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Response of Oxidation-Reduction Potential to Changes in Hydrology and Vegetation in an Agricultural Drainage Ditch with WeirsShoemaker, Cory 17 August 2013 (has links)
Excess nutrients entering aquatic systems cause negative effects downstream. Oxidation-reduction potential (Eh) is an inexpensive proxy which can be used to define the potential nutrient reducing capacity of a system, in particular denitrification. My thesis attempts to determine effects of hydrology and vegetation manipulations on Eh in an agricultural drainage ditch with weirs using continuous automated data loggers to monitor the system. Accuracy and precision of the continuous automated data loggers was confirmed through laboratory and field testing. Effects of hydrology and vegetation on Eh were quantified during testing from May-September 2012 in east-central Mississippi. Vegetation affected Eh (t=-1.75, P=0.08, df=9,754) whereas changes in hydrology also affected Eh (t=7.05, P<0.001, df=9,754). Modeling of these variables indicated the interaction of hydrology and vegetation was the most influential factor measured. Through management of hydrology and vegetation in ditches, Eh can be managed to create conditions conducive for denitrification.
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Geochemistry of Forest Rings in Northern Ontario: Identification of Ring Edge Processes in Peat and SoilBrauneder, Kerstin M. 24 August 2012 (has links)
Forest rings are large features common in Ontario’s boreal forests that comprise circular topographic depressions in carbonate mineral soil that are filled with peat. This thesis documents differences in peat and soil chemistry along transects across the “Bean” and “Thorn North” rings, which are centered on accumulations of CH4 and H2S, respectively. Within the mineral soil, ring edges are characterized by strong negative anomalies in pH, ORP and carbonate, as well as positive anomalies of Al, Fe and Mn in the results of aqua regia and hydroxylamine-hydrochloride digestions. Within the peat, positive carbonate and pH anomalies are recorded. This antithetic relationship suggests vertical migration of carbonate species from clay to peat. An inverse relationship exists between ORP, versus redox inferred from aqua regia. Strong ORP lows occur where oxidized products show highest concentrations. This is interpreted to reflect the proliferation of autotrophic organisms occupying the strong redox gradient at the ring edge.
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Geochemistry of Forest Rings in Northern Ontario: Identification of Ring Edge Processes in Peat and SoilBrauneder, Kerstin M. January 2012 (has links)
Forest rings are large features common in Ontario’s boreal forests that comprise circular topographic depressions in carbonate mineral soil that are filled with peat. This thesis documents differences in peat and soil chemistry along transects across the “Bean” and “Thorn North” rings, which are centered on accumulations of CH4 and H2S, respectively. Within the mineral soil, ring edges are characterized by strong negative anomalies in pH, ORP and carbonate, as well as positive anomalies of Al, Fe and Mn in the results of aqua regia and hydroxylamine-hydrochloride digestions. Within the peat, positive carbonate and pH anomalies are recorded. This antithetic relationship suggests vertical migration of carbonate species from clay to peat. An inverse relationship exists between ORP, versus redox inferred from aqua regia. Strong ORP lows occur where oxidized products show highest concentrations. This is interpreted to reflect the proliferation of autotrophic organisms occupying the strong redox gradient at the ring edge.
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Modelling uranium leaching kineticsSililo, Bernard Liswani January 2016 (has links)
The uranium price decline has negatively impacted on the uranium mining industry. This
decline in price requires that uranium metallurgical processes be made to operate more
efficiently. Some key parameters that influence the dissolution and kinetics of leaching
uraninite (one of the main minerals from which uranium can be extracted) are pH, oxidationreduction
potential and iron concentration. A good understanding of the effect these
parameters have on the leach kinetics would lead to an efficient operation of metallurgical
processes. The objective of this work was therefore to investigate the effects of these key
drivers on leach kinetics of Rӧssing Uranium ore. Added to this, was an attempt to come up
with a mathematical model which can successfully replicate the leach kinetics. A series of
laboratory leach experiments were performed on Rӧssing ore where the pH, oxidationreduction
potential and total iron were varied, one at a time, to establish the effects they
have on the leach kinetics and on the uranium extraction.
Analysis of the data collected from this study showed that the leach kinetics are more
dependent on the oxidation-reduction potential, followed by the iron concentration and least
affected by the pH. It was further shown that oxidation-reduction potential is a function of
total iron. An integral method was used to analyse the kinetic data. A literature study reveals
that uraninite dissolution follows first order kinetics, but of interest in these results was that
the uranium dissolution was found to closely follow the second order. Further research is
recommended to look at ascertaining these results. Two models were developed, one using regression and the other by curve fitting method. Both models could fit the
experimental data well enough. / Dissertation (MSc)--University of Pretoria, 2016. / Materials Science and Metallurgical Engineering / MSc / Unrestricted
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Development of a Plasma Biomarker to Test Oxidative Stress in Frail Elders with Traumatic InjuryBourg, Pamela Wilkinson January 2016 (has links)
Background: Physically injured elder adults present challenges in the emergent injury phase. Oxidative stress contributes to cellular deterioration, resulting in decreases in physiological reserve. Imbalance of oxidative stress pathways lead to damage and drive the aging process and frailty. Goals of this study were to determine if a new plasma biomarker of oxidative stress is related to: 1) oxidation reduction status in patients who have experienced traumatic injury as well as healthy community dwellers, 2) outcomes of patients who have experienced trauma, 3) frailty measured by established frailty scales in healthy community dwellers. Methods: Prospective study included 1) trauma patients ≥65 admitted to Level I trauma center 2) age, gender matched healthy, community-dwelling participants. Plasma samples tested in duplicate for capacity oxidative reductive potential (cORP, μC; antioxidant reserve), and static oxidative reductive potential (sORP, mV; the current state of oxidative stress). Frailty assessments were performed in healthy participants using established frailty scales. ORP measurements were analyzed using correlation analyses. Univariate analysis analyzed cORP and sORP for differences by the variables gender, age, smoking, diabetes, statin use, vitamin use and any alcohol use in both the injured and healthy populations. Results: 186 subjects included in study (N=93 for both groups). Trauma groups's cORP values were significantly lower in patients with diabetes (p<0.05) and patients that smoked (p<0.01). Similarly the healthy group's cORP was significantly lower for those who smoked and those with diabetes (p<0.05). Non-vitamin use in the healthy group was related to lower cORP values (p<0.05). Trauma patients who smoked and those with diabetes exhibited higher sORP values (p<0.05). In the healthy group, sORP did not differ when considering the variables. No12significant differences were found based on gender, statin or alcohol use for either group. Significant correlation was found for both sORP and cORP with CSHA Clinical Frailty Scale in the healthy group. Conclusion: Findings suggest that the variables of smoking and diabetes are contributory to frailty trajectory. Data suggest the capacity to tolerate oxidative stress, measured by cORP, is lower in aged individuals that smoke or are diabetic and contributes to frailty as a result of oxidative damage.
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Quantum chemical studies of spectroscopy and electrochemistry of large conjugated molecular systemsCho, Sangik 03 September 2009 (has links)
The molecular identity of the green emission of polyfluorene is investigated in the view point of the molecular interactions between modeled segments. The semi-empirical quantum methods, ZINDO/S and AM1 (AM1-CIS), are used in combination to provide reasonable explanations for experimental spectroscopic properties of monodisperse fluorene oligomers and fluorene oligomers with a central keto defect in dilute solutions. Applying the same method, the molecular interactions between model segments are found to exist and are significant. However, the spectroscopic property change from the molecular interactions is negligible. In addition, the effects of mechanical stress and multi-defects on fluorene oligomers are investigated. On the other hand, the redox mechanisms proposed for the oxidation of an amphiphilic cyanine (C8S3) J-aggregates immobilized at ITO electrode and the subsequent dehydrogenated dimmer formation during cyclic voltammetry based on analysis of absorption spectra during the process are verified with the combined semi-empirical quantum methods similar to the previous methods. The absorption spectra assigned by experiment for electrochemical species involved in the proposed mechanism show reasonable match to the theoretically estimated absorption energies of the corresponding simplified model systems. In addition, the standard reduction potentials of the fairly large molecules, C8S3 monomer and its dehydrogenated dimer, are pursued with quantum mechanical calculations. The free energy difference between the oxidized and reduced states of the target systems is decomposed to electronic energy, solvation energy and temperature-dependent free energies terms. Based on AM1 ground state geometries and with the corresponding temperature dependent free energies, the electronic energies and the solvation energies are each evaluated by two different methods. The electronic energies are calculated with AM1 method and DFT calculation and, also, the solvation energies are obtained based on the atomic partial charges from AM1 and DFT wavefunctions with continuum dielectric solvent approximation. The four calculation schemes from the combinations of the electronic and solvation energy estimation methods are tested with the redox compounds with various molecular weights and the estimations are compared with the corresponding experimental redox potentials. The relative redox potentials between two different redox systems are found to be reasonably estimated with the four calculation schemes. / text
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Computational studies of protein pK(a)s and metalloprotein reduction potentialsLi, Hui 01 January 2004 (has links)
Protein pK(a)s and metalloprotein reduction potentials are studied with computational methodologies based on an ab initio quantum mechanics (QM) description of the protein and a linearized Poisson-Boltzmann Equation (LPBE) description of the solvent.
The practical applicability of the QM/LPBE method is extended to proteins by using a QM description of the ionizable residue and a molecular mechanics (MM) description of the rest of the protein. This QM/MM/LPBE method is used to predict the pKa of Lys55 in the serine protease inhibitor turkey ovomucoid third domain (OMTKY3) and the prediction of 11.0 is in good agreement with the experimental value of 11.1. This is the first time a protein pKa value has been predicted with QM/MM methods.
The QM/LPBE method is used to predict and interpret the pKa values of the five carboxyl residues (Asp7, Glu10, Glu19, Asp27, and Glu43) in OMTKY3. All the predicted pKa values are within 0.5 pH units of experiment, with a root mean square deviation of 0.31 pH units. We find that the decreased pKa values observed for some of the residues are primarily due to hydrogen bonds to the carboxyl oxygens. Hydrophobic effects are also shown to be important in raising the pKa. Interactions with charged residues are shown to have relatively little effect on the carboxyl pKa values in this protein, in general agreement with experiment.
The relative Cu2+/Cu+ reduction potentials of six type-1 copper sites (cucumber stellacyanin, P. aeruginosa azurin, poplar plastocyanin, C. cinereus laccase, T. ferrooxidans rusticyanin and human ceruloplasmin), which lie in a reduction potential range from 260 mV to over 1000 mV, have been studied with the QM/LPBE method. For the first time, the range and relative orderings of the reduction potentials are reproduced well compared to experimental values. The study suggests that the main interactions determing the relative reduction potentials of blue copper sites are located within 6 Å of the Cu atoms. Further analysis suggests that the reduction potential differences of type-1 copper sites are caused by axial ligand interactions, hydrogen bonding to the S(Cys), and protein constraints on the inner sphere ligand orientations.
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Optimalizace metod hodnocení fosfátovacích lázní / Optimalisation of evaluation methods for phosphating bathesBrzuchańská, Anna January 2008 (has links)
This work deals with phosphating technology of steel. In theoretical part are summarized facts about conventional phosphating process, including steel surfaces pretreatment. In the next chapter the latest contemporary technology of phosphating is discussed, i.e. electrolytic phosphating. This chapter contains principles and characteristics of this technique. Than follow comparisons of electrolytic phosphating and conventional process, concerning economical and ecological aspects. In experimental part is firstly stated nowaday situation of process analyses of phosphating bath for electrolytic phosphating. Intention of experimental part is finding of analytical technique which can be used in operating conditions of phosphating production line. Next chapter render an account of all analytical techniques – measuring of density, refractive index, conductance, reduction potential, pH, turbidity and determination of sulphate, iron and phosphate by indicator papers. Discussion of all results leads to conclusions on tested techniques in connection with practical use in operating conditions of phosphating production line and recommendations for use of individual analytical techniques.
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Oxidation-reduction potential as an indicator of disease activity in pediatric patients with inflammatory bowel diseaseCataldo, Giulio F. 07 October 2023 (has links)
INTRODUCTION: Inflammatory bowel disease (IBD) is a complex, chronic, autoimmune disease of the gastrointestinal tract. Reactive oxygen species (ROS), a product of active leukocytes, have been implicated in the pathogenesis of IBD. The ability to reliably measure ROS in blood, urine, and stool samples could represent a new approach to assessing disease activity and response to therapy in pediatric patients with IBD.
OBJECTIVES: To assess the relationship between redox measurements and clinical disease activity in pediatric patients with IBD.
METHODS: Biological specimens, including stool, urine, blood plasma, and intestinal aspirates, were collected from patients at Boston Children’s Hospital. Each sample’s oxidation-reduction potential was measured by two oxidation-reduction potential probes (an Arrowdox probe and a Mettler Toledo probe). Probes were directly immersed into the sample, returning a millivolt measurement of oxidation-reduction potential. Linear regression was performed to explore the relationship between patient-reported outcome measures (PROMs) and redox measurements of biological specimens. Patients were also stratified by disease severity, and ANOVA testing was performed to test for differences in oxidation-reduction potential observed in patients with remittent, mild, moderate, and severe disease activity.
RESULTS: Redox values in stool, urine, plasma, and intestinal aspirate did not significantly correlate with PROMs or differ significantly among groups categorized by disease severity.
CONCLUSIONS: Measurements of oxidation-reduction potential from stool, urine, plasma, and intestinal aspirate do not appear to be useful for assessing disease severity in pediatric patients with inflammatory bowel disease.
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Stratified Arrays of Needle-Type Oxidation Reduction Potential SensorsRadhakrishnan, Praveen Kumar 22 December 2009 (has links)
No description available.
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