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Our ability to understand and predict the fate and transport of contaminants in natural systems is vital if we are to be successful in protecting our water resources. One important aspect of understanding chemical fate and transport in natural systems is identifying key kinetic controls on important redox reactions such as sulfate reduction. Anaerobic microbial activities like sulfate reduction are of particular interest because of the important role they play in the degradation of contaminants in the subsurface. However, current rate estimates for sulfate reduction have a wide range in the literature making it difficult to determine representative rates for a given system. These differences in rate data may be explained by varying kinetic controls on reactions. Push-pull tests were used to evaluate sulfate reduction rates at the wetland-aquifer interface. Anaerobic aquifer water containing abundant sulfate was injected into sulfate-depleted wetland porewater. The injected water was subsequently withdrawn and analyzed for geochemical indicators of sulfate reduction. Complexities in rate data, such as presence of a lag phase, changing rate order and spatial variability, were observed and are hypothesized to be linked to activities of the native microbial population. Subsequent experiments explored the response of native microorganisms to geochemical perturbations using a novel approach to measure directly the effects of a geochemical perturbation on an in situ microbial population and measure rates of resulting reactions. In situ experiments involved colonization of a substrate by microorganisms native to the wetland sediments followed by introductions of native water amended with sulfate and tracer. Experimental results showed that higher sulfate concentrations and warmer seasonal temperatures result in faster sulfate reduction rates and corresponding increases in sulfate reducing bacteria. Findings from this research provide quantitative evidence of how geochemical and microbiological processes are linked in a system not at equilibrium.

Perchlorate has entered human and environmental food chains and has received a great deal of attention because of its toxicity to humans. In this study, chemical degradation of perchlorate was investigated using partially oxidized titanium ions (Ti2+ and Ti3+) in solutions and as part of an ion exchange membrane reactor system. Aqueous titanium ions (Ti2+ and Ti3+) were applied to remove perchlorate ions and its destructive mechanism, reaction kinetics, and the effect of environmental factors were investigated. Titanium ions were able to degrade perchlorate ions very rapidly with half life less than one hour under conditions of high acid concentrations. A new reactor system with an ion exchange membrane was adapted to apply better the reactions of perchlorate destruction to water treatment practice. A novel treatment method was developed by integrating partially oxidized titanium ions with an ion exchange membrane, and it is named the Titanium and Membrane Hybrid System (TMH System). The results shown in this research demonstrate the feasibility of TMH System for perchlorate reduction. The perchlorate ions were rapidly adsorbed onto the ion exchange membrane and diffused through it, but they were reduced by titanium ions in the degradation zone relatively slowly. To enhance the overall rate of reaction, high concentrations of acid and Ti(III) are needed, but transport of hydrogen ions through the anion permeable membrane was observed and would be greater at higher acid concentrations. The proposed mathematical model predicts the performance and behavior of the TMH system for different physical and chemical conditions. It successfully described adsorption, diffusion and reduction of perchlorate in the system. This model could be used as an important tool for process design and optimization.

The purpose of this study is to identify and analyze the geochemical facies of the Hushpuckney Shale using XRF scanning data and the bioturbation indices, which will contribute to a better understanding of the biogeochemical environment prevalent during the deposition of the Hushpuckney Shale. The Hushpuckney Shale Member of the Swope Formation (Kasimovian Stage) preserved in KGS Spencer core 2 - 6, consists of a black shale submember overlain by bioturbated gray shale. Millimeter-scale core description and analysis of XRF scanning data enables identification of geochemical facies within the study core and contributes to understanding the environment of shale deposition. The XRF spectrometer produces X-ray image of the core and abundance values of selected major and trace elements, including iron (Fe), calcium (Ca), sulfur (S), molybdenum (Mo), zinc (Zn), vanadium (V), chromium (Cr), copper (Cu), nickel (Ni), titanium (Ti), zircon (Zr), potassium (K) and phosphorous (P). Canfield and Thamdrup's (2009) classification of geochemical environments is used to recognize oxic/aerobic, manganous-nitrogenous, ferruginous and sulfidic facies within the black shale submember. A modification of Droser and Bottjer's (1986) semi-quantitative field classification of bioturbation is used to identify facies variations within the gray shale submember. Abundance of apatite nodules and lamina in the black shale submember of the study core suggest that black shale sediments accumulated slowly in a sediment-starved basin. A high abundance of sulfide-scavenged elements, including Mo, Zn, V, Ni and Cr, identifies the sulfidic facies in the black shale submember, and indicates deposition in an oxygen-depleted environment with a high concentration of hydrogen sulfide. The overlying ferruginous facies has lower abundances of sulfide-scavenged elements and lacks cryptic Fe-laminations. The uppermost black shale submember facies, the manganous-nitrogenous facies, has cryptic Fe laminations and a relatively high P/Ca ratio. Abundance of cryptic iron laminations and apatite nodules and lamina indicates the syngenetic deposition of iron and phosphate due to Fe-P coupling mechanism. The gray shale submember is burrowed, indicating deposition under oxygenated conditions. Bioturbation indices reveal the variations in the intensity and nature of burrows within the gray shale, which corresponds to the changes in the depositional environment that may be related to the rise and fall of sea-level.

Marine aquaculture has become one of tendencies as many countries aware of that the marine resources are not in the sustainable development from the threat of over fishing. Marine aquaculture will eventually replace the world fishing harvest as being a major stream industry in the future. Meanwhile, fast growing marine aquaculture has caused the potential problems in marine environment. A successful marine aquaculture must rely on comprehensive environmental information and monitoring, including well-designed planning and management scheme. This study research the suitable environmental indicators to predict the impact of marine environment related to marine aquaculture including comprehensive environmental data information and suitable modeling. The use of approaches consists of environmental monitoring program (EMP), sediment metals, organic carbon, redox potential, and sulfide as indicators. The survey results at Chuwan and Erkan of Penghu Island showed that sediment, redox potential, and sulfide are important environmental indicators with exception of metals. Under water survey showed that Chuwan and Erkan sites have no major accumulation of wastes from cage aquaculture operation. The current flow of these sites is downstream outward to the sea that results no serious deposition of wastes. These influence the geochemical composition and sediment, suggesting the complexity of marine environmental problems on the use of environmental indicators for monitoring and assessing the impacts. Because of the special environmental condition, we have used the geographic information system (GIS) to evaluate the affect and condition of marine cage sites. The survey results will be useful for farming management strategies and environmental carrying capacity to reduce the risk of cage farming or to accomplish the guidelines and sustainable development of marine aquaculture. This research also reports the economic effective analysis on major farming operators in Penghu, include the data envelopment analysis (DEA), to measure the variables of production inputs and outputs related to farming operation. The evaluation on the relationship of variable products should be useful in the operation and data management of cage farming. The regulations on marine aquaculture are also made to compare with Norway, United States, Japan, China, and Canada.

Elevated levels of reactive oxygen species (ROS) cause or aggravate a variety of pathological conditions such as cardiovascular disease, cancer and rheumatoid arthritis. Despite known links between oxidative stress and disease, years of clinical studies have failed to show clear benefits of antioxidant therapy. It is now recognized that ROS such as hydrogen peroxide can act as signaling molecules and are required for physiological functioning of a number of signaling pathways. Therefore, a mechanistic basis of ROS-mediated regulation of cell signaling must be established to enable rational design of antioxidant-based therapies. The challenges in quantification of transient changes mediated by ROS during cell signaling have impeded investigation of redox-regulated signaling. In the present work, computational modeling is used to circumvent these technical challenges and to test competing hypotheses of redox regulation. Using a quantitative, systems level approach to study interactions between ROS dependent and independent regulatory mechanisms, the most comprehensive model of the IL-4 signaling pathway to date has been developed and validated with experimental data. The model is capable of predicting kinase phosphorylation dynamics under new oxidative conditions, and our analyses suggest that reversible oxidation of tyrosine phosphatases is the primary mechanism of redox regulation in this pathway. Additional computational methods have been developed to study ROS as mediators of crosstalk between signaling pathways, to optimize model parameters, and to interrogate model dynamics for the purpose of model selection. Collectively, these modeling tools provide a new systems-level perspective for investigating reversible protein oxidation as a means of control over cellular signal transduction.

Capping is typically used to control contaminant release from the underlying sediments. However, the presence of conventional caps often eliminates or slows natural degradation that might otherwise occur at the surface sediment. This is primarily due to the development of reducing conditions within the sediment that discourage hydrocarbon degradation. The objective of this study was to develop a novel active capping method, an electrode enhanced cap, to manipulate the redox potential to produce conditions more favorable for hydrocarbon degradation and evaluate the approach for the remediation of PAH contaminated sediment. A preliminary study of electrode enhanced biodegradation of PAH in sediment slurries showed that naphthalene and phenanthrene concentration decreased significantly within 4 days, and PAH degrading genes increased by almost 2 orders of magnitude. In a sediment microcosm more representative of expected field conditions, graphite cloth was used to form an anode at the sediment-cap interface and a similar cathode was placed a few centimeters above within a thin sand layer. With the application of 2V voltage, ORP increased and pH dropped around the anode reflecting water electrolysis. Various cap amendments (buffers) were employed to moderate pH changes. Bicarbonate was found to be the most effective in laboratory experiments but a slower dissolving buffer, e.g. siderite, may be more effective under field conditions. Phenanthrene concentration was found to decrease slowly with time in the vicinity of the anode. In the sediment at 0-1 cm below the anode, phenanthrene concentrations decreased to ~70% of initial concentration with no bicarbonate, and to ~50% with bicarbonate over ~70 days, whereas those in the control remained relatively constant. PAH degrading gene increased compared with control, providing microbial evidence of PAH biodegradation. A voltage-current relationship, which incorporated separation distance and the area of the electrodes, was established to predict current. A coupled reactive transport model was developed to simulate pH profiles and model results showed that pH is neutralized at the anode with upflowing groundwater seepage. This study demonstrated that electrode enhanced capping can be used to control redox potential in a sediment cap, provide microbial electron acceptors, and stimulate PAH degradation. / text

This dissertation explores cathodic electrodeposition mechanisms that describe the synthesis of redox-active electrode materials. Several interesting elements are known to deposit at negative potentials (e.g., Mo, Re, Se), and by extending this work, we can tailor the growth of new binary systems (e.g., MoxRe₁₋xOy, MoxSe₁₋xOy) that have enhanced optical and electronic properties. To grasp the subtleties of deposition and understand how the growth of a particular phase is influenced by other species in solution, several analytical methodologies are used to thoroughly characterize film deposition, including chronocoulometry, voltammetry, nanogravimetry, UV-Visible spectroelectrochemistry, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and inductively coupled plasma mass spectrometry (ICPMS). Chapter 1 is a general introduction that discusses the growth of redox-active metal oxides and alloys with an emphasis on tuning the composition to enhance material performance. Chapter 2 proposes a mechanistic pathway for the deposition of rhenium films from an acidic perrhenate (ReVIIO₄⁻) solution containing both metallic and oxide components. Unlike many other metal anions, it was observed that ReVIIO₄⁻ adsorbs to the electrode surface prior to reduction. As such, ReVIIO₄⁻ is ideally situated to be a redox-active mediator for other electrochemical reactions, and in Chapter 3, this dissertation explores how ReVIIO₄⁻ increases the deposition efficiency of Mo oxide deposition. Depth profiling XPS supported by electrochemical studies demonstrated that Mo and Re deposit separately to form an inhomogeneous material, MoxRe₁₋xOy (0.6 < x ≤ 1.0). Over a limited potential range from –0.3 V to –0.7 V (vs Ag/AgCl) the rhenium mole fraction increases linearly with the applied voltage. Chapter 4 explores the deposition of MoxSe₁₋xOy, and in this case, the incorporation of Mo species in solution shifts the deposition of Se⁰ to more positive potentials. Depending on the applied potential used, voltammetry experiments suggest that a small amount of Mo (<5%) reduces to the zero-valent phase to yield the photosensitive alloy, MoxSey. Chapter 5 discusses future work and presents preliminary data describing the deposition of Se⁰ on ITO using adsorbed ReVIIO₄⁻ as a redox mediator. / text

Cumulative evidence suggests that redox dysregulation in cancer cells represents a chemical vulnerability that can be targeted by pharmacological modulation of cellular oxidative stress. According to this emerging mechanism, pharmacological prooxidants may induce deviations from redox homeostasis causing cytotoxicity confined to malignant cells already at a high set point of constitutive oxidative stress leading to functional impairment, cell cycle arrest, and cell death. In contrast, the same prooxidant deviation from redox homeostasis is tolerated by nonmalignant cells that operate at a lower redox set point. This work focuses on experimental redox drug discovery targeting metastatic melanoma cells by pursuing the following specific aims: I. To identify drug-like lead compounds containing redox-directed pharmacophores for prooxidant intervention targeting melanoma in relevant models of the human disease. II. To investigate the molecular mechanism of action underlying antimelanoma activity of our lead compounds comprising Michael acceptors [cinnamaldehyde (CA) and 2,6-dichlorophenolindophenol (DCPIP)] and endoperoxides [dihydroartemesinin (DHA)]. III. To explore the therapeutic potential of drug-like electrophiles for non-melanoma indications including skin photoprotection and genotype-directed cancer chemotherapy. First, we have explored the possibility that prooxidant dietary constituents containing an electrophilic Michael acceptor pharmacophore may display chemotherapeutic activity. Focusing on the cinnamon-derived Michael acceptor CA we have demonstrated significant anti-melanoma activity of this dietary prooxidant observed in vitro and in vivo. Second, we have demonstrated that the synthetic quinoneimine and redox dye DCPIP targets human melanoma cells in vitro and in vivo. DCPIP-apoptogenicity observed in the human melanoma cell lines A375 and G361 was inversely correlated with NAD(P)H:quinone oxidoreductase (NQO1) expression levels. Efficacy against tumors with low NQO1 enzymatic activity including those displaying the human homozygous NQO1*2 missense genotype suggests feasibility of DCPIP-based genotype-directed redox intervention. Third, we demonstrated that the endoperoxide-based antimalarial DHA may serve as an experimental redox chemotherapeutic that selectively induces iron-dependent melanoma cell apoptosis without compromising viability of primary human melanocytes. Given the causative role of redox dysregulation in melanoma and the shortage of efficacious agents currently available, it seems that the emerging therapeutic potential of redox-directed chemotherapeutics for melanoma intervention deserves further evaluation.

Iron (Fe) exerts strong control over environmental biogeochemistry. As the fourth most abundant element, Fe is present in nearly all earth environments, where it plays important roles in governing the transformation and movement of organic and inorganic constituents, and in microbial respiration. Consequently, the body of work on Fe biogeochemistry is vast. This study is specifically concerned with the dynamic changes in the oxidation state of Fe (i.e., redox cycling) and their impact on the inorganic, organic and microbial components in soil. I constructed a special apparatus to fluctuate redox potential on soil slurries while concurrently sampling a wide range of biogeochemical variables (pH, redox potential, major and trace elements, CO2 release, DNA community composition charges, etc.). Previous research has documented redox fluctuations along a climate gradient in Hawaii and a primary goal of this dissertation was to reconstruct these redox fluctuations, subjected to experimental constraints afforded by a laboratory setting, with minimal disruption to the biogeochemical processes controlling Fe redox cycling. By recasting the spatial and temporal characteristics of in situ Fe redox cycling in the laboratory, I was able to form testable hypotheses regarding the importance of Fe redox oscillations to soil mineral transformations, colloid composition/dynamics and microbial community structure. A second goal of this dissertation was to explore the utility of Fe isotopic composition for providing information on soil weathering processes along age and climate gradients at the field scale in Hawaii. This portion of the study tested emerging theories of Fe isotope fractionation during mineral dissolution using well-characterized sequences in soil weathering intensity.The principal findings of the laboratory redox fluctuation experiments are that Fe redox oscillations: (1) trigger an increase in the crystallinity of Fe-oxides; (2) mobilize colloids containing refractory elements (e.g., Zr, Nb, U, etc.); (3) reveal redox sensitive rare earth element (REE) anomalies in the aqueous phase; and (4) induce changes in the microbial community favoring microbes capable of growth under both oxic and anoxic conditions. The principal finding of the Fe isotope measurements is that isotopic composition is directly related to weathering intensity in the field, consistent with theoretical predictions.