Physical Sciences and Mathematics Commons^™

Molecular Evidence For The Export Of Terrigenous Organic Matter To The North Gulf Of Mexico By Solid-State 13C Nmr And Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Of Humic Acids, Sarah Ann Ware

Chemistry & Biochemistry Theses & Dissertations

Marine organic matter is mainly believed to originate from autochthonous organic matter, while terrigenous organic matter is assumed to be largely degraded prior to reaching the open ocean or more recently replaced by marine organic matter via a stripping process. Sediment samples along a transect extending from the Mississippi River Birdsfoot Delta to the Mississippi Canyon on the Louisiana continental shelf were examined by advanced analytical techniques, electrospray ionization coupled to a 12T Fourier transform ion cyclotron resonance mass spectrometer (ESI-FTICR-MS) and quantitative solid-state multiple cross polarization magic angle spinning (multi-CPMAS) ¹³C NMR in an effort to understand the …

Improvement Of Biochar Through Ozonization And Biosafety Of Genetically Engineered Cyanobacteria, Oumar Sacko

Chemistry & Biochemistry Theses & Dissertations

Through the innovative technique of biochar post-production surface oxygenation by ozonization, we were able to improve certain properties of biochar. In project one, the incubation of an insoluble phosphate rock material (hydroxyapatite) with the wet ozonized pine 400 biochar and its filtrate resulted in a solubilization of 80 times more phosphate from hydroxyapatite (569.0 mg/L ± 6.4) compared to the pure water-hydroxyapatite control (7.2 mg/L ± 0.3). The ozonized biochar may provide a new possible way to unlock the phosphorus from insoluble phosphate mineral phases. The cation exchange capacity (CEC) is a key property of biochar when used as a …

Advances In The Understanding Of Sourcing And Fate Of Pyrogenic Organic Matter In The Environment, Aleksandar Ivaylov Goranov

Chemistry & Biochemistry Theses & Dissertations

With higher occurrences of forest fires worldwide, there has been an increase in scientific interest surrounding the chemistry of pyrogenic organic matter (pyOM). The main structural components of pyOM, the condensed aromatic compounds (ConAC), exhibit intriguing physico-chemical properties and have been one of the main focuses of biogeochemical research. The overwhelmingly large number of scientific articles regarding pyOM and ConAC are guided by the assumption that ConAC in the environment are exclusively of pyrogenic origin, even though some recent studies have suggested that some of these ConAC could also be derived from non-pyrogenic radical-driven processes. To evaluate this controversial proposition, …

Lignin: A Likely Precursor Of A Significant Fraction Of Humic Substances Via Oxidative Transformations, Seyyedhadi Khatami

Chemistry & Biochemistry Theses & Dissertations

Lignin is a major component of decaying terrestrial vegetation in soils and has been arguably reported to contribute substantially to the formation of soil carbon humus, and natural dissolved organic matter (DOM). To better understand the process by which this humification occurs, lignin and lignin-derived monomers were subjected to both biotic and abiotic oxidation processes. Two well-known oxidative transformation strategies were employed. The first involved the fungal degradation of brown-rot degraded wood subjected to a white-rot fungus (Phanerochaete chrysosporium) whose enzymes are particularly effective in lignin degradation via enzymatic oxidation. This enzymatic attack was monitored by ultrahigh resolution …

Observations Of Greenhouse Gas Isotopologues With Ace-Fts And Waccm, Eric Michael Buzan

Chemistry & Biochemistry Theses & Dissertations

Increases in greenhouse gas concentrations in the atmosphere are the major driver of climate change. Quantifying the sources and sinks of these gases is a major focus of research. Measuring isotopologues, or molecules that differ in isotopic composition, is one useful way of constraining the budget of a molecule as they are highly sensitive to different sources and sinks. However, measurements above the surface have been restricted to a few locations and have only reached the lower stratosphere. Satellite-based remote sensing can achieve nearly global measurement coverage, but so far no satellites have measured isotopologues.

Presented here are measurements of …

Artificial Maturation Studies Of Polymethylenic Plant Biopolymers: Investigating The Chemical Alterations From Plant Material To Coal, Blaine Elizabeth Hartman

Chemistry & Biochemistry Theses & Dissertations

The thermal maturation and alternation of vascular plant material into coals and as expelled petroleum-like compounds is the main focus of this dissertation. Utilizing artificial maturation studies, like hydrothermal liquefaction, yields useful information regarding how plant material is preserved in coals and the potential certain plant biopolymers possess to generate liquid fuels is acquired. The studies within this dissertation focus on utilizing the aliphatic biopolymers, cutin, cutan, and suberan, found in the epidermis of certain plants. These biopolymers contain minimal amounts of heteroatoms and are comprised of long polymethylenic chains, which are desirable characteristics in generating bio-oils. Additionally, understanding the …

Advances In Understanding The Molecular Composition Of Dissolved Organic Matter And Its Reactivity In The Environment, Rajaa Mesfioui

Chemistry & Biochemistry Theses & Dissertations

Dissolved organic matter (DOM) is the ultimate product of Earth's systems dynamics. DOM chemical signature is strongly shaped by the interaction among Earth's spheres, such as the atmosphere, the geosphere, the biosphere, and the hydrosphere, but also life and human activity. DOM source, composition, photochemical alteration and availability affect freshwater ecosystems, their carbon and nitrogen fluxes and, thus, the global carbon and nitrogen cycles. The aim of this thesis was to gain an understanding of the molecular composition of DOM and its photochemical and biological reactivity in an environment impacted by anthropogenic disturbance. The York and James River systems within …

Bacterial Degradation Of Disinfection By-Products In Drinking Water, Laura Inga Fauntleroy

Chemistry & Biochemistry Theses & Dissertations

Chlorine became a major disinfectant for the removal of microbial contaminants in 1914. Current water chlorination procedures yield halogenated disinfection byproducts (DBPs), such as haloalkanes and haloacetic acids (HAAs), due to the reaction of chlorine with naturally occurring organic compounds. Various water utilities have observed decreased HAAs levels in maximum residence time locations (MRTLs), where they were expected to be higher. These MRTLs have low free chlorine residual and high heterotrophic bacteria plate counts. Xanthobacter autotrophicus, GJ-10, is a bacterium that has been shown to contain dehalogenase enzymes and, therefore, can biodegrade HAAs. A number of water-system bacteria were …

Determination Of The N-Terminal Amino Acid Residues On Polypeptides In Secondary Wastewaters, Edward L. Creecy

Chemistry & Biochemistry Theses & Dissertations

The N-terminal amino acid residues on polypeptides and proteins were determined in wastewaters prior to chlorination. The terminal amino groups'ere first derivatized with the well known derivatizing agent dansyl chloride, and then the resulting dansyl amino acid hydrolyzed from the peptide chain by a propionic acid/ hydrochloric acid mixture. The resulting dansyl amino acids were then separated and detected using reversed phase high performance liquid chromatography with fluorescence detection. The majority of N-terminal residues detected were the more polar amino acids. Concentrations ranged from 1 x 10^-10 to 3 x 10^-7 moles/liter. It is suggested that the shorter …

Evaluation Of Solid Phase Extraction Followed By Supercritical Fluid Elution Of Semi-Volatile Organic Compounds In Toxicity Characteristic Leachates, William Edward Corl Iii

Chemistry & Biochemistry Theses & Dissertations

The Environmental Protection Agency (EPA) developed the toxicity characteristic leaching procedure (TCLP) to determine the potential for unknown wastes to leach haz.ardous constituents into the environment. Methods currently being used for the extraction of semi-volatile organic compounds from aqueous TCLP leachates involve acid/base partitioning into methylene chloride. The concentrated extract is then analyzed by gas chromatography/mass spectrometry (GC/MS). The methods are either timeconsuming or labor intensive and they generate significant volumes of haz.ardous wastes themselves. Considering the haz.ards and disposal costs of methylene chloride wastes, great interest has been elicited by the EPA in other extraction techniques which would reduce …

Development Of A Fluorescent Indicator For Inorganic Monochloramine, Xiaojun Dong Zou

Chemistry & Biochemistry Theses & Dissertations

Current methods used to determine combined residual chlorine cannot distinguish between inorganic monochloramine (NH₂Cl) and organic chloramines. Studies described in this thesis were carried out to develop a novel method of determining the concentration of inorganic monochloramine in aqueous solutions. Based on the observation that the reaction of 3-formyl-1-methylpyridinium chloride (3FMPCl) with NH₂Cl produces a solution which is fluorescent, experiments were conducted to characterize the reaction and optimize the experimental conditions. Using the finalized protocol, NH₂Cl measurements were made in the presence and absence of organic amines and compared with a commonly used N, …

A Study Of The Chlorination Products Of Methionine In Model Solutions And In Wastewater, D. Scott Winters

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid methionine were chlorinated to seven chlorine-to-nitrogen (Cl₂/N) molar ratios. After 30 minutes, the solutions were analyzed by high performance liquid chromatography (HPLC). At a Cl₂/N molar ratio of 1, methionine sulfoxide was found to be the main product. At Cl₂/N molar ratios ≥ 2, a mixture of methionine sulfoxide, methionine sulfone, an unidentified sulfoxide (product 1), and N-chloro-3-(methylsulfonyl) propionaldimine are formed. These products were identified by comparison to synthesized standards which were characterized by ¹H-NMR and ¹³C-NMR nuclear magnetic resonance spectroscopy, ion trap mass spectroscopy, …

Chlorination Products Of Glycylphenylalanine In Model Solutions And A Wastewater, Daniel J. Keefe

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the dipeptide glycylphenylalanine were chlorinated to five different chlorine-to-amino nitrogen (Cl/N) mole ratios and analyzed after 30 min by high performance liquid chromatography. At mole ratios of ≤ 1, N-chloroglycylphenylalanine (I) appeared to be the only major product. At a mole ratio ≤ 2, N, N-dichloroglycylphenylalanine (II) was the only product. Compound II decomposes in model solutions (t_1/2= 6.4 hr) at pH 7.0 to form a compound tentatively identified as an H-chloroaldimine (III). Compound III in turn decomposes (t_1/2= 36 hr) in model solutions at pH 7. o to (IV) . From ^{13 …}

Stable N-Chloraldimines And Other Chlorination Products Of Phenylalanine In Model Solutions And In A Wastewater, Barbara L. Conyers

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid phenylalanine were chlorinated to seven Cl/N mole ratios. The by-products were characterized using gas chromatography, high performance liquid chromatography, GC/MS, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. At the lower Cl/N ratios N-chlorophenylalanine and phenylacetaldehyde were identified as the main products while phenylacetonitrile and N-chlorophenylacetaldimine were the major products at Cl/N ratios of 2.0 and beyond. The concentration of phenylalanine in a municipal wastewater was determined. Using a radiotracer the chlorination products of phenylalanine in the wastewater at the 7 Cl/N ratios were identified as those seen in the model solutions. The distribution of …

Reactions Of Organic N-Chloramines In The Gastric Fluid Of The Rat, Kathryn E. Mazina

Chemistry & Biochemistry Theses & Dissertations

Using chlorine as a drinking water disinfectant may have potential health effects due to its reactivity with organic amino nitrogen compounds found in the stomach. Organic N-chloramines have been shown to form in the stomachs of laboratory rats. The possible reactions of N-chloramines in the stomach fluid were examined in this study using a model radiolabeled N-chloramine. ³⁶Cl-N-Chloropiperidine, was synthesized and purified to remove ³⁶Cl-chloride. Stomach fluid was obtained from Sprague-Dawley rats which had been first fasted for 24 or 48 hours and then administered 3 mL of deionized water. Different concentrations of radiolabeled chloramine were reacted with …

Determination Of Amino Acids And Chloramino Acids In Municipal Wastewater, Jeffrey Taylor Jewell

Chemistry & Biochemistry Theses & Dissertations

It is well known that unchlorinated municipal wastewater contains high levels of organic and inorganic amino nitrogen compounds, the single most abundant amino-N species being ammonia. Upon chlorination, these compounds are transformed almost instantaneously and quantitatively into N-chloramino derivatives. The organic chloramines have been shown to

interfere with disinfection and have lower disinfection capacities than their inorganic counterpart monochloramine. The environmental effects imposed by the discharge of these compounds into natural receiving waters is unknown. This study has shown that amino acid precursors for N-chloramino acids range in concentration from 1.4 X 10^-7 M to 9.0 X 10^{-7 …}

Analysis Of Organic N-Chloramines In Chlorinated Drinking Water, John Po Wen Yang

Chemistry & Biochemistry Theses & Dissertations

This thesis describes the development of a sensitive method for the separation and quantitation of organic N-chloramines in chlorinated tap water. 5-Dimethylaminonaphthalene- l-sulfinic acid has been synthesized and characterized. It yields highly fluorescent dansyl derivatives on reaction with N-chloramines. Conditions of the derivatization were optimized for the detection of N-chloropiperidine at concentrations in aqueous solution of 10^-7 M. The technique gives a quantity of derivative which is proportional to the concentration of chloramine present over the range examined (10^-7 M to 10^-4 M). High pressure liquid chromatographic separation of dansyl derivatives of amines and amino acids has …