EVENTS AND APERIODIC MOTIONS(2019) Wang, Rui; Balachandran, Balakumar; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The era of big data, high-performance computing, and machine learning has witnessed a paradigm shift from physics-based modeling to data-driven modeling across many scientific fields. In this dissertation work, transient events and aperiodic motions of complex nonlinear dynamical system are studied with the aid of a data- driven modeling approach. The goal of the work has been to further the ability for future behavior prediction, state estimation, and control of related behaviors. It is shown that data on extreme waves can be used to carry out stability analysis and ascertain the nature of the transient phenomenon. In addition, it is demonstrated that a low number of soliton elements can be used to realize a rogue wave on the basis of nonlinear interactions amongst the basic elements. The pro- posed nonlinear phase interference model provides an appealing explanation for the formation of ocean extreme wave and related statistics, and a superior reconstruction of the Draupner wave event than that obtained on the basis of linear superposition. Chaotic data, another manifestation of aperiodic motions, which are obtained from prototypical ordinary differential and partial differential systems are considered and a neural machine is realized to predict the corresponding responses based on a limited training set as well to forecast the system behavior. A specific neural architecture, called the inhibitor mechanism, has been designed to enable chaotic time series forecasting. Without this mechanism, even the short-term predictions would be intractable. Both autonomous and non-autonomous dynamical systems have been studied to demonstrate the long-term forecasting possibilities with the de- veloped neural machine. For each dynamical system considered in this dissertation, a long forecasting horizon is achieved with a short historical data set. Furthermore, with the developed neural machine, one can relax the requirement of continuous historical data measurements, thus, providing for a more pragmatic approach than the previous approaches available in the literature. It is expected that the efforts of this dissertation work will lead to a better understanding of the underlying mechanism of transient and aperiodic events in complex systems and useful techniques for forecasting their future occurrences.Item Soot Oxidation in Flames: Nanostructure, Morphology, and Chemical Kinetics(2019) Anderson, Paul Marcus; Sunderland, Peter B.; Mechanical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Soot produced from the combustion of hydrocarbons is of immense scientific interest owing to its deleterious effects on human health and the environment. Despite decades of research, existing soot models are accurate across only a narrow range of combustion conditions. A substantial portion of this inaccuracy is rooted in the multitude of factors affecting soot oxidation that remain ill-understood. In the current work, a novel flame system allowed soot oxidation to be observed in isolation from competing soot formation processes. Measurements tracked evolving soot structures, oxidation rates, temperatures and gas species concentrations. Transmission electron microscopy (TEM) was used to characterize soot structure at aggregate, primary particle, and nanostructural scales. For this, a program called Aerosol Image Analyzer was developed, incorporating new algorithms for processing and measuring TEM images of mass-fractal aerosols, like soot. For the first time, TEM image measurement uncertainties incorporating sample, operator, and random effects, were quantified through gage repeatability and reproducibility analysis. Successful methods for reducing operator bias were presented, and automated measurement methods from literature were tested and found to be unreliable. Measurements of surface area by N2 adsorption validated TEM as a technique for determining soot specific surface area, provided that the polydispersity and partial sintering of primary particles is taken into account. TEM measurements of soot undergoing oxidation showed continuously decreasing primary particle size distributions and increasing specific surface area. Measurements of soot aggregate morphology found a fractal dimension of 1.74 that was unchanged by oxidation. The breakup of aggregates by oxidative fragmentation was observed for the first time using methods that combined TEM analysis with laser extinction. Soot nanostructure was characterized through high resolution TEM measurements of lattice fringe length, tortuosity, orientation, and separation distance. It was observed that primary particles could be divided into an inner 80%, where lattice fringes showed greater graphitic order with increasing radial location, and an outer 20%, where this trend was reversed. While oxidation proceeded in a shrinking-sphere manner at the particle surface, the interior underwent thermal and oxidation-induced graphitization, challenging the assumption that the nanostructure of mature soot is “locked-in.” This results in a surface nanostructure that is effectively unchanging from the perspective of the oxidizing gases and corresponds to a constant collision efficiency kinetics model.Item Characterizing Atmospheric Turbulence with Conventional and Plenoptic approaches(2017) Ko, Jonathan; Davis, Christopher C; Electrical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Atmospheric turbulence is a phenomenon of interest in many scientific fields. The direct effects of atmospheric turbulence can be observed in everyday situations. The twinkling of stars is an indicator of weak atmospheric turbulence while the shimmering of objects above a hot surface is an indicator of strong atmospheric turbulence. The effects of atmospheric turbulence are generally considered a nuisance to optical applications. Image blurring effects are often present when observing distant objects through atmospheric turbulence. Applications that require maintaining the coherence of a laser beam, such as in free space optical communication, suffer from poor link quality in the presence of atmospheric turbulence. Attempts to compensate for the effects of atmospheric turbulence have varied in effectiveness. In astronomical applications, weak cases of atmospheric turbulence have been successfully compensated with the use of a Shack-Hartmann wavefront sensor combined with adaptive optics. Software techniques such as “Lucky Imaging” can be useful when clear images briefly appear through the presence of weak turbulence. However, stronger cases of atmospheric turbulence often found in horizontal or slant paths near the Earth’s surface present a much more challenging situation to counteract. This thesis focuses primarily on the effects of strong or “deep” atmospheric turbulence. The process of compensating for the effects of strong atmospheric turbulence begins with being able to characterize it effectively. A scintillometer measures the scintillation in the intensity of a light source to determine the strength of current turbulence conditions. Thermal fluctuation measurements can also be used to derive the strength of atmospheric turbulence. Experimental results are presented of a developed large aperture scintillometer, thermal probe atmospheric characterization device, and a transmissometer. While these tools are effective in characterizing atmospheric turbulence, they do not provide for a means to correct for turbulence effects. To compensate for the effects of atmospheric turbulence, the development of the Plenoptic Sensor is presented as a wavefront sensor capable of handling strong turbulence conditions. Theoretical and experimental results are presented to demonstrate the performance of the Plenoptic Sensor, specifically in how it leads to adaptive optics algorithms that can rapidly correct for the effects of turbulence.Item OBSERVATIONS AND EMISSIONS OF ENERGY-ASSOCIATED OZONE PRECURSORS IN THE MID-ATLANTIC UNITED STATES(2016) Vinciguerra, Timothy P.; Ehrman, Sheryl H.; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Surface ozone is formed in the presence of NOx (NO + NO2) and volatile organic compounds (VOCs) and is hazardous to human health. A better understanding of these precursors is needed for developing effective policies to improve air quality. To evaluate the year-to-year changes in source contributions to total VOCs, Positive Matrix Factorization (PMF) was used to perform source apportionment using available hourly observations from June through August at a Photochemical Assessment Monitoring Station (PAMS) in Essex, MD for each year from 2007-2015. Results suggest that while gasoline and vehicle exhaust emissions have fallen, the contribution of natural gas sources to total VOCs has risen. To investigate this increasing natural gas influence, ethane measurements from PAMS sites in Essex, MD and Washington, D.C. were examined. Following a period of decline, daytime ethane concentrations have increased significantly after 2009. This trend appears to be linked with the rapid shale gas production in upwind, neighboring states, especially Pennsylvania and West Virginia. Back-trajectory analyses similarly show that ethane concentrations at these monitors were significantly greater if air parcels had passed through counties containing a high density of unconventional natural gas wells. In addition to VOC emissions, the compressors and engines involved with hydraulic fracturing operations also emit NOx and particulate matter (PM). The Community Multi-scale Air Quality (CMAQ) Model was used to simulate air quality for the Eastern U.S. in 2020, including emissions from shale gas operations in the Appalachian Basin. Predicted concentrations of ozone and PM show the largest decreases when these natural gas resources are hypothetically used to convert coal-fired power plants, despite the increased emissions from hydraulic fracturing operations expanded into all possible shale regions in the Appalachian Basin. While not as clean as burning natural gas, emissions of NOx from coal-fired power plants can be reduced by utilizing post-combustion controls. However, even though capital investment has already been made, these controls are not always operated at optimal rates. CMAQ simulations for the Eastern U.S. in 2018 show ozone concentrations decrease by ~5 ppb when controls on coal-fired power plants limit NOx emissions to historically best rates.Item Controlling ammonia emissions from concentrated feeding operations(2011) Satam, Chinmay Charuhas; Ehrman, Sheryl H; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Ammonia is an essential component in the formation of particulate matter which has been a growing concern for areas along the Mid-Atlantic region. Also, animal husbandry operations have been isolated as the single largest sources of ammonia. Hale III (2005) suggests a strategy to reduce ammonia emissions from chicken manure using a dietary gypsum-zeolite infusion and slight crude protein reductions. A follow up study conducted by Wu-Haan et al. (2007) places the ammonia reduction values at 39 %. Simulations of this strategy for the MANEVU region find PM2.5 reductions of up to 37.5% for the Delmarva Peninsula. Additionally, 6 hours of improved compliance (15 μg/m3 standard) is seen in this region, during moderate PM2.5 episodes. It was also observed that regions near the source, and down wind, with high available nitric to sulfuric acid ratios are benefited by this strategy which primarily targets ammonium nitrates.