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 …

The Use Of Electrospun Nanofibers With Gold And Silver Nanostars For The Detection Of Fentanyl Using Surface Enhance Raman Spectroscopy, The Modification Of Current Gc-Ms Methods To Increase Separation And Detection Of Synthetic Cathinones In Mixtures, Daniel Rubin

FIU Electronic Theses and Dissertations

Many criminal cases involve the use or sale of illicit substances. The forensic analyst has many different techniques they can use to analyze samples to determine which illicit substance is present. This project aims at developing electrospun nanofibers with nanoparticles to analyze fentanyl by surface enhanced Raman spectroscopy, as well as modifying current GC-MS parameters to enhance separation and analysis of synthetic cathinones. Using the fibers with nanoparticles allowed for the detection of fentanyl standards at 1mg/ml while slowing the oven ramp rate and modifying the hold times led to an increase in separation and better fragmentation patterns for determination. …

The Utilization Of Volatile Organic Compounds And Human Leukocyte Antigen Genes For Ethnic-Specific Differentiation Within Target Populations, Alice Breia Boone

FIU Electronic Theses and Dissertations

Human scent has been previously defined as a complex mixture of volatile organic compounds (VOCs) detected in the headspace above a scent sample. Humans generate odor from several areas of the body including hair, mouth, hand, axillae, and foot. Due to the novelty of human scent research, human scent evidence has been undervalued in the court of law. However, this type of evidence has significant value when physical evidence is not available at crime scenes. To increase the individualization and differentiation power of human scent evidence, this study aimed to further investigate the identification of chemical signatures within axillae of …

An Investigation To Corroborate Volatile And Biological Profiles Of Human Odor For Forensic Subject Identification, Chantrell J.G. Frazier

FIU Electronic Theses and Dissertations

Hands are an integral part in transferring complex microbial communities to and from our surroundings. As a result, hands are significant in provenance investigations as specific microbiota can be deposited on everyday objects through touch interactions. Skin microbiome, including bacteria, fungi, and viruses, are unique to each person, and this ‘uniqueness’ can be exploited and applied to forensic identification. Skin microbiota and volatile organic compounds (VOCs) are closely related due to specific bacteria breaking down non-volatile organic compounds to volatile organic compounds that are characteristically present in human scent. However, analyses of microbiota from touch interactions have proven to be …

Evaluation And Improvement Of Capillary Microextraction Of Volatiles Coupled To Gas Chromatography-Mass Spectrometry For The Analysis Of Ignitable Liquid Residues In Fire Debris, Michelle Nikole Torres

FIU Electronic Theses and Dissertations

A key aspect of fire debris analysis is the ability to extract the remnants of an ignitable liquid from a matrix with a high degree of reliability and sensitivity. Although there are several robust, standardized methods, there is no single technique universally applicable to casework. In this work a novel extraction technique – Capillary Microextraction of Volatiles (CMV) – has been applied, for the first time, for ignitable liquid residue (ILR) extraction. A 20-minute dynamic sampling laboratory protocol from traditional 1 L paint cans was established and optimized based upon ASTM guidelines. The development of new adsorption phases for CMV …

Aptamer-Based Voltammetric Biosensing For The Detection Of Codeine And Fentanyl In Sweat And Saliva, Rosa Lashantez Cromartie

FIU Electronic Theses and Dissertations

Despite the many governmental and medicinal restrictions created to combat the opioid epidemic in the United States, opioid abuse and overdose rates continue to rise. The development of an aptamer-based voltammetric sensor and biosensor is described in this dissertation. The aim was to develop a low-cost, sensitive, and specific aptamer-based sensor for on-site, label-free determination of codeine and fentanyl in biological fluids. To do this, the surfaces of screen-printed carbon electrodes (SPCE) were modified with gold nanoparticles (AuNPs), followed by the addition of single-stranded DNA aptamers. These were covalently bound to the electrode surface. Operations of the sensors were collected …

Characterization Of Biological Samples Using Multi-Modal Mass Spectrometry, Yarixa L. Cintron-Diaz

FIU Electronic Theses and Dissertations

There is a need for fast, accurate and cost-effective protocols capable of assessing biomolecules at the molecular level (e.g., proteins, lipids and metabolites) from biological specimens. Mass spectrometry (MS) based techniques have become the analytical gold standard for identification and characterization of biomarkers in biological samples. The high throughput and short analysis time scales enables to follow biological processes while providing detailed chemical and spatial characterization. One of the current challenges in biological MS, is the high molecular complexity, chemical diversity and dynamic range. In this dissertation, the use of multi-modal mass spectrometry workflows -mass spectrometry imaging and ion mobility …

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 …

Utilizing Headspace Solid-Phase Microextraction For The Characterization Of Volatile Organic Compounds Released From Contraband And Its Implications For Detector Dog Training, Kelvin Joseph Frank Jr

FIU Electronic Theses and Dissertations

Improving the accuracy and reliability of odor detection dogs is of utmost importance particularly for legal reasons. Field testing in conjunction with headspace analysis of volatile organic compounds (VOCs) has in recent times allowed for these improvements, by providing scientifically based recommendations for optimum training protocols. The current project leveraged on these established capabilities to enhance three areas of odor detection: illicit drugs, explosives and mass storage devices.

With hemp being legalized under the 2018 Farm Bill, legal questions have been raised regarding a dog’s ability to ignore hemp if trained to detect marijuana, as both are types of Cannabis …

Evaluation Of Harvesting Time For Industrial Hemp (Cannabis Sativa L,) Pilot Project Varieties Grown In South Florida, Jordan W. Prats

FIU Electronic Theses and Dissertations

A field study was conducted to observe the natural development of cannabinoids in three daylength sensitive industrial hemp varieties Bubba Kush (BK), Emerald Flower (EF), and Golden Sunset (GS). Plants were configured in a randomized block design with 3 replications. Once 50% of the plants within a variety reached reproductive growth, plants were sampled weekly until senescence and analyzed through a HPLC-UV/DAD. The results from the study indicate that all three varieties of industrial hemp tested in field study reached reproductive growth within the first week of transplanting. This is due to a 12-hour day-length at the time and 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 …

Surface Enhanced Raman Spectroscopy (Sers) As A Nanoscale Adsorption Phenomenon: Development Of Tailored Nanomaterials For Applications In Drug Detection, Chiara Deriu

FIU Electronic Theses and Dissertations

Surface Enhanced Raman Spectroscopy (SERS) is an analytical technique in which nanostructured substrates amplify the inherently weak Raman signal of an adsorbed species by several orders of magnitude, enabling the detection of trace compounds, up to the single molecule level. While this may be an exceptional tool for any analytical scientist, SERS is at present relegated to the role of academic sensation, and is underutilized in everyday analytical practice. The SERS community is increasingly attributing this setback to a poor understanding of nanoscale surfaces and their chemical environment; since molecular adsorption at the nanostructured surface enables SERS detection, uncertainty about …

The Development Of A Surface Enhanced Raman Spectroscopy Method For The Detection Of Synthetic Cannabinoids In Urine, Thaddeus Mostowtt

FIU Electronic Theses and Dissertations

The use and abuse of synthetic cannabinoids has increased significantly in recent years due to their easy access and growing popularity. Despite having more known drugs become illegal, new synthetic versions of these drugs are being made that have not yet been recognized or classified as illegal substances. Therefore, standard methods may not be able to detect these drugs.

The most common method of screening detection for drugs of abuse in biological samples is the immunoassay. However, the immunoassay method presents some disadvantages, particularly for newly synthesized compounds. More advanced methods have also been used, such as LC-MS; however, these …

Use Of Laser Induced Breakdown Spectroscopy For The Detection And Analysis Of Chemical Taggants, Cole Andrew Pajunen

FIU Electronic Theses and Dissertations

Chemical taggants impart a unique imprint on an object so that, if stolen, the ownership or original source of the object can be unambiguously identified. A commercially available tagging system from SmartWater® Technology Ltd. utilizes a polymer-based solution that solidifies upon application and contains a unique combination of up to 27 rare-earth elements as the chemical identification system. Currently, Laser ablation inductively coupled mass spectrometry (LA-ICP-MS) is used as the primary means to determine the presence/absence of these elements. This current study investigates the use of a commercial laser induced breakdown spectroscopy (LIBS) system as an alternative detection method due …

Systematic Comparison Of Pre-Treatment Parameters In Forensic Hair Analysis And Investigating Hair-Drug Interactions, Jennett Chenevert Aijala

FIU Electronic Theses and Dissertations

Forensic toxicological analysis for the purposes of protecting human health and supporting criminal justice activities can be achieved, in part, by means of analysis of human head hair for detection of abused substances. Hair is considered an alternative sample matrix (compared to blood and urine) because of persistent interpretive challenges caused by a lack of standardization in analytical approaches and poor understanding of the biases resulting from physicochemical interactions between major hair components (e.g., melanin) and drugs of abuse. Some of the uncertainty regarding optimal techniques for the pre-treatment of hair specimens results from the unknown nature of the …

Structural Characterization Of Biomolecules Using Tandem Non- Linear And Linear Ion Mobility, Action Spectroscopy, Mass Spectrometry And Molecular Dynamics, Jacob Edward Porter

FIU Electronic Theses and Dissertations

The following thesis comprises the use of novel gas-phase spectroscopic and spectrometric techniques complemented with molecular dynamics for the structural characterization of biomolecules: from small model systems to large proteins. In particular, complementary linear and non-linear ion mobility, mass spectrometry and action spectroscopy has been applied to the separation and characterization of native and kinetic intermediate states of biomolecular ions. This suite of tools, comprising ion mobility in tandem with non-ergodic fragmentation and action spectroscopy, provided unique information on the conformational space, folding and binding dynamics of single stranded DNA, peptides, peptide-cofactor and protein systems. Theoretical modeling provided candidate structures …

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 …

Functionalized Aptamers For Detection Of Small-Molecule Targets, Haixiang Yu

FIU Electronic Theses and Dissertations

Aptamers have recently gained considerable attention for small-molecule detection in diverse applications such as drug identification, medical diagnostics, and environmental monitoring. However, the performance of aptamer-based sensors has been greatly limited by the low target affinity and responsiveness of small-molecule binding aptamers. This dissertation describes several novel aptamer engineering and isolation strategies to remedy this problem. Specifically, we first develop a generally applicable strategy to engineer split aptamers containing two binding domains termed cooperative-binding split aptamers (CBSAs). CBSAs exhibit higher target binding affinity and are far more responsive in terms of target-induced split aptamer assembly compared to single-domain parent split …

Development Of Improved Extraction/Purification Methods And Comprehensive Screening/Confirmation By Lc-Qqq-Ms Analysis For Novel Psychoactive Substances, Ashley N. Kimble

FIU Electronic Theses and Dissertations

The presence of novel psychoactive substances (NPS) in forensic casework poses major difficulties for detection, since there are many structural variations of NPS circulating in the street market. There are currently no comprehensive screening/confirmatory/quantitation methods available that encompass the majority of NPS encountered in forensic toxicology. A major issue faced with developing such a method is that full validation is extremely time consuming. The use of a liquid chromatography triple quadrupole tandem mass spectrometry (LC-QqQ-MS/MS) method makes the detection of a large number of NPS possible because of high selectivity and sensitivity.

This research included four main tasks: 1) development …

Comprehensive Analysis Of Synthetic Cannabinoids And Metabolites In Oral Fluid By Liquid Chromatography Triple Quadrupole Mass Spectrometry, Carmen T. Mulet

FIU Electronic Theses and Dissertations

According to NIDA, synthetic cannabinoids (SC) include man-made, mind-altering chemicals. Their typically rapid metabolism and instability in biological matrices requires fast analytical methods for detection and confirmation; therefore, the use of oral fluid (OF) matrix is advantageous because collection is fast and non-invasive. The use of liquid chromatography triple quadrupole mass spectrometry (LC-QqQ-MS) and online solid phase extraction (SPE) for sample pretreatment minimizes bias and facilitates low level detection.

This study demonstrates the first use of online SPE for sample pretreatment in the comprehensive analysis of 100 SC and metabolites in OF by LC-QqQ-MS. The method was validated according the …

Interrogation Of Ion-Neutral Complexes By Trapped Ion Mobility-Mass Spectrometry And Theoretical Calculations, Alan A. Mckenzie Coe

FIU Electronic Theses and Dissertations

In the present study, the fundamentals of molecular ion trapping and the application of trapped ion mobility spectrometry coupled to mass spectrometry (TIMS-MS) to the separation and identification of molecular components in complex mixtures are shown. In particular, ion-neutral complexes lifetimes, relative stability, binding energies and candidate structures are described for common explosives during TIMS-MS, as well as the effect of the micro-environment, during complex sample analysis. A novel TIMS-MS workflow was developed for the detection of both inorganic residues (IGSR; inorganic gunshot residues) and organic residues (OGSR) of firearm discharge residue from skin swabs, capable of high specificity and …

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 …

Elemental Analysis Of Adhesive Tapes By Laser-Based Methods, Claudia Martinez Lopez

FIU Electronic Theses and Dissertations

Adhesive tapes are a common type of evidence involved in violent crimes and national security threats. This research evaluated the utility of LA-ICP-MS and LIBS for the characterization of the trace elemental signature in adhesive tapes for forensic comparisons. LA-ICP-MS and LIBS methods were developed, for the first time, for the qualitative and quantitative analysis of adhesive tapes.

The backings of 90 black electrical tapes, previously characterized by conventional techniques (physical examination, IR, Py-GC-MS, and SEM-EDS), were analyzed by LA-ICP-MS to evaluate the ability of the technique to discriminate samples originating from different sources and to associate pieces of tapes …

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 …

Forensic Toxicological Screening And Confirmation Of 800+ Novel Psychoactive Substances By Lc-Qtof-Ms And 2d-Lc Analysis, Melanie N. Eckberg

FIU Electronic Theses and Dissertations

Novel psychoactive substances (NPS) represent a great challenge to toxicologists due to the ability of illicit drug manufacturers to alter NPS chemical structures quickly and with ease to circumvent legislation regulating their use. Each time a new structure is introduced, there is a possibility that it has not been previously recorded in law enforcement or scientific databases. Many toxicology laboratories use targeted analytical methods that rely on libraries of known compounds to identify drugs in samples. However, these libraries do not include large numbers of NPS which could result in non-identification or detection.

High-resolution mass spectrometry (HRMS) has been suggested …

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 …

Predicting The Geographic Origin Of Heroin By Multivariate Analysis Of Elemental Composition And Strontium Isotope Ratios, Joshua S. Debord

FIU Electronic Theses and Dissertations

The goal of this research was to aid in the fight against the heroin and opioid epidemic by developing new methodology for heroin provenance determination and forensic sample comparison. Over 400 illicit heroin powder samples were analyzed using quadrupole and high-resolution inductively-coupled plasma mass spectrometry (Q-ICP-MS and HR-ICP-MS) in order to measure and identify elemental contaminants useful for associating heroin samples of common origin and differentiating heroin of different geographic origins. Additionally, 198 heroin samples were analyzed by multi-collector ICP-MS (MC-ICP-MS) to measure radiogenic strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) with high-precision for heroin provenance determination, for the …

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 …