Dissertations / Theses: 'Redox condition'

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Igboamalu, Tony E. "Kinetic studies of Cr(VI) reduction in an indigenous mixed culture of bacteria in the presence of As(III)." Diss., University of Pretoria, 2014. http://hdl.handle.net/2263/46240.

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An indigenous mixed culture of bacteria collected from a Wastewater Treatment Plant (Brits, North West Province, South Africa), biocatalytically reduced Cr(VI) in the presence of As(III). Both the reduced chromium (Cr(III)) and the oxidised arsenic (As(V)) readily form amorphous hydroxides that can be easily separated or precipitated from the aqueous phase as part of the treatment process. Treatment of Cr(VI) and As(III) before disposal of wastewater is critical since both compounds are known to be carcinogenic and mutagenic at very low concentrations, and acutely toxic at high concentrations. Batch experiments were conducted to evaluate the rate of Cr(VI) reduction under anaerobic condition in the presence of its co-contaminant As(III) typically found in the groundwater and mining effluent. Results showed near complete Cr(VI) reduction under initial Cr(VI) concentrations up to 70 mg/L in a batch amended with 20 mg/L As(III). However, increasing Cr(VI) concentrations up to 100 mg/L resulted in the inhibition of Cr(VI) reduction activity. Further investigation was conducted in a batch reactor amended with 70 mg/L Cr(VI) concentration at different As(III) concentrations ranging from 5-70 mg/L to evaluate the effect of varying As(III) concentration on Cr(VI) reduction efficiency. Results showed that Cr(VI) reduction efficiency increased as As(III) concentrations increased from 5-40 mg/L. However, further increase in As(III) concentration up to 50 mg/L resulted in incomplete Cr(VI) reduction and decrease in Cr(VI) reduction efficiency. These results suggest that the rate of Cr(VI) reduction depends on the redox reaction of As(III) and As(V) with Cr(VI). Moreover, the inhibitory effect observed at high Cr(VI) and As(III) concentration may also be attributed to the dual toxicity effect of Cr(VI) and As(III) on microbial cell. From the above batch kinetic studies lethal concentration of Cr(VI) and As(III) for these strains was evaluated and established. Initial evaluation of the bacteria using 16S rRNA partial sequence method showed that cells in the mixed culture comprised predominantly of the Gram-positive species: Staphylococcus sp., Enterobacter sp., and Bacillus sp. The biokinetic parameters of these strains were estimated using a non-competitive inhibition model with a computer programme for simulation of the Aquatic System “AQUASIM 2.0”. Microbial reduction of Cr(VI) in the presence of As(III) was further investigated in continuous-flow bioreactors (biofilm reactor) under varying Cr(VI) loading rates. The reactor achieved Cr(VI) removal efficiency of more than 96 % in the first three phases of continuous operation at lower Cr(VI) concentration ranging from 20-50 mg/L. However, 20 % decrease in Cr(VI) removal efficiency was observed as Cr(VI) concentration increase up to 100 mg/L. The reactor was able to recover from Cr(VI) and As(III) overloading phase after establishing the resilient nature of the microorganism. Similarly to the batch reactor studies the overall performance of the reactor also demonstrated that the presence of As(III) greatly enhance Cr(VI) reduction in a bioreactor. This was evident by near complete removal of Cr(VI) concentration up to 50 mg/L. The basic mass balance expressions on Cr(VI) along with the non-competitive inhibition model were used to estimate the biokinetic parameters in the continuous flow bioreactor system. Cr(VI) reduction efficiency along the longitudinal column was also evaluated in this study. Results showed that Cr(VI) efficiency increased as Cr(VI) concentration travels along the longitudinal column. Other important factors such as oxygen and pH during biological Cr(VI) reduction in the presence of As(III) oxidation were also evaluated.
Dissertation (MEng)--University of Pretoria, 2014.
tm2015
Chemical Engineering
MEng
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Pham, Thu Ha. "Modifications de la physiologie de la levure Saccharomyces cerevisiae par des changements d’environnements redox et gazeux en condition de brasserie." Dijon, 2008. http://www.theses.fr/2008DIJOS001.

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Modifier les flux métaboliques chez Saccharomyces cerevisiae présente un intérêt non seulement pour l’étude du métabolisme cellulaire mais aussi pour le développement de nouvelles technologies en industries des boissons alcoolisés afin d’améliorer les performances de la production, baisser le niveau d’alcool et développer des sous-produits valorisables. En condition de brasserie, l’utilisation de gaz a permis de modifier l’environnement redox de S. Cerevisiae au cours de la fermentation alcoolique. Les environnements gazeux et redox extrêmes ont altéré partiellement la croissance ainsi que la morphologie cellulaire. Cependant, la performance de la fermentation a été améliorée de 13 à 15% sous atmosphères gazeuses (hydrogène et hélium). Le profil des métabolites de fermentation y compris des composés d’arômes a été différemment modifié par l’effet de gaz et du redox (augmentation de la production de glycérol, de succinate et de certains alcools supérieurs importants pour la flaveur de la bière ; diminution de la quantité des certains esters aromatiques). Au cours d’une conservation à 4°C en condition nutritive limitée, la survie de S. Cerevisiae issue des cultures sous gaz a été améliorée de 55% grâce à sa teneur importante en glycogène intracellulaire et son adaptation morphologique. Ces résultats apportent un éclairage nouveau sur le comportement physiologique de la levure S. Cerevisiae face à des changements d’environnements gazeux et redox. Ils ouvrent également des perspectives pour l’étude de l’application des gaz et du redox dans les industries utilisant S. Cerevisiae
Modifying metabolic fluxes in Saccharomyces cerevisiae presents an interest both for cellular metabolism studies and the development of new technologies in alcohol beverage-related industries. This will permit to improve the production performances, to lower the alcohol level and to develop by-products of interest. During brewing fermentation, the use of gases modified the redox environment of S. Cerevisiae. The gaseous environments and extreme redox conditions altered partially the growth as well as the cellular morphology. However, the fermentation performances were improved up to 13-15% in gaseous environments (hydrogen and helium). Fermentation metabolite profiles including aroma compounds were modified differently by the effect of gas and redox (increasing in the production of glycerol, succinate and some higher alcohols important for the flavour of beer; decrease in the levels of some flavour-active esters). During storage at 4°C under limited nutritive condition, the survival of S. Cerevisiae cultivated with gas was improved up to 55%. This is due to its high intracellular glycogen content and its morphological adaptation. These results provide new information on the physiological behaviour of S. Cerevisiae in gaseous and redox environments. They also offer perspectives for the studying of gas and redox applications in S. Cerevisiae-related industries

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Sansotta, Stefano [Verfasser], Dirk [Akademischer Betreuer] Zahn, Dirk [Gutachter] Zahn, and Bernd [Gutachter] Meyer. "Molecular Simulations Study of Silver Precipitation from Aqueous Solution and on Silica Substrate. Control of Shape and Charge via Redox Condition / Stefano Sansotta ; Gutachter: Dirk Zahn, Bernd Meyer ; Betreuer: Dirk Zahn." Erlangen : Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), 2020. http://d-nb.info/1219303453/34.

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Xiong, Yijun. "Phosphorus cycling under different redox conditions." Thesis, University of Leeds, 2018. http://etheses.whiterose.ac.uk/22045/.

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Phosphorus is a basic but essential nutrient element for life, as a major limiting nutrient, is also important for controlling primary productivity on geological timescales. However, P cycling is highly redox dependent through Earth history. The fate of P cycling in many environments is still not clear. This thesis is to investigate mineralogical controls on P cycling under different redox conditions. New geochemical data is reported in the low sulfate, euxinic Lake Cadagno, Switzerland, to investigate the behaviour of the phosphorus cycle. Sulfide-driven release of phosphorus from organic matter and Fe (oxyhydr)oxide minerals is re-trapped by Fe(II) phosphate to constrain the extent of P recycling, and this process is highly sulfate dependent. New experiments are designed to investigate what minerals control P cycling in the water column under different conditions. With the increase of P, Green rust is transformed to vivianite which shows that P concentrations exert first order controls on the mineralogy of Fe minerals, with strong implications for the availability of dissolved P in the water column. In order to quantify the extent of P cycling versus fixation in the sediments under different redox conditions, mass balance models are made based on 4 key redox scenarios. Analogous to those which were prevalent at various intervals in Earth history, under ancient episodes of ferruginous conditions, low flux of recycled P back to water column is controlled by both P re-uptake by Fe(III) (oxyhydr)oxide and the formation of Fe(II) phosphate. During the mid-Proterozoic and during Phanerozoic, under low sulfate euxinia, the flux of recycled P is constrained by Fe(II) phosphate formation. This study provides supporting evidence to the suggestion that the positive primary productivity feedback is constrained by these processes.

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Masters-Waage, Nicholas. "Redox cycling under nuclear legacy conditions." Thesis, University of Manchester, 2016. https://www.research.manchester.ac.uk/portal/en/theses/redox-cycling-under-nuclear-legacy-conditions(abb173ad-0a8c-47b9-a2e7-99ea2048d2c2).html.

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Subsurface contamination is common at nuclear sites and it is likely that radioactive wastes will be managed in the long-term via burial in a deep Geological Disposal Facility (GDF). The migration of radionuclides in the geosphere from such sites is a major societal concern. In particular, long-lived, redox-active radionuclides (in the case of this thesis: 99Tc and Np) can migrate over large distances due to their high solubility under oxic conditions. Bioremediation has been proposed as a mechanism to limit the migration of 99Tc and Np in the environment. Here, an electron donor is supplied to the subsurface and soluble Tc(VII) and Np(V) are reduced to poorly soluble Tc(IV) and Np(IV), respectively. Reduction occurs via direct microbial action (termed bioreduction) or through radionuclide reaction with the by-products of microbial metabolism (primarily Fe(II)). Given the ubiquity of microorganisms and Fe in the geosphere, similar reactions can be expected in the deep subsurface surrounding a GDF. Once reduced, the long-term stability of the Tc(IV) and Np(IV) phases will significantly impact migration rates. Oxidative dissolution of Tc(IV)- and Np(IV)-bearing solids has been demonstrated in the literature and can be pervasive, thus questioning the efficacy of bioreduction. However, these studies have been conducted over short time-scales and during a single period of oxidation. Given the long half-life of 99Tc and Np and the ephemeral nature of redox conditions in the subsurface, there is a need to better understand 99Tc and Np biogeochemistry during longer time-scales and across multiple redox cycles. In this thesis, microcosm experiments have been used to address this knowledge gap. Sediment and groundwater used in the microcosms were representative of the Sellafield Ltd. nuclear site. For Tc, three successive redox cycles (reduction followed by oxidation with O2) over 2 years, gradually reduced the extent of Tc remobilisation during oxidation, and molecular scale characterisation of solids revealed that sediment associated Tc was always present as Tc(IV). Further, over time sequential extractions and EXAFS revealed an increased significance of Tc-Fe bonding in the sediment at the expense of TcO2. Despite this, a small but significant fraction of Tc(IV) was also found to be stable in solution during the experiments and XAS and TEM analysis suggested this was Tc(IV) associated with magnetite colloids. In other experiments completed with higher concentrations of bioavailable Fe (added as ferrihydrite to sediments, and in pure culture experiments with Geobacter sulfurreducens), the significance of Tc-Fe bonding was again highlighted, and potential Tc(IV) incorporation into biogenic magnetite was also documented. In experiments with Np, virtually all of the Np(V) added to oxic groundwater was removed to the sediment commensurate with microbially mediated Fe(III) reduction. Further, in systems with elevated bioavailable Fe, Np removal from solution was more extensive. Taken together, the data for Tc and Np reveals critical links between redox-active radionuclides and Fe cycling in sediments over periods of years and across multiple redox cycles. Furthermore, these processes help to predict the long-term fate of radioactive contamination at the Sellafield Ltd. nuclear site and have implications for contaminated land worldwide.

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Brown, Kevin Robert. "Cytochrome c₄ : characterisation, location and effect of growth conditions." Thesis, University of Edinburgh, 1988. http://hdl.handle.net/1842/30037.

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Rupp, Erik C. "Catalytic Dechlorination of Volatile Organic Carbons under Redox Conditions." Diss., The University of Arizona, 2009. http://hdl.handle.net/10150/194518.

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Chlorinated hydrocarbons, such as perchloroethylene (PCE) and trichloroethylene (TCE), are persistent environmental hazards, due to improper disposal, affecting groundwater sources located near a variety of industrial processes. As many chlorinated hydrocarbons are suspected carcinogens, there is great interest in developing inexpensive and environmentally sound technologies for the remediation of contaminated sites. Current efforts focus on the use of soil-vapor extraction (SVE) to pass gas phase contaminants through a granular activated carbon bed (GAC), which creates solid toxic waste, and possibly more harmful by-products during GAC regeneration. This research focuses on the use of hydrogen and short-chain alkanes, in combination with oxygen, to promote the conversion of PCE over a Pt/Rh three-way catalyst. The use of both of a hydrocarbon and oxygen creates mixed reducing-oxidizing (redox) conditions. Results indicate that redox conditions result in the complete removal of the target compound and produces primarily CO₂, H₂O and HCl. The process has proven to be most effective near stoichiometric conditions with respect to the reducing and oxidizing agents (2:1 for H₂:O₂ and 1:5 for propane:O₂). Residence times in the reactor are typically on the order of 0.1 to 0.5 seconds and catalyst surface temperatures range from 200 °C to 550 °C, with PCE conversion greater than 99% starting at 450 °C under slightly reducing (H₂:O₂ > 2) conditions. Laboratory results suggest that the catalytic mechanism is a multiple step surface reaction involving the three reactants (H₂/C₃H₈, O₂ and PCE). A mechanism based on Langmuir- Hinshelwood kinetics has been developed in an attempt to model the process. The role of the cerium oxide present in a three-way catalyst on the direct oxidation of perchloroethylene (PCE) has also been explored. Experiments have shown that in the absence of an external oxidizing agent, PCE can be converted over an alumina supported Pt/Rh catalyst. This work hypothesizes that the chlorine atoms in the adsorbed PCE interact with oxygen in oxidized cerium, CeO₂, reducing the cerium and replacing the oxygen atoms to create CeCl₃. This process begins at a catalyst surface temperature of 300 °C and reaches 100% conversion at 400 °C.

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Markelova, Ekaterina. "Interprétation du potentiel redox et évaluation de la mobilité des oxyanions contaminants (As, Sb,Cr) au cours de cycles redox successifs." Thesis, Université Grenoble Alpes (ComUE), 2016. http://www.theses.fr/2016GREAU028/document.

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Cette thèse démontre qu'une approche expérimentale systématique de complexité croissante permet de réévaluer le sens du potentiel redox (EH), et fournit une mise à jour sur l'interprétation de sa valeur dans les assemblages complexes de matrices minérales, des consortiums microbiens, des nutriments et des contaminants sous dynamique, oxydoréduction oscillant conditions. Pour étudier l'utilité des mesures EH dans les systèmes environnementaux saturés d'eau une cascade complète redox 500 à -350 mV (pH ~7.4) a été reproduit dans le laboratoire. Les expériences ont révélé que l'électrode de Pt classique redox répond à des processus microbiens dans une mesure différente en fonction de l'oxygénation et de la présence d'un tampon d'oxydo-réduction physique, chimique et. Les mesures du EH dans des matrices argileuses appauvris dans le tampon redox, tels que le couple électroactif Fe3 + / Fe2 +, par conséquent, se révèlent avoir une utilité limitée. Dans de tels environnements, les couples redox sensible abondantes, cependant, non électroactif, tels que O2 / H2O, CrO42- / Cr (OH) 3, NO3- / NO2- / NH 4 +, Sb (OH) 6- / Sb2O3, et HAsO42 - / H3AsO3 ne pas d'impact mesuré EH. Pour quantifier l'effet de l'oxydation des perturbations sur la mobilité des oxyanions dans la matrice argileuse, j'ai effectué des expériences de traitement par lots sous oscillations redox contrôlées. cycles successifs de conditions oxiques et anoxiques ont été imposées sur les suspensions argileuses modifiées avec un mélange d'oxyde As (V), Sb (V), Cr (VI) et N (V). la mobilité des oxyanions a été étudiée dans des conditions stériles, avec l'addition de carbone organique labile (éthanol), et avec l'addition de microbienne du sol inoculum. Spéciation analyses ont révélé des réactions irréversibles de réduction avec ou sans ajouts d'éthanol. Fraîchement réduite As (III), Sb (III), Cr (III) et N (III) ne sont pas ré-oxydée pendant les périodes subséquentes oxiques démontrant un comportement non-oscillant. Microbiologiquement induit des transformations de réduction a diminué les concentrations aqueuses de Sb et Cr par précipitation, enlevés N par volatilisation, alors préservé Comme dans la solution. En fonction de la diversité microbienne, altérées par l'addition d'inoculum dans le sol, deux types de contaminants imbrications sont caractérisés comme inhibiteurs de réduction et de non-inhibiteurs. Ces données, le représentant de l'environnement souterrain saturé (sous-sol> 20 m), est en outre par rapport à oxyanion mobilité dans l'environnement proche de la surface (la couche arable <0,15 m). Les principales différences entre les systèmes de la couche arable et du sous-sol sont dans la fraction d'oxyhydroxyde Fe-, Mn- et minéraux Al-, la diversité microbienne, pCO2, et la gamme des valeurs EH développées au cours des cycles d'oxydo-réduction. Par exemple, la gamme EH de plus de 900 mV (500 à -300 mV) dans la suspension de la couche arable est opposée à la gamme EH de 100 mV (350-250 mV) dans la suspension du sous-sol. En outre, dans la suspension de la couche arable, fort cycle redox de Fe et Mn coïncide avec la mobilité d'oscillation de As et Sb. Cette corrélation suggère le rôle crucial des minéraux oxyhydroxyde agissant non seulement comme principaux sorbants, mais aussi comme catalyseurs pour des réactions d'oxydation éventuellement contrôlant la réversibilité de la séquestration des contaminants. Par conséquent, appauvri en minéraux oxyhydroxyde, matrice argileuse est révélée environnement propice à la rétention des contaminants, car il peut supporter des oscillations périodiques redox sans libérer les contaminants de retour à la phase aqueuse sur l'échelle de temps expérimental
This thesis demonstrates that a systematic experimental approach of increasing complexity allows reassessing the meaning of the redox potential (EH), and provides an update on the interpretation of its value in complex assemblages of mineral matrices, microbial consortiums, nutrients, and contaminants under dynamic, redox-oscillating conditions. To study the usefulness of EH measurements in water-saturated environmental systems a full redox cascade from +500 to -350 mV (pH ∼7.4) was reproduced in the laboratory. The experiments revealed that conventional Pt redox electrode responds to physical, chemical, and microbial processes to a different extent depending on oxygenation and on the presence of a redox buffer. The measurements of EH in argillaceous matrices depleted in the redox buffer, such as the electroactive Fe3+/Fe2+ couple, thus, are shown to have limited usefulness. In such environments, the abundant redox-sensitive couples, yet non-electroactive, such as O2/H2O, CrO42-/Cr(OH)3, NO3-/NO2-/NH4+, Sb(OH)6-/Sb2O3, and HAsO42-/H3AsO3 do not impact measured EH. To quantify the effect of oxidizing perturbations on the mobility of oxyanions in the argillaceous matrix, I performed batch experiments under controlled redox oscillations. Successive cycles of oxic and anoxic conditions were imposed on the argillaceous suspensions amended with a mixture of oxidized As(V), Sb(V), Cr(VI), and N(V). Oxyanion mobility was investigated under sterile conditions, with the addition of labile organic carbon (ethanol), and with the addition of soil microbial inoculum. Speciation analyses revealed irreversible reduction reactions with and without ethanol additions. Freshly reduced As(III), Sb(III), Cr(III), and N(III) were not re-oxidized during subsequent oxic periods demonstrating non-oscillating behavior. Microbially induced reduction transformations decreased aqueous concentrations of Sb and Cr via precipitation, removed N via volatilization, while preserved As in the solution. Depending on microbial diversity, altered by the addition of soil inoculum, two types of contaminant interplays are characterized as inhibitory and non-inhibitory reductions. These data, the representative of saturated subsurface environment (subsoil > 20 m), is further compared to oxyanion mobility in the near-surface environment (topsoil < 0.15 m). The key differences between the topsoil and subsoil systems are in the fraction of oxyhydroxide Fe-, Mn-, and Al- minerals, microbial diversity, pCO2, and the range of EH values developed during redox cycles. For example, the EH range over 900 mV (from +500 to -300 mV) in the topsoil suspension is contrasted to the EH range of 100 mV (from +350 to +250 mV) in the subsoil suspension. Furthermore, in the topsoil suspension, strong redox cycling of Fe and Mn is coincident with the oscillating mobility of As and Sb. This correlation suggests the crucial role of oxyhydroxide minerals acting not only as major sorbents, but also as catalysts for oxidation reactions eventually controlling the reversibility of contaminant sequestration. Therefore, depleted in oxyhydroxide minerals, argillaceous matrix is shown to be suitable environment for contaminant retention, as it can stand periodical redox oscillations without releasing contaminants back to the aqueous phase on the experimental time scale

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Gaborieau, Marion. "Caractérisation des conditions redox du manteau terrestre dans différents contextes géodynamiques." Thesis, Université Clermont Auvergne‎ (2017-2020), 2019. http://www.theses.fr/2019CLFAC084.

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Plusieurs études ont permis de mettre en évidence que les basaltes d’arc sont plus oxydés (~ ∆QFM+1.5 ± 1) que les basaltes de rides médio-océaniques (MORB ; ∆QFM-1.2 à ~ ∆QFM). Cependant, l’état redox du manteau sous les arcs est toujours débattu. L’utilisation de différents proxys de la détermination de la fugacité d’oxygène (fO2) sur un même jeu d’échantillons a pour objectif de déterminer plus précisément l’état d’oxydation des magmas, de contraindre l’effet des processus secondaires tels que la différenciation et le dégazage sur leur état d’oxydation et ainsi de mieux caractériser la fO2 des magmas primaires et du manteau supérieur dans les différents contextes géodynamiques. Pour cela, les rapports Fe3+/ΣFe, les coefficients de partage du V entre les liquides silicatés et les olivines (DvOl/Liq) ainsi que les rapports V/Sc et V/Yb ont été déterminés dans des magmas piégés précocement après la fusion du manteau sous forme d’inclusions magmatiques dans des olivines magnésiennes (Fo > 80 %) provenant de différents contextes géodynamiques (i.e. contexte de dorsale médio-océanique, de zone de subduction et de point chaud). La détermination des rapports Fe3+/ΣFe par spectroscopie XANES avec des conditions analytiques permettant d’éviter les processus de photo-oxydation des verres hydratés et par spectroscopie Mössbauer a permis de confirmer que les basaltes d’arc sont plus oxydés que ceux des points chauds (OIB) et des MORB. La corrélation entre les rapports Fe3+/ΣFe et les teneurs en H2O des inclusions magmatiques suggère que la différence d’état d’oxydation serait liée à une variation de l’état d’oxydation du coin de manteau causée par le processus de subduction. De plus, les fO2 obtenues à partir de ces rapports indiquent qu’au sein de la population des magmas d’arc, l’état d’oxydation des magmas est variable d’une zone de subduction à l’autre. Par la suite, une évaluation de l’effet du dégazage des éléments volatils et de la cristallisation fractionnée sur la fO2 des magmas a été menée pour chaque population d’inclusions des différentes localités. Après avoir reconstitué les compositions des liquides magmatiques primaires, leur fO2 a été estimée à partir des différents proxys de la mesure de la fO2. Les résultats obtenus à partir des rapports Fe3+/ΣFe, des coefficients de partage DvOl/Liq et des rapports V/Yb indiquent que les magmas primaires d’arc sont plus oxydés que ceux des rides médio-océaniques et des points chauds. Cependant, les valeurs de fO2 obtenues à partir de ces trois proxys diffèrent. Par ailleurs, la corrélation entre les rapports Fe3+/ΣFe, les fO2 calculées à partir de ces rapports et les teneurs en H2O des magmas primaires suggère que la différence d’état d’oxydation des magmas n’est pas liée à l’effet des processus secondaires. Toutefois, la comparaison entre les rapports Fe3+/ΣFe, les fO2 calculées à partir de ces rapports et les rapports Th/La et Ba/La des magmas primaires ne permet pas d’affirmer que les variations observées seraient liées à l’influence d’un liquide silicaté provenant de la fusion des sédiments recouvrant la plaque plongeante ou d’un fluide aqueux libéré par la plaque au cours de la subduction. A l’opposé, les fO2 obtenues à partir des rapports V/Sc suggèrent que les magmas primaires d’arc ont un état d’oxydation comparable à ceux des MORB et des OIB
Many studies have demonstrated that arc basalts are more oxidized (~ ∆QFM+1.5 ± 1) than mid-ocean ridge basalts (MORB; ∆QFM-1.2 à ~ ∆QFM). However, the oxidation state of the sub-arc mantle is still debated. The use of various proxies on the same set of samples aims to determine the oxidation state of magmas, the effects of secondary processes on their oxidation state and to better constrain the fO2 of primary magmas from different geodynamic settings and that of their mantle source. For that purpose, Fe3+/ΣFe ratios, V partition coefficients between silicate melts and olivines (DvOl/Melt) as well as V/Sc and V/Yb ratios were measured in melt inclusions from high-Mg olivines (Fo > 80 %) from subduction zones, mid-oceanic ridges and hot spots. The analysis of Fe3+/ΣFe ratios by XANES spectroscopy using analytical conditions that prevent beam damage during analysis of hydrous glasses and by Mössbauer spectroscopy confirmed that arc magmas are more oxidized than those from hot spots and mid-ocean ridges. A positive correlation between Fe3+/ΣFe ratios and water contents in melt inclusions suggests that the oxidation state recorded in primitive arc magmas is likely to be due to changes in the oxidation state of the mantle beneath arcs because of subduction processes. The calculation of the fO2 from Fe3+/ΣFe ratios also indicates that the range of oxidation state recorded in arc melt inclusions varies from one subduction zone to another. An evaluation of the effects of volatile degassing and differentiation processes on the magmatic fO2 was carried out on each melt inclusion population. fO2 values were then estimated for reconstructed primary melt compositions using the different redox proxies. Results obtained from Fe3+/ΣFe ratios, DvOl/Melt partition coefficients and V/Yb ratios suggest that arc primary magmas are more oxidized than those from hot spots and mid-ocean ridges. However, fO2 values differ from one proxy to another. Furthermore, the positive correlation between the Fe3+/ΣFe ratios, the fO2 calculated from these ratios and the water contents of primary magmas suggests that the difference in the oxidation state of magmas is not due to secondary processes. However, the comparison between the Fe3+/ΣFe ratios, the fO2 values calculated from these ratios and Th/La and Ba/La ratios of primary magmas does not confirm that the observed changes in redox state can be simply linked to the influence of silicate melt or aqueous fluids coming from the slab to the mantle wedge. On the opposite, fO2 values calculated from V/Sc ratios suggest that primary arc magmas are comparable to those from mid-ocean ridges and hot spots

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Smedborn, Pausson Eva. "Chemical Stabilization of Arsenic in Contaminated Soil under Low Redox Conditions." Thesis, Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, 2019. http://urn.kb.se/resolve?urn=urn:nbn:se:ltu:diva-72340.

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Remediation techniques for arsenic contaminated soil have previously focused mostly on the surface soil layers where aerobic conditions are prevalent. In this master thesis, chemical stabilization by adding zero-valent iron (Fe(0)) and calcium oxide (CaO) to an arsenic-contaminated soil under low redox conditions have been studied through up-flow percolation tests. Over a time of 2 months, pH, conductivity, redox potential and concentrations of major and minor elements including As, Zn, Cu, Cd, Fe and Ca under both fluctuating and continuous flow were measured. Results indicate that CaO is a very promising amendment to use under conditions of low redox, immobilizing 98% of the As and 50-65% of Zn, Cd and Cr over the 8 weeks of testing, compared to the untreated soil. Copper on the other hand was mobilized by the treatment; but as the concentrations of Cu in the soil was low the increased leaching would in this case not be problematic. The leached water also had a very alkaline pH at 13, while conductivity was relatively high at 6.5 mS cm-1 and the redox potential remained negative throughout the two months. Geochemical modelling indicate that the immobilization of As is most likely controlled by precipitation of Ca-As-complexes as well as ettringite and portlandite. The precipitation of these minerals are controlled by pH, while redox conditions were shown to not be a controlling factor. The alkalinity of the CaO-amended soil was very high and it is expected that the alkaline conditions controlling the immobilization of As will prevail for hundreds of years. Fe(0) that previously has shown good results in stabilizing As under oxidized conditions did not effectively immobilize As under the low redox conditions in this study. Rather, the leaching of As and metals like Cr, Cd, Cu and Zn showed very similar results as the untreated soil. The results signifies the importance of activating the Fe(0) beforehand to allow amorphous Fe-oxides to form to which the metal(loids) can sorb to. In the study it was also observed that a fluctuating groundwater table could have an effect on both untreated and treated soil as wet and dry cycles influenced the leached concentrations of As and many other elements. More As was leached during the dry days in the untreated soil and the soil treated with Fe(0), while the opposite was true for the CaO-treated soil. The results suggests that using CaO as an amendment to treat As-contaminated soil is a method that potentially can be used for soils that have low redox conditions, for example soils below the groundwater table and landfills, although caution should be used in situations with more complex contamination, e.g. where both As and Cu are present.
Efterbehandlingsmetoder för arsenikförorenad jord har tidigare fokuserat på ytliga jordlager där syre finns tillgängligt och förhållandena är oxiska. I denna masteruppsats har kemisk stabilisering av arsenik under anoxiska förhållanden i en förorenad jord studerats. I perkolationsförsök över två månader har effekten av två olika kemiska tillsatser, nollvärt järn (Fe(0)) och kalciumoxid (CaO), på utlakningen av halvmetaller och metaller som As, Zn, Cd, Cu och Cr samt påverkan på pH, konduktivitet och redoxpotential undersökts under både fluktuerande och konstanta flöden. Resultaten visar att CaO är en lovande tillsats att använda för kemisk stabilisering av As i jordar som har anoxiska förhållanden. 98% av As immobiliserades jämfört med den obehandlade jorden. Behandlingen med CaO resulterade även i ett stabilt basiskt pH på 13. Konduktiviteten hölls också på en stabil nivå på 6,5 mS cm-1 medans redoxpotentialen varierade en del men var negativ under hela experimentet. Den utlakade koncentrationen av As låg mellan 0.059 och 0.021 mg L-1. CaO immobiliserade även Zn, Cd och Cr med en effektivitet som låg mellan 50-65%, jämfört med den obehandlade jorden. Koppar däremot mobiliserades och lakades ut i större utsträckning; men då Cu-koncentrationen i jorden var låg från början utgör detta inget större problem. Geokemisk modellering indikerade att immobiliseringen av As kontrolleras av pH, men förblev opåverkad av redoxpotentialen. Då alkaliniteten i den CaO-behandlade jorden var hög förväntas de basiska förhållandena som kontrollerar den kemiska stabiliseringen av As att kvarstå under flera hundra år. Tidigare studier har visat att Fe(0) till stor del stabiliserar As under oxiska förhållanden, men under de anoxiska förhållandena i denna studie hade den Fe(0)-behandlade jorden liknande resultat som den obehandlade jorden, både vad gäller utlakning av metaller, pH, konduktivitet och redoxpotential. Detta markerar vikten av att aktivera Fe(0) genom att låta den reagera med syre och vatten i jorden för att bilda amorfa Fe-oxider som (halv)metallerna kan adsorbera till. I detta fall tillsattes inget vatten i förväg, vilket ledde till att det mesta av järnet lakades ut direkt, utan att bilda fler ytor som speciellt As kan binda till. För båda dessa jordar var utlakningen av As två storleksordnar större jämfört med den CaO-behandlade jorden. Studien visade också att en fluktuerande grundvattennivå kan ha en effekt på utlakningen av grundämnen både behandlad och obehandlad jord, då cykler av anoxiska och oxiska förhållanden påverkade koncentrationerna i utlakningsvattnet. Mer As lakades ut under de dagar som hade mer anoxiska förhållanden jämfört med oxiska dagar för den Fe(0)-behandlade jorden och den obehandlade jorden, medans det motsatta var sant för den CaO-behandlade jorden. Resultaten indikerar att CaO har en potential till att användas för att kemiskt stabilisera As i jordar som har låga redox-förhållanden, exempelvis i jordar som är under grundvattenytan och i deponier, men att försiktighet ska användas i jordar som har en mer komplex föroreningssituation, speciellt i jordar som är förorenat av både As och Cu.

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11

Giles, Hamilton. "Biotransformation potential of phytosterols in biological treatment systems under various redox conditions." Thesis, Georgia Institute of Technology, 2012. http://hdl.handle.net/1853/48993.

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Phytosterols are naturally occurring compounds which regulate membrane fluidity and serve as hormone precursors in plants. They also have the potential to cause endocrine disturbances in aquatic animals at concentrations as low as 10 µg/L. Wastewaters from several industries which process plant matter can contain phytosterols at concentrations in excess of the above-stated level. Despite their endocrine disruption potential, very little is known about phytosterol physical properties and their biotransformation potential in biological treatment systems. Aerated stabilization basins (ASBs) are common biological treatment systems in North American pulp and paper mills. ASBs are large open lagoons which use tapered surface aeration to remove COD and prevent sulfate reduction in the water column. Phytosterols are released from wood during the pulping process and a small fraction enters the wastewater stream during washing of the pulp. Therefore, phytosterols may be exposed to aerobic or anaerobic environments depending on their solubility and solid-liquid partitioning behavior. The overall objective of this research was to systematically and quantitatively assess the biotransformation potential of phytosterols in biological treatment systems and to examine conditions leading to reduction of these compounds in wastewater effluent streams. The results of this research showed that phytosterols are sparingly soluble with aqueous solubility below 1 µg/L when present as a mixture. Phytosterols have a strong affinity to adsorb to solids and dissolved organic matter. The affinity for aerobic biomass was greater than for wastewater solids. The stigmasterol desorption rate and extent from wastewater solids increased with an increase in pH from 5 or 7 to 9. Phytosterols were biotransformed under aerobic conditions but not under sulfate-reducing or methanogenic conditions by stock cultures developed in this study. Biotransformation under nitrate-reducing conditions could not be confirmed conclusively. The continuous-flow system was successful in removing 72 to 96% of phytosterols. Biotransformation accounted for 23, 14 and 41 % of campesterol, stigmasterol and β-sitosterol removal, respectively. Phytosterols accumulated in the reactor sediment and accounted for 97 % of the total phytosterols remaining in the system. Phytosterols can be removed from wastewater streams during biological treatment by a combination of biotransformation and solids partitioning and control of system pH, DO and available carbon and energy sources can increase the degree of phytosterols removal. The results of this research can be used to engineer effective biological treatment systems for the removal of phytosterols from pulp mill wastewaters and other phytosterol-bearing wastewater streams.

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12

Ritter, Daniel James. "Relationship Between Recharge, Redox Conditions, and Microbial Methane Generation in Coal Beds." Diss., The University of Arizona, 2015. http://hdl.handle.net/10150/577493.

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Natural gas is an important transitional energy source to replace more carbon intensive coal combustion in the face of climate change and increasing global energy demands. A significant proportion of natural gas reserves (~20%) were recently generated by microorganisms that degrade organic-rich formations (i.e. coal, shale, oil) in-situ to produce methane. Recent studies have shown that these microbial communities may be potentially stimulated to generate more methane to extend the lifetime (~10 years) of existing biogenic gas wells. This dissertation investigates how microbial coalbed methane (CBM) systems are impacted by geochemical conditions, microbial community composition, and groundwater recharge. The first study is a review and synthesis of existing basic research and commercial activities on enhancement of microbial CBM generation, and identification of key knowledge gaps that need to be addressed to advance stimulation efforts. The second study couples water and gas geochemistry with characterization of microbial communities in coalbeds in the Powder River Basin (PRB), Wyoming to investigate the influence of microbiology on water and gas geochemistry. Geochemistry results indicated that nutrients are likely source in situ from coal, and that all sulfate must be removed from the system before methanogenesis will commence. Increased archaeal (i.e. methanogens) diversity was observed with decreasing sulfate concentration, while sulfate reducing bacterial communities were different in wells with high sulfate concentrations (sulfate reducing conditions) when compared to wells with low sulfate concentrations (methanogenic conditions). The third study uses noble gases to constrain the residence time of groundwater associated with CBM in the PRB. Measured diffusional release rates of 4He from PRB coals were ~800 times greater than typical rates observed in sandstone or carbonate aquifers, and measured 4He values far exceeded expected values from in-situ decay of U and Th. Groundwater 4He residence times ranged from <1 to ~800 years using the measured diffusion rates versus ~130 to 190,000 years using a standard model. Coal waters with the longest residence time had the highest alkalinity concentrations, suggesting greater extents of microbial methanogenesis, although there was no relationship between groundwater "age" and methane concentrations or isotopic indicators of methanogenesis. Constraining the relationship between microbial activity (e.g. mechanisms of coal biodegradation and methane generation), environmental geochemical conditions, and groundwater flow is important to better understand subsurface hydrobiogeochemical processes and to ensure the success of future projects related to stimulation of microbial CBM.

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13

Spain, Jackson M. "Characterization of redox conditions in a petroleum contaminated aquifer: Implications for bioremediation potential." Thesis, Virginia Tech, 2002. http://hdl.handle.net/10919/35250.

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Currently, the application of bioremediation requires extensive and costly monitoring due to limited understanding of the terminal electron accepting processes (TEAPs) that control biodegradation, which impairs the accurate quantification of contaminant mass loss. The measurement of redox conditions and evaluation of TEAPs are critical in assessing the capacity for bioremediation at any site. A series of batch microcosm experiments, using sediment collected from a gasoline-contaminated aquifer at Fort McCoy, Wisconsin, was designed to: 1) evaluate the role of Fe(III) in the development of TEAPs during biodegradation of benzene, toluene, ethylbenzene, and the xylenes (BTEX); 2) examine the biodegradation potential in different portions of the plume; and 3) compare methods of TEAP characterization. In general, the presence of Fe-oxides in microcosms inhibited methanogenesis. Although Fe-reducers did not actively degrade BTEX, Fe-reduction did occur, and most probable number (MPN) counts showed that added Fe(III) increased numbers of Fe-reducers in the microcosms. Methane production in microcosms constructed from sediment near the source area was ~5 times lower than levels produced by the mid-plume sediment. No Fe-reduction occurred in microcosms containing sediment from the source area. These results suggest that the source area has much lower biological activity than the mid-plume. TEAP characterization was conducted using a variety of methods, including geochemical indicators, redox dyes, MPN, and hydrogen concentrations. Monitoring of CH4 concentration yielded useful information in delineation of redox processes; Fe(II) monitoring was unreliable as a geochemical indicator. Redox dyes supplied basic information on reducing environments. MPN counts estimated microbial populations in lieu of faulty geochemical indicators, i.e., Fe(II). The measurement of H2 proved to be one of the more simple and reliable methods for TEAP identification. Results of this study indicate that TEAP characterization should include use of multiple methods; relying on geochemical indicators alone is not sufficient.
Master of Science

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14

Wilkes, Austin. "Phosphorus Mobility and Speciation Under Dynamic Redox Conditions in Shallow Eutrophic Freshwater Systems." ScholarWorks @ UVM, 2019. https://scholarworks.uvm.edu/graddis/1145.

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Internal loading of phosphorus (P) from lake sediments can delay the recovery of lakes from eutrophication for years to decades following decreases in external nutrient inputs. While internal P loading is a pervasive problem in freshwater systems, molecular speciation of P in benthic sediments of these systems remains poorly characterized. As different P species will exhibit different responses to changing sediment-water interface (SWI) geochemistry, quantifying P speciation in sediments is a critical step in understanding P dynamics in sediment-water systems. Here, various synchrotron-based techniques were employed to directly probe the bonding environments of P and iron (Fe) in natural and experimentally manipulated lake sediments in order to link chemical speciation to chemical behavior and to identify the geochemical drivers that mediate this linkage. We manipulated SWI redox conditions in mesocosm experiments to investigate the impacts of prolonged anoxia and redox oscillations on P mobility and speciation in sediments. Mesocosm experiments demonstrate that oscillating redox conditions near the SWI may drive accelerated P release from sediments relative to uninterrupted reducing conditions. Sediment P is found to be predominantly associated with Fe oxyhydroxides, calcium carbonate, and apatite minerals in three shallow hyper/eutrophic lakes in northern Vermont. In Missisquoi Bay and Lake Carmi, Fe redox cycling controls P mobility via precipitation and dissolution of Fe oxyhydroxides. In the hypereutrophic Shelburne Pond, the presence of Fe sulfides precludes redox-driven P cycling and P mobility is instead dominated by organic matter mineralization. Our results demonstrate that internal P loading can manifest differently in similar shallow lake systems due to differences in lake configuration, sediment P and Fe speciation, and organic content of sediments. This work demonstrates the potential utility, as well as the limitations, of P K- edge X-ray absorption near edge structure spectroscopy in determining sediment P speciation in freshwater lakes.

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15

Smith, Dean A. "The demonstration of electron-transfer reactions and their effect on model lignin condensation reactions under alkaline pulping conditions." Diss., Georgia Institute of Technology, 1986. http://hdl.handle.net/1853/5700.

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16

Dias, Gilberto Pereira. "Avaliação das condições redox das águas intermediárias do Oceano Atlântico Sudoeste nos últimos 40 mil anos." Universidade de São Paulo, 2018. http://www.teses.usp.br/teses/disponiveis/21/21137/tde-29012019-163323/.

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O conhecimento da paleoceanografia do Oceano Atlântico Sul tem aumentado nas últimas décadas, porém ainda são raros os trabalhos sobre o Atlântico Sudoeste que utilizam dados de proxies de condições redox de massas d\'água, relacionados às mudanças climáticas entre os períodos Pleistoceno superior e Holoceno. Diante disso, esta Dissertação de Mestrado avaliou as condições redox das águas intermediárias do Atlântico Sudoeste nos últimos 40 mil anos. Este trabalho fez estudos de proxies geoquímicos - de condições redox (V/Sc, V/Cr, V/Al, Mn/Al e Ni/Co), de aporte de sedimentos terTMTMrígenos (Fe/Ca e Ti/Ca), de produtividade (COT, CaCO3) e origem da matéria orgânica (δ13C e C/N) - em um registro sedimentar marinho coletado na região do talude continental da margem sudeste brasileira, e os relacionou com as mudanças da Célula de Revolvimento Meridional do Atlântico (sigla em inglês AMOC - Atlantic Medirional Overturning Circulation) e com os principais eventos climáticos em escala orbital, como o Último Máximo Glacial, e de escala milenar, como os eventos tipo Heinrich Stadials, Younger Dryas e 8.2. Os resultados demonstram que, nos últimos 40 mil anos, as águas intermediárias que banham a costa sudeste brasileira apresentam níveis óxicos, o que classifica o ambiente como oxidante, porém foi possível observar variações na quantidade de oxigênio dissolvido nessas águas durante determinados eventos climáticos, bem como variações no aporte de sedimentos terrígenos e na produtividade. Em escala orbital a insolação de verão do Hemisfério Sul e a variação do nível do mar, governadas pelo ciclo de precessão, apresentam-se como os principais mecanismos que influenciam essas variações. Em escala milenar a variabilidade da AMOC apresenta-se como o principal mecanismo responsável por essas variações. Dentre os eventos climáticos de escala milenar, o evento 8.2 demonstrou complexa variabilidade nas condições redox das águas intermediárias do Atlântico Sudoeste, uma vez que, durante sua ocorrência, observamos aumento das concentrações de oxigênio dessas águas e baixos valores de produtividade.
The interest in the paleoceanographic history of the South Atlantic Ocean has increased in the last decades, however there are still few studies regarding the redox conditions of the intermediate water masses of the Southwest Atlantic and their relationship to the climatic changes during the upper Pleistocene and Holocene. Within this context, this work aims to evaluate the redox conditions of the intermediate waters of the Southwest Atlantic in the last 40 ka. For this, geochemical proxies - of redox conditions (V/ Sc, V/ Cr, V/ Al, Mn/ Al and Ni/ Co), of terrigenous sediments supply (Fe/ Ca and Ti/ Ca), of productive (COT, CaCO3), and organic matter source (δ13C and C / N) - were applied to marine sediments from a core collected on the continental slope of the Brazilian Southeastern margin and then related it to changes in the Atlantic Meridional Overturning Circulation (AMOC) and with the main cold climatic events of North Atlantic, such as the Last Glacial Maximum and millennial scale, such as events type the Heinrich Stadials, Younger Dryas and 8.2. Our results show that, over the last 40,000 years, the redox conditions of the intermediate waters of the Brazilian Southeast margin present oxic levels, which classifies the environment as oxidant, however, variations was noticed in the amount of oxygen dissolved in these waters influenced by certain climatic events, as well as changes in the input of terrigenous sediments and in the productivity. In orbital scale, the summer insolation of the Southern Hemisphere and the variation of sea level, leaded by the cycle of precession, are presented as the main mechanisms that influence these variations. On the other hand, at millennia scale, the AMOC variability is the main mechanism responsible of these variations. Among the climate events at millennia scale, the event 8.2 demonstrated a complex variability of the redox conditions of the intermediate waters of the Southwest Atlantic, once during its occurrence we observed increase concentrations of oxygen in these waters and a decrease of productivity.

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17

Kabbes, Jason E. "Diamond Formation under Lower Mantle Redox Conditions: Experimental Constraints on the Mineralogical Host of Carbon in Earth’s Mantle." The Ohio State University, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=osu1282152005.

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18

Erbs, Marianne. "Formation and redox reactions of green rusts under geochemical conditions found in natural soils and sediments /." Zürich, 2004. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=15492.

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19

Schaller, Tobias Lukas. "Redox-sensitive metals in recent lake sediments proxy-indicators of deep-water oxygen and climate conditions /." [S.l.] : [s.n.], 1996. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=11901.

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20

Gennaro, Mimma Emanuela. "Sulfur behavior and redox conditions in Etnean hydrous basalts inferred from melt inclusions and experimental glasses." Thesis, Orléans, 2017. http://www.theses.fr/2017ORLE2005/document.

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Le soufre est un composant volatil important des magmas qui présente différents états d'oxydation en fonction des conditions d’oxydoréduction et de la phase dans laquelle il se trouve : dans le liquide silicaté, il est typiquement dissous comme S⁶⁺ et/ou S²⁻ , dans la phase gazeuse il se trouve principalement comme SO₂ (S⁴⁺ ) et H₂S (S²⁻). L’Etna, pour lequel les conditions d’oxydoréduction sont faiblement contraintes, est utilisée comme cas d’étude pour examiner le comportement du soufre dans les magmas basaltiques hydratés pendant la différenciation et le dégazage. Cette recherche combine l'étude des inclusions vitreuses avec une étude expérimentale en conditions magmatiques sur la solubilité du S dans les basaltes alcalins hydratés.Les résultats expérimentaux suggèrent l’important contrôle de la ƒO₂ sur la teneur en S dans les magmas hydratés de l’Etna, et le partage du S entre les phases fluid and liquid. Les inclusions vitreuses ont été piégées à différentes profondeurs à l'intérieur du système magmatique. Elles décrivent une tendance continue de différenciation, marquée par une cristallisation fractionnée, à partir de la composition picritique (FS) vers le basalte plus récent dégazé (2013). Le contenu en S dans le liquide de l'Etna est extrêmement variable et atteint 4150 ppm dans les inclusions vitreuses les plus primitives. Les spectres XANES Fe³⁺/ΣFe des certaines inclusions vitreuses donnent des rapports Fe³⁺/ΣFe généralement décroissants à partir du liquide le plus primitif (FS) jusqu’au plus évolué (2013). Les simulations effectué par le logiciel MELTS confirme que la diminution du rapport Fe³⁺/ΣFe est principalement due au processus de différenciation magmatique, renforcé par le dégazage du S à ƒO₂ < NNO + 1. Cette réduction du magma provoque à son tour la diminution de la solubilité du S dans les basaltes hydratés de l’Etna, et peut constituer un éventuel activateur de l’exsolution du S, à l’origine de l’important dégazage du S observé au cours des dernières décennies à l’Etna
Sulfur is an important volatile component of magmas that presents different oxidation states, depending on the redox conditions and on the phase of occurrence: in silicate melts it is typically dissolved as S⁶⁺ and/or S²⁻ , in the gas phase it occurs principally as SO₂ (S⁴⁺ ) and H₂S (S²⁻). Mount Etna, in which magmatic redox conditions are poorly constrained, is used as a case study to investigate sulfur behavior in hydrous basaltic magmas during magma differentiation and degassing. This research integrates the study of natural olivine-hosted melt inclusions with an experimental study on S solubility in hydrous alkali basalts at magmatic conditions.Experimental results suggest the important control of ƒO₂ on the S abundance in Etnean hydrous magma and its partitioning between fluid and melt phases. Melt inclusions were entrapped at different depths inside the magmatic system (up to ~ 18 km, below crater level). They delineate a continuous differentiation trend, marked by fractional crystallization, from the picritic basalt (FS) toward the most evolved and degassed (2013) basalt. S content in Etnean melt is extremely variable and reaches 4150 ppm in the primitive melt inclusions. XANES Fe³⁺/ΣFe spectra in some glass inclusions, resulted in the generally decreasing of Fe³⁺/ΣFe ratios from the most primitive (FS) to the most evolved (2013) melts. MELTS software confirms that the Fe³⁺/ΣFe decrease is due principally to the melt differentiation process, enhanced to the S degassing at ƒO₂ < NNO+1. Magma reduction, in turn, induces the decrease of the sulfur solubility in the hydrous Etnean basalt, as well as of the sulfide saturation, and may constitute a possible enhancer of S exsolution, triggering the important S degassing observed in the last decades in Mt. Etna

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21

Merrett, Greg Lee. "Groundwater redox conditions at a petroleum contaminated site, Kuils River, South Africa : pathways for BTEX biodegradation." Master's thesis, University of Cape Town, 2003. http://hdl.handle.net/11427/8588.

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Includes bibliographical references (leaves 84-88).
A shallow sandy aquifer, contaminated by petrol from an underground storage tank, was studied to determine if intrinsic bioremediation of the hydrocarbons is taking place. Groundwater samples taken from 32 monitoring wells were analysed for NO₃-,NH₄+, Mn²+, Fe²+, SO₄²-, and ΣH₂S. Portable electrodes were used to make field measurements of electrical conductivity, redox potential, and pH. The variation and distribution of these redox-sensitive groundwater constituents show that bioremediation via NO₃- reduction, Fe³+ reduction, and SO₄²- reduction (and possibly methanogenesis in the most reduced part of the plume) is occurring. In some cases redox processes are taking place simultaneously resulting in redox zones that overlap. Iron and sulphate reduction are the dominant processes taking place.

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22

Goncharov, Aleksey. "Redox - pressure - temperature conditions in the continental upper mantle in relation to C-O-H fluid speciation." Phd thesis, Université Jean Monnet - Saint-Etienne, 2012. http://tel.archives-ouvertes.fr/tel-00974462.

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The thesis is based on a petrologic and geochemical study of mantle xenoliths from the central Siberian craton and the Baikal-Mongolia region of central Asia. Its goal is to establish the redox regime of the lithospheric mantle in these two domains with distinct tectonic settings and age and relate it to thermal regime and the speciation of C-0-H fluids. Oxygen fugacity is calculated based on Fe2+/Fe3+ ratios in spinel and garnet of mantle peridotites obtained by Mössbauer spectroscopy. The study deals with the following topics: (i) microstructures, chemical and mineralogical composition of the xenoliths; (ii) Fe2+/Fe3+ ratios in minerals by Mössbauer spectroscopy; (iii) equilibration temperatures and pressures using mineral thermo-barometry; (iv) oxygen fugacity from mineral compositions using oxybarometry; (v) proportions of molecular components in C-0-H fluids coexisting with the studied rocks. The three main conclusions of this study are: (1) Oxygen fugacity in the lithospheric mantle in the central Siberian craton decreases from +1 to -4 ΔlogʄO2 (FMQ) at depths from 70 to 220 km and shows significant lateral variations. (2) The lithospheric mantle beneath the Baikal-Mongolia region shows important redox heterogeneities, with a sharp decrease in oxygen fugacity (from +0 to -3 AlogfO2 (FMQ)) during the transition from the spine! to garnet facies peridotites at 50 to 90 km. (3) The speciation of C-O-H fluids changes with depth from essentially H2O-CO2 in the shallow lithospheric mantle to H2O-CH4 at the lithosphere-asthenosphere boundary regardless of the thermal state and the thickness of the lithosphere

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Gronowski, Adrian. "Effects of uranium mining on groundwater - Geochemical modeling of aqueous uranium speciation due to changing redox conditions." Thesis, KTH, Mark- och vattenteknik, 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-161064.

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As a consequence of rising uranium prices an interest in Sweden’s U deposits has emerged. This raises the important question of the possible environmental impacts of U mining operations. One of the most significant and serious issues is the contamination of groundwater by U following mining activities. The processes of uranium release and subsequent transport in groundwater is closely tied to its aqueous chemistry i.e. aqueous speciation, adsorption to mineral surfaces and dissolved organic carbon (DOM). The chemical parameters exerting the most control over these processes are pH and redox potential. The redox potential plays a decisive role because it controls the solubility of uraninite, a common uranium mineral and ore in Sweden’s bedrock deposits. Thus, by gaining insight into how changing redox conditions affect uraninite solubility, assessments can be made in order to estimate the extent of uranium transport by groundwater. Therefore the effects of the redox po-tential on U mobility will be examined in this work by means of computer modeling in the geochemical software VISUAL MINTEQ 3.0. The composition of the water used for modeling resembled that of a typical bedrock groundwater of Northern Sweden in the areas above the highest coastline. The simulations were carried out under different redox potentials at different pH levels in the presence of ferrihydrite and DOM to include the effects of U adsorption. The results show that the redox potential at which the uraninite mineral dissolves varies depending on the pH of the groundwater. From pH 4.0 to 7.5 the redox potential at which uraninite oxidizes decreases from 240-250 mV to 50-60 mV. This means higher redox conditions are needed for the dissolution of uraninite at low pH. Additionally, it is further concluded that the adsorption of U to ferrihydrite and DOC is important at pH 5-8 and pH < 7 respectively, which therefore play an important role in controlling the mobility of U in the modeled groundwater.

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Barbieri, Manuela. "Effect of redox conditions on the fate of emergin organic micropollutants during artificial recharge of groundwater: batch experiment." Doctoral thesis, Universitat Politècnica de Catalunya, 2011. http://hdl.handle.net/10803/109161.

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La recarrega artificial de les aigües subterrànies consisteix en infiltrar aigua als aqüífers per mitjà de les instal·lacions dissenyades per a tal fi i representa una eina important en la gestió dels recursos. A més de l’augment dels recursos d'aigües subterrànies, la recàrrega pot suposar una millora natural de la seva qualitat durant el seu pas pel subsòl. Els processos que tenen lloc en el sistema sòl-aqüífer (filtració, adsorció, reaccions de mescla , redox, biodegradació, etc) han demostrat produir una millora integral de la qualitat de l'aigua, eliminant també de manera efectiva una sèrie de contaminants orgànics. En l'actualitat, la qüestió és saber si la contaminació pels microcontaminants orgànics emergents, és a dir, productes farmacèutics, cosmètics, hormones, drogues il·lícites, pesticides i tensioactius, també es poden atenuar de forma natural. Alguns d’aquests compostos no són completament eliminats pels tractaments d'aigua residual convencionals, essent introduïts contínuament en els cursos d’aigua superficials pels efluents de les plantes de tractament. Malgrat la baixa concentració (ng/L i μg/L), la seva presència en el medi ambient és actualment un problema per a la vida aquàtica i la salut humana. En aquest context, la recàrrega artificial pot esdevenir una alternativa potencial o un tractament complementari per a l'eliminació de microcontaminants orgànics de l’aigua. Hi ha evidències que les condicions redox predominants podrien influir en el comportament d’aquests productes en l'aqüífer. No obstant, en el cas dels microcontaminants emergents, el coneixement sobre aquest tema és encara molt limitat. L’objectiu principal d’aquesta tesi és doncs investigar el possible efecte de les condicions redox sobre el destí de microcontaminants orgànics, la majoria dels quals són contaminants emergents. El treball està motivat pels projectes de recàrrega artificial amb aigua del riu Llobregat (Barcelona, Espanya). L’estudi es basa en experiments de laboratori (batch) utilitzant materials naturals de l'aqüífer, microcontaminants en concentracions ambientals (1 μg/L de cada compost), i unes condicions ambientals similars als llocs de recàrrega artificial. Afegint les quantitats adequades d’acceptors i donadors d’electrons s’han obtingut i mantingut les diferents condicions redox anaeròbies en cada conjunt de microcosmos. Els experiments inclouen sèries biòtiques i abiòtiques per separar la biodegradació de contaminants de l’adsorció a la superfície dels sòlids i altres processos abiòtics. També s’ha dut a terme un experiment amb una major concentració de contaminants (1 mg/L de cada compost), per comprovar la representativitat dels estudis convencionals. Els objectius finals del treball són: 1) identificar les condicions redox més favorables per eliminar de l'aigua els compostos seleccionats, a fi de ser promogudes en l’assaig de camp; i 2) mesurar les velocitats de les reaccions de degradació per tal de preveure el comportament dels micrcontaminants en el aqüífer.
La recarga artificial de acuíferos, que consiste en la infiltración de agua subterránea en instalaciones diseñadas para tal fin, constituye una importante herramienta en la gestión de recursos hídricos. Más allá de aumentar los recursos de aguas subterráneas, suscita gran interés la capacidad de tratamiento natural que confiere el tránsito sub-superficial a las aguas. Los procesos que tienen lugar en el sistema suelo-acuífero (filtración, adsorción, mezcla, reacciones redox, biodegradación, etc.) permiten una mejora general de la calidad del agua, eliminando incluso diversos contaminantes orgánicos. En la actualidad, el reto es entender si los microcontaminantes orgánicos emergentes, es decir farmacéuticos, productos de cuidado personal, hormonas, drogas ilícitas, plaguicidas y tensioactivos, puedan también ser atenuados. Muchos de ellos no son completamente eliminados en tratamientos de agua convencionales, siendo introducidos constantemente en aguas superficiales por los efluentes de las plantas de tratamiento de aguas residuales. A pesar de sus baja concentraciones (ng/L and μg/L), su omnipresencia en el medioambiente es actualmente causa de preocupación para la vida acuática y la salud humana. En este contexto, la recarga artificial puede representar un tratamiento alternativo o complementario para la eliminación de microcontaminantes orgánicos de las aguas. Hay evidencias de que las condiciones redox dominantes pueden influenciar el comportamiento de contaminantes orgánicos convencionales en los acuíferos. Sin embargo, en el caso de los microcontaminantes emergentes los conocimientos sobre este tema es todavía limitado. El principal objetivo de esta tesis, motivada por proyectos de recarga artificial con aguas del río Llobregat (Barcelona, España), es investigar el efecto potencial de las condiciones redox sobre el comportamiento de microcontaminantes orgánicos seleccionados (la mayoría de los cuales son contaminantes emergentes) durante la recarga artificial. El estudio se basa en experimentos batch de laboratorio usando material natural del acuífero, microcontaminantes en concentraciones ambientales (1 μg/L cada compuesto), y condiciones verosímiles en enclaves de recarga artificial. Añadiendo cantidades adecuadas de aceptadores y donadores de electrones, fueron establecidas y se mantuvieron diferentes condiciones redox anaeróbicas (condiciones nitrato-, manganeso-, hierro- y sulfato-reductoras) en cada grupo de microcosmos. Se llevaron a cabo series bióticas y abióticas para separar la biodegradación de los contaminantes (mineralización biótica o transformación) de los procesos de adsorción y de otros procesos abióticos. También fue realizado un experimento para alta concentración de contaminantes (1 mg/L cada compuesto), para comprobar la representatividad de los estudios convencionales. El objetivo final de este trabajo es identificar 1) las condiciones redox más favorables para la eliminación del agua de los contaminantes seleccionados, para su posterior simulación en el sitio piloto, y 2) las tasas de eliminación de esos contaminantes, para predecir sus comportamientos en el acuífero.
Artificial recharge of groundwater, consisting in infiltrating water into aquifers by means of properly designed facilities, represents an important tool in water resources management. Beside its quantitative benefits (augmentation of groundwater resources, long term underground storage, etc.), a great interest for this technique is related to the natural treatment provided to water by subsurface passage. The processes occurring in the soil-aquifer system (filtration, sorption, mixing, redox reactions, biodegradation, etc.) have indeed proven to yield an overall improvement of water quality, removing effectively also a number of organic contaminants. At present time, the issue is to understand whether emerging organic micropollutants, i.e. pharmaceuticals, personal care products, hormones, illicit drugs, pesticides and surfactants, can also be removed. A number of these compounds are not completely removed by conventional water treatments, being thus introduced continuously into surface water bodies by the discharge of wastewater treatment plants effluents. In spite of their low concentration (ng/L and μg/L), their ubiquitous presence in the environment is currently a cause of concern for aquatic life and human health. In this context, artificial recharge may represent a potential alternative or complementary treatment for the removal of organic micropollutants from water. Evidences showed that, among the factors influencing the fate of conventional organic contaminants in the aquifer, the predominant redox conditions could play an important role. Yet, in the case of emerging micropollutants the knowledge on this topic is still limited. The main objective of this thesis, motivated by artificial recharge practices using Llobregat river water (Barcelona, Spain), is to investigate on the potential effect of redox conditions on the fate of selected organic micropollutants, most of them being emerging contaminants, during artificial recharge of groundwater. The study is based on batch experiments involving natural aquifer material, micropollutants at environmental concentrations (1 μg/L each compound), and settings feasible at artificial recharge sites. Different anaerobic redox conditions (namely, nitrate-, manganese-, iron- and sulphate-reducing conditions) were promoted and sustained in each set of microcosms by adding adequate quantities of electron donors and acceptors. The experiments included biotic and abiotic series to separate contaminant’s biodegradation (i.e. biotic mineralization or transformation) from sorption and other abiotic processes. An experiment at higher pollutants concentration (1mg/L each compound) was also carried out, to check the representativeness of studies at concentrations easier to be tested and analysed. The ultimate aim of the work is to identify 1) the most favourable redox conditions for the removal of the target compounds from water, for their following stimulation in the field test site, and 2) pollutants’ removal rates, to predict their behaviour in the aquifer.

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Glock, Nicolaas [Verfasser]. "Benthic foraminifera as geochemical and micropaleontological proxies for redox conditions in the Peruvian oxygen minimum zone / Nicolaas Glock." Kiel : Universitätsbibliothek Kiel, 2011. http://d-nb.info/1020245891/34.

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Barton, John Leonard. "Method development for the analysis of electrochemical and transport processes in redox flow batteries at practical operating conditions." Thesis, Massachusetts Institute of Technology, 2019. https://hdl.handle.net/1721.1/121901.

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Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemical Engineering, 2019
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 113-134).
The focus of this thesis is the development and assessment of techniques for the analysis of electrochemical and transport processes in redox flow batteries (RFBs) at moderate to high active species concentrations under direct current conditions. RFBs hold promise as an energy-intensive storage technology suitable for supporting the integration of intermittent renewable energy sources into the grid, but further improvements in technical performance and reductions in system cost are needed for broad deployment. At their core, all thesis projects are aimed at enabling the development of system descriptors that correlate material properties (e.g., viscosity, conductivity), cell geometry (e.g., flow field design), and operating parameters (e.g., flow rate, current density) to system performance metrics, such as cycle efficiencies and area-specific resistance.
More specifically, the investigation is divided into three primary projects: the development and assessment of a research-scale flow cell; measurements of mass-transfer coefficients; and integration of a polarization model into a standalone application useful for assessing system performance. The differential flow cell is engineered leveraging validation material from industrial collaborators. Not only is the performance is consistent with that of a ten-fold larger cell, but its smaller modular design enables rapid assessment of new chemistries and cell components with minimal materials requirements. Mass-transfer coefficients are then measured using this cell with a well-behaved redox active electrolyte (RAE), in which glucose is added in various amounts to modify the system viscosity with minimal changes to other properties.
The results or methodology developed could be extended other similar RAE systems either as preliminary estimates of mass-transfer performance or as a protocol for carefully evaluating the impact of new system parameters on mass-transfer. Finally, results of this mass-transfer analysis are incorporated into a simple flexible stack model, which can be used to estimate system performance as a function of key materials properties with limited empiricism.
by John Leonard Barton.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Chemical Engineering

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Struckhoff, Garrett Cletus. "Plant-assisted bioremediation of perchlorate and the effect of plants on redox conditions and biodiversity in low and high organic carbon soil." Diss., University of Iowa, 2009. https://ir.uiowa.edu/etd/441.

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Perchlorate is a known inhibitor of the human thyroid gland. Perchlorate is destroyed by ubiquitous perchlorate-reducing bacteria. The bacteria often lack sufficient electron donor. Research was undertaken to evaluate the relationship between plants and perchlorate-reducing bacteria. To what degree can plant-produced electron donors stimulate perchlorate reduction in low organic carbon (LOC) and high organic carbon (HOC) soil? A complication is that plants have been shown to influence redox conditions which may inhibit perchlorate reduction. The removal of perchlorate in a flow-through reactor was monitored with variables of soil organic carbon, hybrid poplar trees, and bioaugmentation. The biodiversity was monitored using denaturing gradient gel electrophoresis. Low oxidation-reduction potential (ORP) was shown to indicate the capacity for greater perchlorate removal in soil. However, in planted LOC soil systems, evidence suggests that perchlorate reduction may also be possible at higher bulk redox conditions than previously observed. Increased hydraulic retention time was shown to both lower bulk ORP and increase perchlorate removal. Radiolabeled perchlorate was used to find that in planted systems as much as 11.7% of the influent perchlorate mass was taken up into the tree and 82% of the perchlorate taken up was accumulated in the leaves. The plant contribution to total perchlorate removal in nonbioaugmented LOC soil was 39%, with the balance of the removal being attributed to microbial reduction. In bioaugmented soil the microbial contribution to perchlorate removal was increased. Just planting poplar trees decreased the diversity of perchlorate reducers in the soil. However, when LOC soil was both planted and bioaugmented, the diversity of perchlorate reducers was not decreased. In HOC soil, the presence of an indigenous population of microorganisms competed with perchlorate reducers. At the increased ORP observed in planted HOC soil, the non-perchlorate-reducing bacteria appear to outcompete the perchlorate reducers and perchlorate removal is decreased. Engineering implications of this research are that perchlorate remediation in HOC soil does not benefit from planting hybrid poplar trees but that remediation in LOC soil is stimulated by planting and bioaugmentation.

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Eberhard, Lisa [Verfasser], and Daniel [Akademischer Betreuer] Frost. "Serpentinite phase relations - An experimental study on redox conditions and fluid migration in subduction zones / Lisa Eberhard ; Betreuer: Daniel Frost." Bayreuth : Universität Bayreuth, 2021. http://d-nb.info/1227444621/34.

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Trincal, Vincent. "Interactions fluide-roche, conditions physico-chimiques et transferts de matière dans des zones de failles en milieux sédimentaires : exemple de failles chevauchantes pyrénéennes." Thesis, Besançon, 2015. http://www.theses.fr/2015BESA2006/document.

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Ce travail a pour but d’étudier les paramètres physico-chimiques qui contrôlent les transferts de matière ainsi que la formation et l’évolution des argiles dans des failles chevauchantes en environnement sédimentaire. Deux failles chevauchantes pyrénéennes de faible grade métamorphique ont été étudiées : la faille de Millaris (cf. Mont Perdu) et le chevauchement du Pic-de-Port-Vieux (cf. Gavarnie). Dans la faille de Millaris, la déformation s’accompagne principalement d’une dissolution de la calcite matricielle par pression-solution induisant un changement de volume de la roche de 20 à 40%. Le chevauchement du Pic-de-Port-Vieux enregistre des modifications importantes au coeur de la faille mais aussi dans la zone d’endommagement. Dans les calcaires du mur du chevauchement, une mylonitisation est associée à une dissolution partielle des dolomites en présence de fluides ne dépassant pas 320-340°C. Dans les pélites du toit du chevauchement, la dissolution de l’hématite par un fluide réducteur entraine un changement de l’état redox de la roche (confirmé par spectroscopie Mössbauer) et la précipitation de chlorite dans des veines syncinématiques. Des chlorites à zonations chimiques oscillatoires présentes dans certaines veines révèlent, en combinant cartographie chimique à la microsonde, mesures de l’état redox par μXANES et thermométrie, des variations cycliques de température d’au moins 50°C au cours de la cristallisation. Un processus de valves sismiques pourrait donc être associé à la mise en place du chevauchement du Pic de Port Vieux
This work aims to study the physical and chemical parameters that control the mass-transfer and the clays formation and evolution in sedimentary environment thrust faults. Two Pyrenean thrust faults in low metamorphic grade were studied: the Millaris fault (related to Mont Perdu) and the Pic-de-Port-Vieux thrust (related to Gavarnie). In the Millaris fault, the deformation is accompanied mainly by dissolution of the matrix calcite by pressure-solution which induces a volume change of the rock from 20 to 40%. The Pic-de-Port-Vieux thrust records significant changes in the fault core-zone, but in the damaged zone also. In the footwall limestone, a mylonitisation is associated with a partial dissolution of dolomite in the presence of not exceeding 320-340°C fluids. In the hanging-wall pelites, the hematite dissolution by a reducing fluid causes a redox state change of the rock (confirmed by Mössbauer spectroscopy) and chlorite precipitation in synkinematic veins. Oscillatory zoning pattern chlorites located in some shearing veins revealed, by combining chemical mapping microprobe, redox state measurements with μ-XANES and thermometry, cyclic temperature variations of at least 50°C during the crystallization. A seismic valves process could be associated to Pic-de-Port-Vieux thrusting

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Kretz, Carole. "Induction du LTR de VIH-1 dans des conditions de stress cellulaire : rôles de NF-κB et de l'état redox intracellulaire." Lyon 1, 1997. http://www.theses.fr/1997LYO10076.

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L'infection par vih-1 est caractérisée par une phase de latence clinique particulièrement longue. La progression de la maladie jusqu'au stade sida nécessite une forte activation de la réplication virale. Parmi les stimuli induisant cette activation, on trouve des stress cellulaires tels que choc thermique, choc oxydant ou irradiation aux uv. L'action de ces agents s'exerce sur la transcription du provirus et, pour certains, (tnfalpha, peroxyde d'hydrogene) a été corrélée à l'activation du facteur de transcription cellulaire nf-kappa b, capable de se lier en deux sites, au ltr de vih-1. Ce travail de thèse s'attache à étudier l'influence d'un stress oxydant ou thermique sur le fonctionnement du ltr de vih-1 et de nf-kappa b. Il précise le rôle des radicaux libres oxygénés (rlo) dans l'activation de nf-kappa b par un choc oxydant. Ainsi, la diminution du taux de rlo intracellulaire par surexpression de la glutathion peroxydase ou de la protéine de stress hsp27 inhibe l'activation, par un stress oxydant, de nf-kappa b et les étapes de phosphorylation et de dégradation de sa sous-unité inhibitrice i kappa b-alpha. D'autre part, il décrit le mécanisme d'activation du ltr de vih-1 par le choc thermique ; ce mécanisme fait intervenir l'activation du facteur nf-kappa b. Cette stimulation de nf-kappa b est indépendante d'une dégradation de sa sous-unité inhibitrice i kappa b-alpha, mais dépend du potentiel redox cellulaire. Enfin, il met en évidence de nouveaux inducteurs du ltr de vih-1, que sont les analogues d'acides aminés. Ces composes exercent leur effet par l'intermédiaire d'une activation de nf-kappa b, concomitante d'une dégradation de i kappa b-alpha, mais sans étape de phosphorylation préalable de la sous-unité inhibitrice ; cette activation dépend, de plus, d'une variation de l'état redox intracellulaire. Ces résultats illustrent l'avantage sélectif que nf-kappa b confère au virus vih-1, dans des conditions de stress cellulaire.

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Llaguno, Jose R. "Paleoenvironments, origin, and relative maturity of organic matter in Barremian-Aptian limestones of the eastern Prada Quarry, Organyà Basin, NE Spain." FIU Digital Commons, 2017. https://digitalcommons.fiu.edu/etd/3510.

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This study is a multi-proxy analysis of a 30-m section of a Barremian-Aptian succession of interbedded, grayish black (N2) and black (N1) limestones from a quarry of the Sierra de Prada. Index taxa include planktic foraminifera Globigerinelloides blowi and Hedbergella sigali, which combined with δ13C data from Cresmina and Gorgo a Cerbara sections indicate a late Barremian to early Aptian age. The rocks are organic-rich with 0.67 - 3.10 wt% total organic carbon (TOC). A marlstone interval (~1m) at 2.24 m has a low bioturbation index (1), TOC ~6.66 wt%, framboidal pyrite, and enrichment spikes of major, biolimiting, and redox-sensitive trace elements (Al, Si, Ti, P, Fe, and Mo, Cr, Cu, V, Th), indicating an anoxic episode. Biomarker analyses show a predominance of n-alkanes (≤nC20) at this level, suggesting an in situ origin of organic matter from phytoplankton. Pr/Phy ratios below 2 imply that organic matter did not reach overmaturity.

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32

Struckhoff, Garrett Cletus Parkin Gene F. "Plant-assisted bioremediation of perchlorate and the effect of plants on redox conditions and biodiversity in low and high organic carbon soil." [Iowa City, Iowa] : University of Iowa, 2009. http://ir.uiowa.edu/etd/441.

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33

Muhammad, Yuzir Muhamad Ali. "Effect of redox conditions in the degradation of (RS)-MCPP during biological treatment of synthetic wastewater in an anaerobic membrane bioreactor (AMBr)." Thesis, University of Newcastle Upon Tyne, 2008. http://hdl.handle.net/10443/528.

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The aim of this research is to investigate the effect of mecoprop (RS-MCPP) degradation in an anaerobic membrane bioreactor (AMBr) under a range of redox conditions (methanogenic, nitrate reducing and sulphate reducing). A method was developed for the analysis of (RS)-MCPP in aqueous form using High Performance Liquid Chromatography (HPLC). The study was carried out in five phases. Initially, Phase I investigated the effect of elevated (RS)-MCPP on AMBr under methanogenic conditions. In this phase, increasing concentrations of (RS)-MCPP (5 - 200 mg. L-1) promoted a progressive increases in the (RS)-MCPP substrate utilisation rate (SUR) (0.15 to 3.19 [ig-mgVSS' 1. d"'). However, the COD removal efficiency decreased gradually from 98 % to 94 % as the (RS)-MCPP concentration increased in the feed from 50 - 200 mg. L-1, respectively. Phase II investigated the effect of denitrifying conditions on (RS)-MCPP degradation. Results showed that (RS)-MCPP removal efficiency and (RS)-MCPP SUR improved from 2- 47 % and 0.5 to 60.7 Rg. mgVSS-l. d-1, respectively as the COD/N-NO3-1 ratio and OLR were reduced from 250 to 0.2 and 1.51 to 0.07 kgCOD M, 3 A-1, respectively. Phase III investigated the effect of sulphate-reducing conditions on (RS)-MCPP degradation. Results showed that sulphidogenic conditions were less effective than nitrate reducing conditions with an average (RS)-MCPP removal and (RS)-MCPP SUR at 20(±10.7) % and 16.4 ýtgm. gVSS-lffl, respectively. Phase IV investigated the effect of HRT on the kinetics of (RS)-MCPP degradation. The robustness and stability of AMBr was also investigated in response to hydraulic shock loads on the biomass imposed. Results showed that the AMBr is stable to a large transient hydraulic shock loads, and it recovered rapidly to baseline performance after the hydraulic shock load had ended. High (RS)-MCPP degradation (up to 75 %) and utilisation rates (43 gg. mgVSS'1. d") were observed at long HRT (16.9 days). Phase V was a confirmatory experiment study to investigate the possible effects of trace quantities of oxygen that had been present in the reactor headspace and the effluent tank during Phase IV. This confirmed that the system performance towards (RS)-MCPP biodegradation had not been affected by trace oxygen levels when comparison are made. The molecular-based method, fluorescent in situ hybridisation (FISH) was used for the direct identification and enumeration of microbial communities in the AMBr sludge. In general, FISH results showed populations were dominated by methanogenic archaea in methanogenic phase (Phase I and IV) comprising between 55-66 % of the DAPI count. However, as anoxic condition were introduced in Phase II and III (nitrate reducing and sulphate reducing), the results identified a definite population shift, with the predominance of eubacteria (70-86 % of the DAPI count). The two methanogenic genera detected were Methanosaeta and Methanosamina. Of these two genera, the former was dominant in the reactor accounting for 57-100 % of the total methanogenic archaea. Furthermore, a comparison of (RS)-MCPP utilisation rates in each phase of the research revealed wide ranges (RS)-MCPP degradation efficiency and (RS)-MCPP SUR, however, although changes were observed in the composition of the bacterial population, no direct linkage could be made with any of the individual groups identified by FISH.

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34

Beckers, Felix [Verfasser]. "Mobilization, Methylation, and Ethylation of Mercury in Contaminated Floodplain Soils under Controlled Laboratory Redox Conditions as Influenced by Potential Immobilizing Agents as well as Mobilization of Mercury under Field Conditions / Felix Beckers." Wuppertal : Universitätsbibliothek Wuppertal, 2019. http://d-nb.info/1206122870/34.

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Rice, Constance Elizabeth. "Examining the effects of plant diversity and community composition on reducing conditions in the soil of experimental wetlands." Columbus, Ohio : Ohio State University, 2009. http://rave.ohiolink.edu/etdc/view?acc%5Fnum=osu1243880360.

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36

Hindersmann, Iris [Verfasser], and Tim [Akademischer Betreuer] Mansfeldt. "Trace elements in floodplain soils - effects of redox conditions on the mobility of trace elements and volatilization of mercury / Iris Hindersmann. Gutachter: Tim Mansfeldt." Köln : Universitäts- und Stadtbibliothek Köln, 2014. http://d-nb.info/1060190427/34.

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37

CACHOIR, CHRISTELLE. "Etude du comportement d'un dioxyde d'uranium en presence d'une eau granitique : role des conditions redox, du rapport s/v et de la concentration en carbonates." Paris 11, 1997. http://www.theses.fr/1997PA112295.

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Cette etude a pour cadre le stockage des dechets nucleaires de haute activite en milieu geologique profond. L'eau represente le principal facteur d'alteration. Il est donc necessaire d'etudier les interactions entre l'eau et le colis. La determination de la stabilite a long terme du combustible irradie, constitue essentiellement d'oxyde d'uranium, passe par l'etude des proprietes chimiques de durabilite du dioxyde d'uranium lui-meme. Cette etude a ete menee en s'attachant a la description et a la comprehension des mecanismes de dissolution du dioxyde d'uranium. L'influence de trois parametres a ete suivie : les conditions redox, le rapport surface de matiere exposee sur volume de solution et la concentration en carbonates. Pour etablir un bilan complet du cycle alteration de la matrice, transport de l'uranium et formation de phases secondaires, une caracterisation complete du solide, une analyse de la solution et un examen de l'interface solide/solution sont menes. L'ensemble des resultats permet, d'une part, d'elaborer des modeles des mecanismes de l'alteration aqueuse du dioxyde d'uranium en fonction des conditions redox imposees et, d'autre part, de determiner les constantes thermodynamiques relatives a la formation de phases secondaires controlant la solubilite du dioxyde d'uranium. Ainsi en conditions oxydantes quand la teneur en carbonate est faible, une phase secondaire susceptible de controler la dissolution du combustible a ete identifiee : la schoepite (oxyde d'uranium hydrate). La solubilite de cette phase est de l'ordre de 2. 10#-#4 mol. L#-#1. Deux autres phases, susceptibles de jouer le meme role que le schoepite mais a des concentrations en carbonate plus elevees, semblent impliquees : la weeksite ou la boltwoodite mais elles n'ont pas formellement ete identifiees. Aucune phase secondaire n'a pu etre observee en conditions reductrices, seul le dioxyde d'uranium lui-meme, hydrate ou non, pourrait controler la dissolution.

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Tasi, Agost Gyula [Verfasser], and H. [Akademischer Betreuer] Geckeis. "Solubility, redox and sorption behavior of plutonium in the presence of α-D-isosaccharinic acid and cement under reducing conditions / Agost Gyula Tasi ; Betreuer: H. Geckeis." Karlsruhe : KIT-Bibliothek, 2018. http://d-nb.info/1164080857/34.

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Estop, Aragonés Cristian Verfasser], and Christian [Akademischer Betreuer] [Blodau. "Impact of extreme hydrological conditions on belowground carbon cycling and redox dynamics in peat soils from a northern temperate fen / Cristian Estop Aragonés. Betreuer: Christian Blodau." Bayreuth : Universität Bayreuth, 2012. http://d-nb.info/1059412691/34.

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Gormley, Mark D. "The Influence of Hydrogeomorphology, Soil Redox Conditions, and Salinity on the Spatial Zoning of Saltgrass, Salt Rush, and Cattails in Scotts Creek Marsh, Swanton Pacific Ranch, CA." DigitalCommons@CalPoly, 2013. https://digitalcommons.calpoly.edu/theses/1167.

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Scotts Creek Marsh (SCM) is a small coastal wetland ecosystem in Davenport, CA. The vegetation of SCM is dominated by three halophytic zones comprised of saltgrass, salt rush, cattails. The objectives of the study were (i) to investigate the variables that influence the zoning of the three dominant halophyte communities in SCM and (ii) to the test the effectiveness of Indicator of Reduction in Soil (IRIS) tubes to indicate the reduction of S. The study examined the following parameters from April 6 to July 21, 2013: (i) the HGM of Scotts Creek Marsh, (ii) soil oxidation and reduction (redox) conditions, (iii) salinity, and (iii) the effectiveness of Adobe Photoshop CS 5.1 (AP5) to analyze IRIS images. All three halophytes were well suited for anoxic, redox, and saline conditions by utilizing morphological adaptations (arenchyma, adventitious roots) to their root systems. The study concluded that the spatial zoning of the three dominate halophyte species within SCM was most likely due to slight differences in the water levels and salinity. The halophytes within SCM were zoned with saltgrass occupying the areas with the lowest water table and highest EC (26.98 dS/m). The cattails dominated the low average saline areas (9.60 dS/m) near the marsh channels with the highest water level. The salt rush zones had a mild EC level of 15.24 dS/m and intermediate water level. The IRIS tubes that were installed as indicators of both sulfur and iron reduction were effective. The tubes that were withdrawn after the closure of Scott’s Creek all had more than 30% reduction of the Fe3+ paint. The results from the IRIS study indicate that they are effective at recording the reduction of sulfur. The use of AP5 seemed to be an effective tool for analyzing IRIS images. The analyzed data from the study suggests that changes to the HGM of SCM could potentially alter the ecology of the marsh.

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Bates, Brittney Lynette. "The Influence of Groundwater Flowpaths, Nutrients, and Redox Conditions on the Extent of Microbial Methanogenesis in Coal Beds Using Solute and Isotope Chemistry: Powder River Basin, USA." Thesis, The University of Arizona, 2010. http://hdl.handle.net/10150/193411.

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Water and gas samples were collected from coalbed methane wells and surface coal mines in the Powder River Basin and analyzed for solute chemistry, isotopes, and gas composition to determine timing and source of recharge, nutrient influxes, extent of methanogenesis, and redox conditions. Delta18O-H2O values and hydraulic gradients show recharge to coal beds is principally from the southern basin margin with inputs from the western and eastern margins. Detectable 14C in coal waters indicates they were recharged <50,000 BP. Correlation of deltaD-CH4 and deltaD-H2O values suggests that methane has accumulated since the Late Pleistocene. Nutrient concentrations were low and did not correlate to groundwater recharge sources. Coal gases from the northwestern basin are isotopically-depleted suggesting 'early stage' methanogenesis, whereas coal gases from the central southeastern basin are isotopically-enriched suggesting 'late stage' methanogenesis. Several wells have elevated SO4 and oxygen, which may be due to recent hydrologic changes from groundwater pumping.

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42

Nifuku, Ko. "Oceanic redox conditions during the Early Aptian Oceanic Anoxic Event (OAEla) in the Vocontian Basin, SE France: A high-resolution reconstruction from a combination of ichnological and geochemical approaches." 京都大学 (Kyoto University), 2010. http://hdl.handle.net/2433/120669.

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43

Maillard, Elodie. "Transport and degradation of pesticides in wetland systems : a downscaling approach." Phd thesis, Université de Strasbourg, 2014. http://tel.archives-ouvertes.fr/tel-01019664.

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A mechanistic understanding of transport and degradation processes of modern agricultural pesticides, including chiral pesticides, is critical for predicting their fate in the environment. In agricultural landscapes, wetlands can intercept pesticide-contaminated runoff or groundwater and improve water quality through various retention and degradation processes, which remain unknown. In a downscaling approach, three different wetlands receiving agricultural runoff were used as 'natural laboratories' to investigate the fate of widely used pesticides. Overall, our results showed that dynamics of hydrological and redox conditions largely influenced pesticide sorption mechanisms and their distribution over time within wetland compartments, thereby controlling degradation processes. While large-scale studies provide integrative information on pesticide dissipation and distribution patterns with respect to wetland functioning, small-scale investigations using novel methods such as isotope and enantiomer analyses characterize underlying molecular processes governing pesticide degradation.

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44

Bernhard, Gert, Katja Schmeide, Susanne Sachs, Karl-Heinz Heise, Gerhard Geipel, Jens Mibus, Adela Krepelova, and Vinzenz Brendler. "Investigation of the Complexation and the Migration Behavior of Actinides and Non-Radioactive Substances with Humic Acids under Geogenic Conditions - Complexation of Humic Acids with Actindies in the Oxidation State IV Th, U, Np." Forschungszentrum Dresden, 2010. http://nbn-resolving.de/urn:nbn:de:bsz:d120-qucosa-28981.

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Objective of this project was the study of basic interaction and migration processes of actinides in the environment in presence of humic acids (HA). To obtain more basic knowledge on these interaction processes synthetic HA with specific functional properties as well as 14C-labeled HA were synthesized and applied in comparison to the natural HA Aldrich. One focus of the work was on the synthesis of HA with distinct redox functionalities. The obtained synthetic products that are characterized by significantly higher Fe(III) redox capacities than Aldrich HA were applied to study the redox properties of HA and the redox stability of U(VI) humate complexes. It was confirmed that phenolic OH groups play an important role for the redox properties of HA. However, the results indicate that there are also other processes than the single oxidation of phenolic OH groups and/or other functional groups contributing to the redox behavior of HA. A first direct-spectroscopic proof for the reduction of U(VI) by synthetic HA with distinct redox functionality was obtained. The complexation behavior of synthetic and natural HA with actinides (Th, Np, Pu) was studied. Structural parameters of Pu(III), Th(IV), Np(IV) and Np(V) humates were determined by X-ray absorption spectroscopy (XAS). The results show that carboxylate groups dominate the interaction between HA and actinide ions. These are predominant monodentately bound. The influence of phenolic OH groups on the Np(V) complexation by HA was studied with modified HA (blocked phenolic OH groups). The blocking of phenolic OH groups induces a decrease of the number of maximal available complexing sites of HA, whereas complex stability constant and Np(V) near-neighbor surrounding are not affected. The effects of HA on the sorption and migration behavior of actinides was studied in batch and column experiments. Th(IV) sorption onto quartz and Np(V) sorption onto granite and its mineral constituents are affected by the pH value and the presence of HA. HA exhibits a significant influence on the transport of U(IV) and U(VI) in a laboratory quartz sand system. In order to provide the basis for a more reliable modeling of the actinide transport, the metal ion complexation with HA has to be integrated into existing geochemical speciation codes. Within this project the metal ion charge neutralization model was embedded into the geochemical modeling code EQ3/6. In addition to that, a digital data base was developed which covers HA complexation data basing on the charge neutralization model.

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45

Bernhard, Gert, Katja Schmeide, Susanne Sachs, Karl-Heinz Heise, Gerhard Geipel, Jens Mibus, Adela Krepelova, and Vinzenz Brendler. "Investigation of the Complexation and the Migration Behavior of Actinides and Non-Radioactive Substances with Humic Acids under Geogenic Conditions - Complexation of Humic Acids with Actindies in the Oxidation State IV Th, U, Np." Forschungszentrum Rossendorf, 2004. https://hzdr.qucosa.de/id/qucosa%3A21725.

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Objective of this project was the study of basic interaction and migration processes of actinides in the environment in presence of humic acids (HA). To obtain more basic knowledge on these interaction processes synthetic HA with specific functional properties as well as 14C-labeled HA were synthesized and applied in comparison to the natural HA Aldrich. One focus of the work was on the synthesis of HA with distinct redox functionalities. The obtained synthetic products that are characterized by significantly higher Fe(III) redox capacities than Aldrich HA were applied to study the redox properties of HA and the redox stability of U(VI) humate complexes. It was confirmed that phenolic OH groups play an important role for the redox properties of HA. However, the results indicate that there are also other processes than the single oxidation of phenolic OH groups and/or other functional groups contributing to the redox behavior of HA. A first direct-spectroscopic proof for the reduction of U(VI) by synthetic HA with distinct redox functionality was obtained. The complexation behavior of synthetic and natural HA with actinides (Th, Np, Pu) was studied. Structural parameters of Pu(III), Th(IV), Np(IV) and Np(V) humates were determined by X-ray absorption spectroscopy (XAS). The results show that carboxylate groups dominate the interaction between HA and actinide ions. These are predominant monodentately bound. The influence of phenolic OH groups on the Np(V) complexation by HA was studied with modified HA (blocked phenolic OH groups). The blocking of phenolic OH groups induces a decrease of the number of maximal available complexing sites of HA, whereas complex stability constant and Np(V) near-neighbor surrounding are not affected. The effects of HA on the sorption and migration behavior of actinides was studied in batch and column experiments. Th(IV) sorption onto quartz and Np(V) sorption onto granite and its mineral constituents are affected by the pH value and the presence of HA. HA exhibits a significant influence on the transport of U(IV) and U(VI) in a laboratory quartz sand system. In order to provide the basis for a more reliable modeling of the actinide transport, the metal ion complexation with HA has to be integrated into existing geochemical speciation codes. Within this project the metal ion charge neutralization model was embedded into the geochemical modeling code EQ3/6. In addition to that, a digital data base was developed which covers HA complexation data basing on the charge neutralization model.

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46

Ståhlberg, Carina. "Mineralisation rates of natural organic matter in surface sediments affected by physical forces : a study of fresh- and brackish-water sediments subjected to changed redox conditions, resuspension, and advective pore water flow /." Linköping : Department of Water and Environmental Studies, [The Tema Institute], Linköping University, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-8332.

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47

Díaz, Ramos Rut Amelia. "Geoquímica do enxofre e morfologia da pirita em sedimentos do sistema de ressurgência de Cabo Frio (RJ)." Niterói, 2017. https://app.uff.br/riuff/handle/1/3021.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica Ambiental. Niterói, RJ
A região de Cabo Frio (RJ) é uma área de ressurgência que favorece a produtividade primária e promove elevado acúmulo de matéria orgânica (MO) nos sedimentos, a qual afeta as condições redox do ambiente de sedimentação e na interface água-sedimento, promovendo efeitos sobre a especiação inorgânica do enxofre (S). O presente estudo utiliza a geoquímica inorgânica das espécies reduzidas do S, operacionalmente definidas como acid-volatile sulfufide (AVS) e chromium-reducible sulfur (CRS), a composição isotópica (δ34S) do sulfato da água intersticial e do CRS, e a razão COT/CRS (carbono orgânico total/CRS) para avaliar a diagênese recente do S e a condição redox nos sedimentos. Adicionalmente foi estudada a morfologia da pirita e a distribuição de tamanho dos frambóides através de microscopia eletrônica de varredura (MEV) para inferir o estado de oxidação do ambiente de formação. Foram coletados quatro box-cores na plataforma continental do Sistema de Ressurgência de Cabo Frio (SRCF) para este estudo. Os conteúdos de COT variam entre 0,8 e 2,3%, as maiores concentrações foram observadas nas estações da porção média da plataforma. Baixos valores de enxofre total (ST) (< 0,2%) e CRS (< 0,05%) foram encontrados nas camadas superficiais, ocorrendo incremento com a profundidade, indicando o aumento da sulfato redução (SR). As estações com o maior conteúdo de ST foram as localizadas na porção média da plataforma, sendo este padrão de acumulação favorecido pela presença dos vórtices sob a plataforma. A razão COT/CRS indica que o fator limitante para a formação da pirita é o enxofre. Até 50% do S pode estar associado a MO, caracterizando o processo de sulfidização da MO. A composição isotópica do sulfato ao longo dos perfis é mantida constante entre +18,7 e +23‰ e sem fracionamento com respeito ao sulfato da água do mar (+ 21‰), indicando baixas taxas de SR. No entanto, a composição isotópica do CRS apresentou sinais altamente empobrecidos em 34S (-25,6 até -40,8 ‰), indicando reações de oxidação no ciclo do S, promovidas pela intensa bioturbaçao na área e/ou pelo regime hidrodinâmico regional. As diferentes características morfológicas, como as superfícies de oxidação nos microcristais, os processos de crescimento secundário e os poliframboides encontrados nas análises morfológicas da pirita, assim como também a variabilidade na distribuição dos diâmetros dos frambóides evidenciaram uma formação sob condição redox altamente dinâmica. Estes resultados confirmam a complexidade hidrodinâmica do SRCF, o qual afeta inúmeros processos sobre a plataforma, dentre os quais a diagênese no ciclo do enxofre
The Cabo Frio region (RJ) is an upwelling area, which favors the high primary productivity and promotes accumulation of organic matter (OM) in sediments, affecting the redox conditions of the sedimentation environment, the sediment-water interface and mainly the speciation of inorganic sulfur (S). Therefore, this study uses the inorganic geochemistry of reduced S species operationally defined as acid-volatile sulfufide (AVS) and chromium-reducible sulfur (CRS), the isotopic composition (δ34S) of pore water sulfate and CRS, and the COT / CRS ratio (total organic carbon / CRS), to evaluate the recent S diagenesis and redox conditions in sediments. Additionally, was study the pyrite morphology and size distribution of framboids by scanning electron microscopy (SEM) to infer the oxidation state of the environment. In this sense, were collected four box-cores on the continental shelf of the upwelling system of Cabo Frio (SRCF). The TOC contents range from 0.8 to 2.3%, the highest concentrations were observed at stations in the middle shelf. Low values of total sulfur (TS) (<0.2%) and CRS (<0.05%) were found in the superficial layers occurring an increase with depth, indicating an increase in sulfate reduction. The stations with the highest content of ST were located in the middle shelf, this pattern of accumulation is favored by the presence of cyclonic eddy under the platform. The COT/CRS ratio indicates that the limiting factor for the pyrite formation is the sulfur. The isotopic composition of sulfate did not vary much with the sediment depths and is kept constant between +18.7 and +23 ‰ and without fractionation of sulfate with respect to sea water (21 + ‰) indicating low net sulfate reductions, but the isotopic composition of the CRS is highly depleted (-25.6 to -40.8 ‰), indicating oxidation reactions in the cycle of S, promoted by the intense bioturbation in the area and the regional hydrodynamic regime. The different morphological characteristics observed, such as surface oxidation in the microcrystals, the processes of secondary growth and poliframboides found, as well as the variability in the framboids diameters distribution, show the formation under highly dynamic redox condition. These results confirm the complexity of SRCF due to the occurrence of different hydrodynamic conditions over the shelf

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48

Shumskykh, Mykyta. "Release of trace elements from contaminated sediments into surface waters during sediments dynamics : an experimental study." Thesis, Tours, 2019. http://www.theses.fr/2019TOUR4008.

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Dans les systèmes aquatiques, la plupart des éléments traces métalliques (ETM) sont piégés dans les sédiments puis peuvent être relargués en fonction des conditions chimiques et de l’activité microbienne à l’interface eau-sédiment. L’objectif de cette étude était d’évaluer l’impact de remise en suspension des sédiments (lors de crues et d’opérations de gestion de barrages) sur la mobilité de certains ETM. Plusieurs conditions expérimentales de lessivage ont été choisies pour simuler ces événements : conditions oxiques et anoxiques sur des sédiments bruts et d’autres irradiés par rayons gamma. L’utilisation d’eau désionisée a permis de maximiser le processus de relargage. Deux types de sédiments, issus de contextes différents, ont été sélectionnés : le barrage de Villerest (France) et la rivière Xiang (Chine). Des expériences à long terme (30 jours) ont permis d’identifier la dégradation de la matière organique, l’activité microbienne et l’altération (voire la dissolution) de phases porteuses d’ETM comme principaux facteurs de contrôle. L’importance de l’activité microbienne n’a pas pu être quantifiée puisque l’irradiation n’a pas stérilisé totalement les sédiments. Enfin, l’impact de tels évènements parait très limité puisque moins de 1% des ETM contenus dans les sédiments ont été libérés
In aquatic systems, most of trace metals (TM) are buried in sediments and then can be released according to chemical conditions and microbial activity occurring at the sediment-water interface. The aim of this study was to assess the impact of resuspension events (flood or maintenance operations for dam reservoir) on the mobility of some TM. Different batch experiment conditions were chosen to mimic those events: under oxic and anoxic conditions on raw sediments and on gamma-irradiated ones (“sterilized” one). The use of deionized water allowed maximizing the release process. Two sediment types issued from different contexts were selected: the Villerest dam reservoir (France) and the Xiang River (China). Long term experiments (30-day long) allowed identifying that organic matter degradation, microbial activity and alteration/dissolution of trace metal bearing phases were the main controlling factors. The gamma-irradiation did not sterilize sediments but only limited aerobic bacteria and enhanced anaerobic activity. The impact of such 24h resuspension event on reservoir waters and downstream biota is very limited as less than 1% of trace elements was released

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Fleurance, Stéphanie. "Métallogenèse de l'uranium associée à des processus superficiels : l'exemple de la Jordanie centrale." Thesis, Université de Lorraine, 2012. http://www.theses.fr/2012LORR0312/document.

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Les différentes lithologies sédimentaires du Groupe Belqa présentent un enrichissement en P et en toute une série d'éléments sensibles aux conditions redox. Il est montré que l'enrichissement en U, Cu, Co, Mo, V résulte d'un dépôt syn-sédimentaire sous conditions suboxiques. Par contre, les éléments Cr, Ni, Cd, Zn sont beaucoup plus enrichis et requierent un flux exogénique de métal probablement relié à l'altération de roches ultrabasiques obductées à la même période au nord de cette région, lors de la collision de la plaque arabo-africaine avec la plaque eurasienne. Les phosphates représentent le principal hôte de l'uranium et des terres rares. L'analyse des apatites par ablation laser ICP-MS a permis de montrer leur évolution, depuis le stade sédimentaire-diagénétique, puis pyrométamorphique, jusqu'à l'altération supergène. La libération de l'uranium de la structure de l'apatite lors du pyrométamorphisme et de l'altération supergène permet sa mise à disposition pour la formation de minéralisations. Le pyrométamorphisme, dû à une combustion des niveaux riches en matière organique, est responsable de la déstabilisation des apatites, et de la formation de roches de compositions semblables à des ciments clinker/Portland. L'uranium a également été libéré de la structure de l'apatite par altération supergène. L'altération météorique et les fluides évaporitiques ont permis le lessivage et le transport des éléments (U, V) des roches carbonatées métamorphiques, et des carbonates puis a conduit au dépôt des vanadates d'uranyles dans les carbonates pulvérulents ayant subi une dissolution importante
The different lithologies of the Belqa Group present an enrichment in P and various redox sensitive elements. The U, Cu, Co, Mo, V enrichment results from synsedimentary deposition in suboxic conditions. However, the higher Cr, Ni, Cd, Zn enrichment requires an exogenic metal flux probably related to the terrestrial leaching of ultrabasic rocks obducted during the collision between African-Arabian and Eurasian plates to the north of the study region, at the same time. Phosphates are the main host lithology for uranium and rare earth elements. The analysis of the apatites by laser ablation ICP-MS shows their evolution along the sedimentary-diagenetic and pyrometamorphic stages, up to the supergene weathering. The uranium liberation from the apatite structure during the pyrometamorphism and surficial weathering led to its availability as supergene ore mineralization. Pyrometamorphism resulted from the combustion of organic-rich layers and caused the destabilization of the apatites, and the formation of rocks which have compositions similar to clinker/Portland cements. Uranium has been also released from the structure of the apatite by supergene alteration. Meteoric weathering and the evaporitic groundwater resulted in the leaching and the transport of the elements (U, V) from the metamorphic carbonated hills, and from the surrounding permeable limestone which has undergone dissolution in the near surface zone

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50

Schulze, Susanne. "Mikrobieller Abbau und Redoxzonierung im Abstrom einer teerölkontaminierten Altablagerung." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2004. http://nbn-resolving.de/urn:nbn:de:swb:14-1093000985218-62401.

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Es wurden die mikrobiellen Abbauprozesse an einem Standort mit gaswerkstypischer Schadstoffkontamination, v. a. BTEX und PAK, untersucht. Ziel war es, die relevanten mikrobiologischen Abbauprozesse mit gängigen Analysemethoden zu identifizieren und das Natural Attenuation-Potential zu bewerten. Neben einer Betrachtung der Schadstoffe im Feld wurde ein ausführliches hydrogeochemisches und mikrobiologisches Analyseprogramm durchgeführt. Der Schadstoffabbau wurde in Labor-Mikrokosmen unter für den Standort charakteristischen, überwiegend anaeroben Bedingungen untersucht. Methodik und Umfang der Untersuchungsmethoden wurden im Hinblick auf eine Anwendung an weiteren Standorten bewertet. Die Schadstoffausbreitung in der Fahne, die Keimzahluntersuchungen und eine deutliche Redoxzonierung mit einer Sukzession von Methanogenese, Sulfatreduktion und Fe(III)-Reduktion spiegelten mikrobielle Abbauprozesse wider. Dabei beeinflussten und überlagerten die Prozesse im Schadensherd die Prozesse in der Fahne stark. Die Felddaten gaben Hinweise auf abiotische Sekundärreaktionen zwischen den Redoxpaaren Fe(III)/Fe(II), Sulfat/Sulfid und O2/H2O. Die Berechnung der Assimilativen Kapazität (AC) zeigte ein gutes Angebot an CO2 und Sulfat, während die übrigen TEA Sauerstoff, Nitrat und auch Fe(III) am Standort stark limitiert waren. Dem stand eine von den Redoxbedingungen abhängige, unterschiedlich gute Abbaubarkeit der Modellschadstoffe Benzen, Toluen, Ethylbenzen, Naphthalin, Acenaphthen, Phenanthren und Pyren im Laborversuch gegenüber. Methanogenese wurde in keinem der Versuchsansätze beobachtet. Unter sulfatreduzierenden Bedingungen fand ein Abbau weniger Modellschadstoffe (Toluen, z.T. auch Ethylbenzen und Naphthalin) statt. Mit den TEA Nitrat und insb. Fe(III) erweiterte sich das Abbauspektrum gegenüber sulfatreduzierenden Bedingungen. Mit Sauerstoff fand ein Abbau aller im Grundwasser enthaltenen BTEX und PAK statt. Vor dem Hintergrund der AC und den Ergebnissen der Mikrokosmen bedarf es für einen vollständigen Schadstoffabbau im Feld einer Kombination verschiedener TEA-Prozesse, insb. eines Zusammenwirkens von Fe(III)- und Sulfatreduktion und eines Einflusses von Sauerstoff an den Fahnenrändern. Die unterschiedlichen Abbaumuster bzw. Abbaugeschwindigkeiten in Abhängigkeit der TEA machen das Einbeziehen der Redoxzonierung in eine Modellierung des Standortes erforderlich. Neben den TEA hatte die Verfügbarkeit der Makroelemente Phosphor und Stickstoff sowie von Mikroelementen einen Einfluss auf den Abbau. In den Respirometeruntersuchungen mit hohen Substratkonzentrationen war Phosphat in allen und Ammonium in einem Teil der Grundwässer, in Abhängigkeit von der Entnahmestelle im Feld, limitierend. Bei niedrigen Substratkonzentrationen in den Mikrokosmen trat kein Mangel an N und P auf. In allen Fällen hatte aber eine Zugabe von Mikroelementen einen förderlichen Effekt auf den Abbau. Die Methodik der Standortuntersuchungen folgte dem Prinzip der multiple lines of evidence. Die hydrochemischen Parameter O2, NO3-, Fe2+, Mn2+, SO42-, S2-, CH4, NH4+, PO43 waren geeignet, einen mikrobiellen Abbau und potentielle Limitationen durch Nährstoffe zu zeigen. Ein Vergleich der Ergebnisse der tiefenhorizontierten Beprobung mit einem stärker räumlich integrierenden Ansatz zeigte, dass ohne eine entsprechende räumliche Auflösung die AC überschätzt würde. Die Summenparameter, insb. die Toxizität, lieferten wertvolle Zusatzinformationen über die Gesamtkontamination. Der Abbau der (Modell-)Schadstoffe in den Mikrokosmen ermöglichte eine Einschätzung der generellen Abbaubarkeit der Schadstoffe am Standort, der Einflussparameter auf den Schadstoffabbau sowie möglicher Stimulationsmaßnahmen.

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