Physical Sciences and Mathematics Commons^™

Uhplc/Ft-Ms Non-Targeted Screening Approach For Biomass Burning Organic Aerosol And Liquid Smoke As Biomass Burning Organic Aerosol Surrogate, D.M.R. Thusitha Dinusha Kumarihami Divisekara

Dissertations, Master's Theses and Master's Reports

Biomass combustion contributes a large amount of aerosol particles to the atmosphere impacting the climate system and human health. Identifying the molecular composition of biomass burning organic aerosol (BBOA) is challenging because of its complex nature. Liquid chromatography mass spectrometric non-targeted screening (NTS) methods provide a comprehensive analysis. However, the instrumentation and data analysis are challenging due to the extreme complexity of environmental samples. In the first part of this study, we implemented a new LC/FT-MS data processing approach by combining existing open-source data processing tools, MZmine2.53 and MFAssignR. The method's validity was checked using the standard polyacrylic acid (PAA) …

The Photo-Transformation Of Free Methionine In The Presence Of Surrogate And Standard Isolate Dissolved Organic Matter Under Sunlit Irradiation, Benjamin J. Mohrhardt

Dissertations, Master's Theses and Master's Reports

Sulfur (S)-containing amino acids are key sources of carbon, nitrogen, and sulfur involved in protein synthesis, protein function, and providing energy for microbial growth. Dissolved free and combined methionine is one of two S-containing amino acids incorporated into proteins and has been attributed to their stability and function. The oxidation of methionine has received considerable attention given its ubiquitous presence in most biological systems and has been associated with losses in protein function and pathological disorders. In natural waters, methionine is rapidly and selectively taken up by microorganisms to achieve cellular requirements of carbon, nitrogen, and sulfur. The abiotic transformation …

High-Resolution Molecular Characterization Of Complex Environmental Mixtures: Aquatic Dissolved Organic Matter And Wildfire-Influenced Aerosol, Amna Ijaz

Dissertations, Master's Theses and Master's Reports

The natural environment is replete with organic matter of varying complexities. Whether it is particulate material in the atmosphere, decades old organic matter trapped within glaciers, or biological debris flowing with rivers and streams, natural organic matter (NOM) is exquisitely complex. High-resolution mass spectrometry allows us to have a glimpse of the molecular composition of NOM and delineate the elemental compositions of thousands of chemical species that form it. In this dissertation, the overarching aim was to explore the molecular diversity of complex mixtures from two sources: Surface water and atmospheric organic aerosol. The first objective of this dissertation was …

Cobalt, Molybdenum, And Nickel Complexes, Natural Zeolites, Epoxidation, And Free Radical Reactions, Nicholas K. Newberry

Dissertations, Master's Theses and Master's Reports

Chapter 2 is based on the synthesis and study of the compounds of the bidentate ligand ((5-phenyl-1H-pyrazol-3-yl)methyl)phosphine oxide with molybdenum and cobalt as the transition metal. The complexes were analyzed via FTIR, NMR, UV-Vis, Fluorescence Spectroscopy, TGA, DFT, and XRD. Chapter 3 resulted in the synthesis of the complexes [Ni(II)SSRRL](PF6)2 and [Ni(II)SRSRL](Cl)(PF6) of which [Ni(II)SRSRL](Cl)(PF6) had not been previously analyzed. Both products were analyzed via FTIR, NMR, UV-Vis, CV, DFT, and XRD. Chapter 5 contains the results of the characterization and modification of 4 natural zeolites (AZLB-Na, AZLB-Ca, NM-CA, NV-Na) from the United States in an attempt to increase the …

Method Considerations For Compound Identification In Complex Mixtures Using Electrospray Ionization Ultrahigh Resolution Mass Spectrometry, Tyler Leverton

Dissertations, Master's Theses and Master's Reports

Biomass burning aerosols are highly complex organic mixtures of thousands of components with consequences for global climate. Complex mixture component identification requires accurate mass measurement capability to separate components on a milli-Dalton scale, frequently using ultrahigh resolution mass spectrometry with electrospray ionization. Certain sample preparations and the ionization process may introduce artifacts that obscure the composition of the sample. Two method considerations were explored using isotopically labeled ¹⁵NH₄OH and MeOH-d₃ to track artifact formation in biomass burning samples. Informatics techniques and a custom molecular formula assignment software were used to identify the isotopic atoms in artifact …

Molecular Characterization Of Free Tropospheric Organic Aerosol And The Development Of Computational Tools For Molecular Formula Assignment, Simeon Schum

Dissertations, Master's Theses and Master's Reports

Organic aerosol affects human health and climate. These effects are largely determined by the composition of the organic aerosol, which is a complex mixture of species. Understanding the complexity of organic aerosol is critical to determining its effect on human health and climate. In this study, long range transported organic aerosol collected at the Pico Mountain Observatory was analyzed using ultrahigh resolution mass spectrometry. Organic aerosol transported in the free troposphere had an overall lower extent of oxidation than aerosol transported in the boundary layer. It was hypothesized that the lower oxidation was related to a more viscous phase state …

Extreme Molecular Diversity In Biomass Burning Atmospheric Organic Aerosol Observed Through Ultrahigh Resolution Mass Spectrometry, Matthew Brege

Dissertations, Master's Theses and Master's Reports

Ambient atmospheric aerosol is ubiquitous in the atmosphere, originating from a variety of natural and man-made sources. These microscopic particles have profound impacts on the global climate system as well as human health. The organic fraction of atmospheric aerosol is an extremely complex mixture which is not yet fully characterized. These unknown organic aerosol species contribute to the uncertainty in the effect of aerosol on climate and uncertainty in overall ambient aerosol toxicity. Light absorbing organic aerosol can interact with incoming solar radiation and contribute to atmospheric heating; however, the source apportionment and overall fate of these absorbing organic aerosol …

Biogeochemical Response To Vegetation And Hydrologic Change In An Alaskan Boreal Fen Ecosystem, Danielle L. Rupp

Dissertations, Master's Theses and Master's Reports

Boreal peatlands store approximately one third of the earth’s terrestrial carbon, locked away in currently waterlogged and frozen conditions. Peatlands of boreal and arctic ecosystems are affected increasingly by shifting hydrology caused by climate change. The consequences of these relatively rapid ecosystem changes on carbon cycling between the landscape and the atmosphere could provide an amplifying feedback to climate warming. Alternatively, the advancement of terrestrial vegetation into once waterlogged soils could uptake carbon as a sink. Previous work suggests that fens will become an increasingly dominant landscape feature in the boreal. However, studies investigating fens, their response to hydrologic and …

A Model To Predict Concentrations And Uncertainty For Mercury Species In Lakes, Ashley Hendricks

Dissertations, Master's Theses and Master's Reports

To increase understanding of mercury cycling, a seasonal mass balance model was developed to predict mercury concentrations in lakes and fish. Results indicate that seasonality in mercury cycling is significant and is important for a northern latitude lake. Models, when validated, have the potential to be used as an alternative to measurements; models are relatively inexpensive and are not as time intensive. Previously published mercury models have neglected to perform a thorough validation. Model validation allows for regulators to be able to make more informed, confident decisions when using models in water quality management. It is critical to quantify uncertainty; …

Wildfire Emissions In The Context Of Global Change And The Implications For Mercury Pollution, Aditya Kumar

Dissertations, Master's Theses and Master's Reports

Wildfires are episodic disturbances that exert a significant influence on the Earth system. They emit substantial amounts of atmospheric pollutants, which can impact atmospheric chemistry/composition and the Earth’s climate at the global and regional scales. This work presents a collection of studies aimed at better estimating wildfire emissions of atmospheric pollutants, quantifying their impacts on remote ecosystems and determining the implications of 2000s-2050s global environmental change (land use/land cover, climate) for wildfire emissions following the Intergovernmental Panel on Climate Change (IPCC) A1B socioeconomic scenario.

A global fire emissions model is developed to compile global wildfire emission inventories for major atmospheric …

Molecular Characterization Of Atmospheric Organic Matter In Biogenic Secondary Organic Aerosol, Ambient Aerosol And Clouds, Yunzhu Zhao

Dissertations, Master's Theses and Master's Reports - Open

Atmospheric aerosol affects the Earth’s energy budget, reduces visibility and influences human health. The organic composition of aerosol is quite complex and continuously evolves through various atmospheric processes. To gain a deeper understanding of the molecular composition of atmospheric organic matter (AOM), chamber-generated biogenic secondary organic aerosol (SOA), ambient aerosol and cloud water samples were studied. Ultrahigh resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry was used to provide detailed molecular characterization of the atmospheric samples. Due to the extremely high mass resolution and mass accuracy, thousands of individual molecular formulas were identified in all of the samples studied. Multivariate …

Modeling Dynamics Of Ozone And Nitrogen Oxides At Summit, Greenland With A 1-D Process-Scale Model, Keenan Anton Murray

Dissertations, Master's Theses and Master's Reports - Open

This work presents a 1-D process scale model used to investigate the chemical dynamics and temporal variability of nitrogen oxides (NO_x) and ozone (O₃) within and above snowpack at Summit, Greenland for March-May 2009 and estimates surface exchange of NO_x between the snowpack and surface layer in April-May 2009. The model assumes the surface of snowflakes have a Liquid Like Layer (LLL) where aqueous chemistry occurs and interacts with the interstitial air of the snowpack. Model parameters and initialization are physically and chemically representative of snowpack at Summit, Greenland and model results are compared to …