Physical Sciences and Mathematics Commons^™

Molecular Level Characterization Of Dissolved Organic Matter Integrating Trapped Ion Mobility Spectrometry And Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Dennys Leyva Bombuse

FIU Electronic Theses and Dissertations

Dissolved organic matter (DOM) is an extremely complex mixture of organic molecules ubiquitous in aquatic systems and a critical component of the global carbon cycle. Little is known about DOM structural composition at the molecular level. The work presented in this dissertation summarizes the development of a novel analytical toolbox based on trapped ion mobility spectrometry and Fourier transform ion cyclotron resonance mass spectrometry (TIMS-FT-ICR MS) that has significantly contributed to expand our knowledge of DOM molecular complexity and diversity. The TIMS-FT-ICR MS/MS analysis provided for the first-time lower and upper estimation of the molecular isomeric diversity. The TIMS-FT-ICR MS/MS …

Crude Oil Characterization Using Gas Chromatography, Ion Mobility Spectrometry And Mass Spectrometry, Clement A. Olanrewaju

FIU Electronic Theses and Dissertations

The characterization of crude oils at the compositional level remains challenging due to their high chemical complexity and isomeric diversity. The present work expands the analytical separation space of chemical components in crude oils by coupling gas chromatography (GC), trapped ion mobility spectrometry (TIMS), and mass spectrometry (GC-TIMS-MS and TIMS-FT-ICR MS) for the effective separation and identification of isomeric compounds. The coupling of GC and TIMS-MS platform enhanced the peak capacity and showed complementary isomeric separation. The combination of GC-TIMS-MS and GC-EI-MS technique provided a comprehensive characterization of PAHs and similar compounds from crude oils on the basis of retention …

Non-Target Analysis Using High-Resolution Mass Spectrometry To Characterize And Remediate Urban Waters, Brian Ng

FIU Electronic Theses and Dissertations

The first part of this dissertation will focus on the development of a simple, robust online solid phase extraction liquid chromatography high resolution mass spectrometry (SPE LC-HRMS) method followed by the use of computational software workflows for non-target analysis (NTA) of environmental samples (development). The benchmarks to assess reproducibility are not well defined for non-target analysis. Parameters to evaluate analytical performance, such as accuracy, precision and selectivity, are well defined for target analysis, but remain elusive for non-target screening analysis. In this study, quality control (QC) guidelines are proposed to assure reliable data in NTA methodologies using a simple …

Ligands For Complexation, Extraction, And Sensing Of Mercury(Ii) For Application To High-Level Waste (Hlw) At The Savannah River Site (Srs), Adenike O. Fasiku

FIU Electronic Theses and Dissertations

Mercury (Hg) separation and sensing is of high significance due to Hg^(II) environmental mobility and toxicity. Furthermore, the use of Hg in nuclear applications has resulted in its accumulation in several DOE sites, such as in Oak Ridge and Savannah River reservations. Organic mercury species have been found in low activity waste (LAW) streams resulting from high-level waste (HLW) processing at the Savannah River Site (SRS), therefore posing a threat to humans and the environment. Mercury, being a soft Lewis acid, has a strong affinity for softer Lewis bases, such as S- or N-donor ligands. Therefore, we focus on …

High And Low Toxin Producing Strains Of Karenia Brevis Differ Significantly In The Redox Proteome, Lipid Profiles, And Xanthophyll Cycle Pigments, Ricardo Colon

FIU Electronic Theses and Dissertations

The dinoflagellate Karenia brevis, blooms annually in the Gulf of Mexico, producing a suite of neurotoxins known as the brevetoxins. The cellular toxin content of K. brevis, however, is highly variable between or even within strains. I investigated biochemical differences between high (KbHT) and low (KbLT) toxin producing cultures both derived from the Wilson strain, related to energy-dependent quenching (qE) by photosystem II, and the content of reduced thiols of the proteome. By characterizing the xanthophyll content of the two strains I was able to determine that KbLT performs qE inconsistently. To investigate the …

Competitive Reductive Removal Of Chromate And Pertechnetate Via Zero-Valent Iron, Jonathan Williams Ramirez

FIU Electronic Theses and Dissertations

Treatment to immobilize radioactive waste is of concern for long-term storage, avoiding future environmental exposure. Most production of Technetium-99 (⁹⁹Tc) occurred as a byproduct of development of legacy nuclear weapons research. Zero-valent iron (ZVI) is a promising reductant of Tc(VII) to a less mobile ⁹⁹Tc(IV). However, more redox-sensitive contaminants can compete in the reductive process. Therefore, it is important to examine the effects of competitive contaminants and quantify the effects on the reductive removal rates of ⁹⁹Tc. Chromate, Cr(VI), is a redox-sensitive contaminant that is expected to be present in legacy waste present in the Hanford …

Uranium Fate And Mineral Transformations Upon Remediation With Ammonia (Nh3) Gas, Silvina A. Di Pietro

FIU Electronic Theses and Dissertations

The fission of uranium (U) for plutonium production was a major activity at the U.S. Department of Energy’s (DOE) Hanford Site in Washington State during World War II and Cold War. This endeavor resulted in the generation of over two million liters of high-level radioactive waste, most of which still remains in 177 underground storage tanks. Due to the improper storage and aging of these tanks in addition to other waste releases across the Site, approximately 200,000 kg of U have been released into the vadose zone. The objective of this study was to determine whether the application of the …

Fundamental Studies Of The Singlet Oxygenation Of Water Soluble Biological And Environmental Important Molecules, Marcela Jaramillo

FIU Electronic Theses and Dissertations

Singlet oxygen, 1O2, can be easily generated by a sensitizer, solar radiation, and molecular oxygen. 1O2 is very important in a range of biological and environmental systems. The products and mechanisms of the 1O2 reactions are well studied in organic solvents, and despite well-established solvent effects, studies on the reactions of the singlet oxygen in aqueous media are limited. Herein, 1O2 reactions with biologically and environmentally relevant conjugated π systems in aqueous solutions are presented. Water-soluble isomeric 1, 3-hexadienes are simple mechanistic probes for the 1O2 reactions since concerted and non-concerted pathways produce distinct products. The isomerization of sorbic acid …

Advanced Oxidation Processes For The Remediation Of Problematic Organophosphorus Compounds And Perfluoroalkyl Substances, A M Abdullah

FIU Electronic Theses and Dissertations

The presence of persistent organic pollutants, including organophosphorus esters (OPEs) and perfluoroalkyl substances (PFASs) in drinking water sources, is a serious threat to the environment and human health. Advanced oxidation processes (AOPs), specifically TiO₂ photocatalysis and sonolysis, were evaluated to degrade these pollutants in water.

The UV/TiO₂ photocatalysis can effectively degrade tris (2-chloroethyl) phosphate (TCEP) to innocuous materials. The degradation follows pseudo-first-order kinetics and consistent with the Langmuir-Hinshelwood model. Intermediate products identified by ³¹P-NMR show sequential oxidation of alkyl chains, ultimately leading to phosphate. Scavenger studies indicate hydroxyl radical (•OH) is the primary species responsible for the …

Aptamer-Based Assay For Detection Of Ochratoxin A, Amanda Nicole Bartley

FIU Electronic Theses and Dissertations

Ochratoxin A (OTA) is a potent mycotoxin found in a wide range of agricultural products that has been linked to mitochondrial damage and renal disease. The standard methods for OTA analysis currently rely on the use of high-performance liquid chromatography (HPLC) coupled to fluorescence detection or mass spectrometry. Toward a highthroughput analysis of OTA, a single-stranded DNA aptamer, modified with a fluorophore, coupled to a complementary sequence, modified with a FRET-based quencher that dissociates in the presence of the target toxin, is proposed. In order to integrate “target trapping,” aptamer immobilization methods were explored to mediate interference issues. Assays were …

Unrefined Humic Substances As A Potential Low-Cost Remediation Method For Groundwater Contaminated With Uranium In Acidic Conditions, Hansell Gonzalez Raymat

FIU Electronic Theses and Dissertations

Anthropogenic activities such as uranium mining and milling, nuclear weapons production, and nuclear reprocessing have left a legacy of groundwater and soil contaminated with uranium that needs to be addressed. Therefore, developing new remediation technologies to sequester uranium in situ is crucial. The objective of the study was to determine if low-cost commercially available unrefined humic substances, such as Huma-K, can be used to facilitate uranium sorption to minerals in soil and sediment. Sediments from the saturated zone beneath the F-Area seepage basins at the Savannah River Site (SRS) in South Carolina were used for the present study. The SRS …

Fundamental Mechanistic Studies On The Ultrasonic Treatment Of Problematic Water Pollutants And Toxins, Danni Cui

FIU Electronic Theses and Dissertations

Problematic organic pollutants in industrial and drinking water sources are a leading cause of water scarcity. Among the advanced oxidation processes, sonolytic degradation has received considerable attention because it combines oxidation processes initiated by reactive oxidant species and a pyrolysis processes associated with the high temperatures produced during cavitation.

The degradation of the semi-volatile compound, MCHM, was rapid and followed pseudo-first order kinetics. The Freundlich kinetic model for heterogeneous systems was successfully applied to describe the non-uniform distribution of MCHM at the gas-liquid interface during ultrasonic treatment. Two primary products were confirmed by GC-MS. Computational studies were also applied to …

Characterization Of The Uranium-Bearing Phases Produced By Novel Remediation Technologies For Sequestration Of Mobile Radiological Contaminants In The Hanford 200 Area Vadose Zone, Robert Michael Lapierre

FIU Electronic Theses and Dissertations

Of the many toxic chemicals released into the Hanford vadose zone over the decades of nuclear weapons production, uranium has emerged as a contaminant of significant interest. The ammonia gas injection remediation method has been identified as a promising approach towards mitigating the risks to the ecosystem by limiting the mobility of the radionuclide in the vadose zone. The remediation method was replicated using synthetic porewater solutions with a range of constituent concentrations equal to that of the Hanford 200 Area vadose zone. The uranium-bearing products of the remediation method were characterized using kinetic phosphorescence analysis for aqueous uranium, scanning …

The Investigation Of Photocatalytic And Adsorptive Properties Of Humic Acid Grafted Magnetite Nanoparticles For The Remediation Of Arsenic, Selenium And Phosphorous From Water, Mohammad Mamunur Rashid

FIU Electronic Theses and Dissertations

The crisis of freshwater has been a big concern worldwide. Water contamination that occurs through the discharge of toxic pollutants from different natural and anthropogenic sources have worsened the situation. Adsorption has emerged as a simple and economical water treatment procedure although the challenge is to find the right adsorbent that can efficiently remove the target contaminant followed by their easy recovery from the reaction vessel. In this dissertation, I have focused on the synthesis, characterizations and applications of environmentally compatible and magnetic humic acid coated magnetite nanoparticles (HA-MNP) as a potential adsorbent for water purification.

Phosphate is an essential …

The Cyclodextrin-Perfluorinated Surfactant Host-Guest Complex: Fundamental Studies For Potential Environmental Remediation And Therapeutic Applications, Mary J. Errico

FIU Electronic Theses and Dissertations

Perfluoroalkyl substances (PFASs) are contaminants of emerging concern, and have been detected in drinking water, wildlife, humans, and the environment. Cyclodextrins (CDs), cyclic sugars composed of glucose monomers, are proposed as a potential remediation strategy. CDs can form host-guest complexes with hydrophobic molecules; this complexation could be capitalized on for PFAS removal and sequestration. These dissertation projects aim to study the fundamental host-guest interactions between a variety of PFASs and CDs for eventual applications in environmental and biological remediation. 1D and 2D Nuclear magnetic resonance (NMR) spectroscopic methods were employed to determine the strength, dynamics, and structure of the CD:PFAS …

Environmental Dynamics Of Dissolved Organic Matter And Dissolved Black Carbon In Fluvial Systems: Effects Of Biogeochemistry And Land Use, J. Alan Roebuck Jr.

FIU Electronic Theses and Dissertations

Black carbon (BC) is an organic residue formed primarily from biomass burning (e.g., wildfires) and fossil fuel combustion. Until recently, it was understood that BC was highly recalcitrant and stabilized in soils over millennial scales. However, a fraction of the material can be solubilized and transported in fluvial systems as dissolved BC (DBC), which represents on average 10% of the global export of dissolved organic carbon (DOC) from rivers to coastal systems. The composition of DBC controls its reactivity, and it has been linked with a variety of in-stream processes that induce both carbon sequestration and evasion of CO₂ from …

Trapped Ion Mobility Spectrometry Coupled To Fourier Transform Ion Cyclotron Resonance Mass Spectrometry For The Analysis Of Complex Mixtures., Paolo Benigni

FIU Electronic Theses and Dissertations

Analytical Characterization of complex mixtures, such as crude oil, environmental samples, and biological mixtures, is challenging because of the large diversity of molecular components. Mass spectrometry based techniques are among the most powerful tools for the separation of molecules based on their molecular composition, and the coupling of ion mobility spectrometry has enabled the separation and structural elucidation using the tridimensional structure of the molecule. The present work expands the ability of analytical chemists by furthering the development of IMS-MS instrumentation by coupling Trapped Ion Mobility Spectrometry to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (TIMS-FT-ICR MS). The TIMS-FT-ICR MS …

Linking Organic Matter Dynamics To Management, Restoration, And Climate In The Florida Everglades, Peter Regier

FIU Electronic Theses and Dissertations

The Florida Everglades is a massive and highly managed subtropical wetland ecosystem, strongly influenced by anthropogenic control of freshwater distribution and highly susceptible to a changing climate, including rising sea-level and changes in temperature and rainfall. Shifting hydrologic regimes impact ecosystem function and biogeochemistry, which in turn control the sources, fate, and transport of organic matter. As a master environmental variable, it is essential to understand how organic matter dynamics will respond to changes in the balance between freshwater and saltwater associated with landscape-scale Everglades restoration efforts and climate change. The research comprising this dissertation improves current understanding of the …

Capture And Densification Of Floating Hydrophobic Liquids By Natural Granular Materials, Daria Boglaienko

FIU Electronic Theses and Dissertations

Densification and submergence of floating crude oil is proposed as a novel oil spills treatment method. Surface application of dry granular materials (e.g., quartz sand, limestone) on top of a floating oil layer increases the density of the floating oil phase/granule mixture and leads to formation of relatively large and stable aggregates with significant amounts of captured oil. The aggregates separate from the floating hydrophobic phase and settle by gravity. Implementation of this method will reduce the impact radius of a spill and its mobility, preventing direct contamination of beaches, coastal flora and fauna.

The major objective of this research …

Going Beyond The Analysis Of Common Contaminants: Target, Suspect, And Non-Target Analysis Of Complex Environmental Matrices By High-Resolution Mass Spectrometry, Anna Katarina Huba

FIU Electronic Theses and Dissertations

The advancements in the field of analytical chemistry, and especially mass spectrometry, have been redefining the field of contaminant detection. While more traditional analysis was sufficient to screen for a small number of well-known compounds, new techniques such as high-resolution mass spectrometry, have enabled a fairly comprehensive screening for previously unknown contaminants. This is enormously beneficial with respect to the analysis of water, air, or soil quality in a society that continuously introduces novel anthropogenic compounds into the environment. This dissertation, thus, focused on the analysis of the uncharacterized portion of compounds in two types of complex environmental matrices (i.e., …

Mercury Sulfide Dissolution In Environmental Conditions: Thermodynamic And Kinetic Approaches, Ping Jiang

FIU Electronic Theses and Dissertations

Mercury (Hg) is a global contaminant of ecosystems and human health risk, with complicated biogeochemical processes. Mercury sulfide (HgS) dissolution has been suggested as a key process in Hg cycling, as it could potentially increase the pool of inorganic Hg (iHg) for the production of methylmercury (MeHg). Despite previous sporadic observations of enhanced HgS dissolution under certain conditions, much remains unclear on mechanisms of HgS dissolution. The objective of my research was to advance the mechanistic understanding of HgS dissolution, concerning re-adsorption of released Hg, effects of thiol-ligands, and Hg speciation.

Considering the lack of feasible techniques to differentiate dissolution …

Hydrogeochemical Modeling Of Saltwater Intrusion And Water Supply Augmentation In South Florida, Yonas T. Habtemichael

FIU Electronic Theses and Dissertations

The Biscayne Aquifer is a primary source of water supply in Southeast Florida. As a coastal aquifer, it is threatened by saltwater intrusion (SWI) when the natural groundwater flow is altered by over-pumping of groundwater. SWI is detrimental to the quality of fresh groundwater sources, making the water unfit for drinking due to mixing and reactions with aquifer minerals. Increasing water demand and complex environmental issues thus force water utilities in South Florida to sustainably manage saltwater intrusion and develop alternative water supplies (e.g., aquifer storage and recovery, ASR).

The objectives of this study were to develop and use calibrated …

Development Of A Maldi-Tof-Ms Method For The Analysis Of Cyanobacterial Neurotoxin Β-N-Methylamino-L-Alanine (Bmaa) In Search Of Bmaa Incorporation In Biological Samples, Laura M. Conklin

FIU Electronic Theses and Dissertations

Beta-N-methylamino-L-alanine (BMAA) is a non-protein amino acid produced by many cyanobacteria, and thought to induce neurotoxic effects through excitotoxicity, contributing to neurodegenerative diseases such as Amyotrophic Lateral Sclerosis/Parkinsonism-dementia complex (ALS-PDC) and Alzheimer’s. The ubiquitous nature of cyanobacteria, and evidence of biomagnification through our food web, creates a dire need for the development of an analytical platform that will provide accurate identification and quantification of BMAA amounts in our ecosystem and potential food supply. The present study evaluated the ability of a MALDI-ToF-MS method to detect and quantify BMAA in a variety of biological matrices. Through validation procedures, it …

The Effect Of Disturbance And Freshwater Availability On Lower Florida Keys’ Coastal Forest Dynamics, Danielle E. Ogurcak

FIU Electronic Theses and Dissertations

Coastal forest retreat in the Florida Keys during the 20^th century has been attributed to a combination of sea level rise and hurricane storm surge impacts, but the interactions between these two disturbances leading to forest decline are not well understood. The goal of my research was to assess their effects over a period spanning more than two decades, and to examine the relationships between these press and pulse disturbances and freshwater availability in pine rockland, hardwood hammock, and supratidal scrub communities. Impacts and recovery from two storm surges, Hurricanes Georges (1998) and Wilma (2005), were assessed with satellite-derived …

Mangiferin As A Biomarker For Mango Anthracnose Resistance, Herma Pierre

FIU Electronic Theses and Dissertations

Mangos (Mangifera indica L.) are tropical/subtropical fruits belonging to the plant family Anacardiaceae. Anthracnose is the most deleterious disease of mango both in the field and during postharvest handling. It is most commonly caused by the Colletotrichum gloeosporioides complex. Mangiferin, a xanthanoid compound found in at least twelve plant families worldwide (Luo et al., 2012), is present in large amounts of the leaves and edible mangos. Even though this compound plays a pivotal role in the plant’s defense against biotic and abiotic stressors, no correlations been made between the compound and mango anthracnose resistance.

Mangos were collected, grouped …

Target And Non-Target Techniques For The Quantitation Of Drugs Of Abuse, Identification Of Transformation Products, And Characterization Of Contaminants Of Emergent Concern By High Resolution Mass Spectrometry, Nubia Vanesa Heuett

FIU Electronic Theses and Dissertations

Development and application of target and non-target techniques for routine analysis, identification of transformation products, and characterization of unknown compounds in water matrices using liquid-chromatography high-resolution mass spectrometry (HRMS) were explored in this dissertation. A novel analytical method based on online-SPE-LC-HRMS was developed for the detection of 18 drugs of abuse (DOAs) in raw sewage water from a college campus. Results showed the presence of 14 DOAs for which amphetamine and 11-nor-9-carcoxy-THC (THC metabolite) were the most prevalent and had the highest potential consumption rates.

A second study dedicated to the identification of transformation products (TPs) generated from DOAs was …

Black Carbon: Sources, Mobility And Fate In Freshwater Systems, Sasha Wagner

FIU Electronic Theses and Dissertations

Black carbon (BC) is a complex mixture of polycondensed aromatic compounds produced by the incomplete combustion of biomass during events such as wildfires and the burning of fossil fuels. Black carbon was initially considered to be a refractory form of organic matter. However, recent studies have shown that BC can be quite mobile and reactive in the terrestrial environment. Black carbon can be translocated from soils and sediments in the form of dissolved BC (DBC). A global correlation between DBC and bulk dissolved organic carbon (DOC) has been established for fluvial systems where DBC comprises approximately 10% of the total …

Advanced Oxidation Processes Of Problematic Toxin And Water Contaminants: Cylindrospermopsin, Iopamidol, 4-Methylcyclohexane Methanol And Propylene Glycol Phenyl Ether, Cen Zhao

FIU Electronic Theses and Dissertations

The occurrences of cyanotoxin and organic contaminants threaten drinking water sources and are a serious human health and environmental concern. The control of these problematic contaminants and the remediation of the associated contaminants are critical for ensuring safe drinking water to significant populations. Advanced oxidation processes (AOPs) have received considerable attention as a potential water treatment for various pollutants. In this dissertation, advanced oxidative degradation of four problematic water toxic contaminants (CYN, iopamidol, 4-methylcyclohexane methanol and propylene glycol phenyl ether) were studied to develop the fundamental understanding required to assess AOPs as a potential water treatment process.

UV and visible …

Changes Of Soil Biogeochemistry Under Native And Exotic Plants Species, Yujie Hua

FIU Electronic Theses and Dissertations

Invasive plant species are major threats to the biodiversity and ecosystem stability. The purpose of this study is to understand the impacts of invasive plants on soil nutrient cycling and ecological functions. Soil samples were collected from rhizosphere and non-rhizosphere of both native and exotic plants from three genera, Lantana, Ficus and Schinus, at Tree Tops Park in South Florida, USA. Experimental results showed that the cultivable bacterial population in the soil under Brazilian pepper (invasive Schinus) was approximately ten times greater than all other plants. Also, Brazilian pepper lived under conditions of significantly lower available phosphorus …

Sources, Fate And Transformation Of Organic Matter In Wetlands And Estuaries, Chao Ya

FIU Electronic Theses and Dissertations

Dissolved organic matter (DOM) is a complex mixture of organic compounds and represents the largest reservoirs of carbon (C) on earth. Particulate organic matter (POM) is another important carbon component in C cycling and controls a variety of biogeochemical processes. Estuaries, as important interfaces between land and ocean, play important roles in retaining and transforming such organic matter (OM) and serve as both sources and sinks of DOM and POM. There is a diverse array of both autochthonous and allochthonous OM sources in wetland/estuarine ecosystems. A comprehensive study on the sources, transformation and fate of OM in such ecosystems is …