Analytical Chemistry Commons^™

Sustained Release Of Persulfate And Iron(Ii) Ions From Inert Inorganic Materials For Groundwater Remediation, Peter Pham

Masters Theses

Contamination of groundwater, initiated from years of human negligence, continues to persist despite major advancements in water remediation technologies. The generated groundwater plumes can continuously replenish contaminants such as dense nonaqueous phase liquids (DNAPLs) through the aid of slow-moving water. Thus, long-term treatment of this flow system has proven to be problematic. A selection of sophisticated sustained diffusion technologies is needed to help prevent further damage to this prominent freshwater source.

Here, a novel in-situ chemical oxidation (ISCO) method was designed to incorporate persulfate into silica mediums such as zeolite, diatom, and silica flour for the treatment of groundwater contaminants …

Novel Methods And Sensors For The Analysis Of Trace Chemicals With Potential Environmental Applications, Samuel Mason Rosolina

Doctoral Dissertations

The work in this dissertation focuses on the detection and analysis of trace chemicals in biological and environmental samples. Methods for the electrochemical detection of heavy metals Cd(II) [cadmium] and Pb(II) [lead], and the catalytic metal Pd(II) [palladium] in pharmaceutical ingredients have been optimized without the necessity of sample pretreatment. The metals can be analyzed simultaneously as well as individually, and the study includes the first known instance of the use of anodic stripping voltammetry (ASV) to detect metals in dimethyl sulfoxide (DMSO) solutions. Another method, based on ASV, has been optimized and evaluated for the purpose of mercury(II) analysis …

Real-Time Spectroscopic Analysis Of Microalgal Adaptation To Changing Environmental Conditions, Robert Ked Byrd

Masters Theses

Increases in anthropogenic pollution are causing many environmental problems; understanding their impact on the environment has become an important issue. Industrialization and the burning of fossil fuels have caused increased levels of carbon dioxide to enter the atmosphere, which is contributing to global warming and ocean acidification. Agricultural runoff has caused levels of inorganic nitrogen and phosphorus to rise, where they have been noted to cause harmful algal blooms. Marine ecosystems have been particularly affected as both of these forms of pollution accumulate in bodies of water. Microalgae are important organisms in these ecosystems because they sequester these pollutants and …

Quorum Sensing And Metabolism In Marine Environments, Amanda May

Doctoral Dissertations

Quorum sensing (QS) is a phenomenon that allows bacteria to communicate with each other. Small molecules known as autoinducers are synthesized and released by bacteria, and once enough members of the community are around to ensure survival, i.e. quorum, a phenotype, e.g. bioluminescence, is expressed. There are two types of QS molecules, intra- and inter-species.

S-4,5-Dihydroxy-2,3-pentanedione (DPD) is a byproduct of the activated methyl cycle which recycles methionine. This has led to the discussion as to whether DPD is a metabolic byproduct or is the interspecies signal as proposed previously. The detection and quantitation of DPD however, has not …

New Approaches To Electroanalysis Of Metals And Pretreatment Of Biological And Environmental Samples, Stefanie Bragg

Doctoral Dissertations

Biological and environmental sample pretreatment followed by electrochemical sensing are the focus of this dissertation. The Advanced Oxidation Process (AOP) treatment using aqueous hydrogen peroxide and UV irradiation with acid deactivation of the enzyme catalase in blood has been developed and optimized. The kinetics of whole blood AOP in a single-cell reactor was studied, and the effect of pH on the AOP process has been investigated. A new method of dry ashing whole blood has been developed and optimized for trace metal analyses. The new method and subsequent metal analyses in the blood samples has been used to confirm results …

A Novel Approach To Assess Environmental Changes In Marine Ecosystems Via Spectroscopic Analyses Of Microalgae, Rebecca Burke Horton

Doctoral Dissertations

Chemical analyses for environmental monitoring encounter many challenges which are imposed by a multitude of chemically complex and interrelated processes. For such investigations, innovative analytical methodologies must be developed which characterize chemical shifts of key environmental parameters in order to deduce insights into their ecological relevance. This dissertation is driven by an analytical chemistry perspective to develop chemical sensing techniques with the ultimate goal of gaining a deeper understanding of environmental changes and their chemical origins.

In order to overcome limitations inherent to any chemical sensor designed for a specific task, new paths are pursued which are based on the …

Surface-Enhanced Raman Scattering: Substrate Development And Applications In Analytical Detection, Deepak Bhandari

Doctoral Dissertations

To advance the capabilities of surface-enhanced Raman scattering (SERS), we developed a silver modified polypropylene filter (AgPPF) substrate which acts as a pseudo stationary phase in harvesting SERS signatures of so called "phytochemical estrogens" and other environmentally significant chemicals. To augment electron beam lithography (EBL) in SERS research, we also introduced an interesting nanotransfer printing (nTP) technique which could circumvent the low throughput and extremely high resolution (< 10 nm) limitations of EBL in designing advanced SERS substrates. In our study, a nominal average thickness of 10 nm silver on the polypropylene microfiber produced nanoglobules of less than 100 nm in diameter. This noble metal nanoroughened layer allowed AgPPF to serve as a SERS active substrate, onto which the noted endocrine disrupting chemicals were passed through and harvested. The intense, multifeatured vibrational Raman spectra of very rarely SERS studied chemical species collected indicates the potential for useful detection via this approach of creating SERS substrates. AgPPF substrates were also used in characterizing the adsorption behavior of hydroxyl complexes of uranium. Interestingly, hydroxyl group on the uranium complexes showed slow sorption kinetics on the nanostructured silver surfaces. Understanding the adsorption behavior of aqueous solution of uranium on nanostructured silver surfaces has opened up the possibilities of SERS detection of these environmental and non-proliferation concerned species without any surface modifications. nTP is a high resolution printing technique and relies on interfacial chemistries to control the transfer of thin metal film from a "stamp" to a "substrate". In our research, high-aspect-ratio AutoCAD designed nanopatterns were created on silicon wafers using e-beam lithography and reactive ion etching. Silicon relief pillars based stamps were then used to integrate a variety of nanostructures on different dielectric materials. Thus created nanopatterns have shown their promise to hold their inherent SERS activity. For its simplicity, cost-effectiveness, and ease of operation, this hyphenated nTP-SERS technique is impressive in the selection of suitable supporting-films for better SERS enhancements and also to manipulate gap between nanodiscs (gap-plasmonic SERS effect).

New Electrochemical And Optical Detection Methods For Biological And Environmental Applications, Royce Nicholas Dansby-Sparks

Doctoral Dissertations

Detection of chromium and vanadium is of interest for biomedical and environmental applications. The two metals have narrow limits between being essential and toxic for humans. Ultra-sensitive techniques have been studied to measure Cr and V at low concentrations found in human blood and environmental samples. Bismuth film and mercury-alloy electrodes have been developed as alternatives to traditional Hg-based electrodes for Cr and V detection. While catalytic adsorptive stripping voltammetry (CAdSV) has been used to detect Cr and V, little is known about the process. The mechanisms of CAdSV have been probed to provide a better understanding of its exceptional …

Classification And Fertility Of Soils In The Big South Fork National River And Recreation Area Based On Landscape Position And Geology, Ryan H. Blair

Masters Theses

The Big South Fork National River and Recreation Area encompasses more than 50,585 hectares (125,000 acres) of the Cumberland Plateau along the border of Tennessee and Kentucky. Highly dissected and steep terrain have made accessibility to much of the park limited, thus little work has been done to investigate the formation of these soils. Seven native soil profiles were selected for chemical and physical analysis representing Pennsylvanian-aged acidic sandstone and shale geology and landforms. The objectives of this study included the characterization of selected native profiles by physical and chemical analysis, as well as classification using US Soil Taxonomy, to …