Thesis (Ph. D.)--University of Washington, 1996. / Vita. Includes bibliographical references (leaves [146]-169).

Thesis (Ph. D.)--University of Washington, 1996. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--Simon Fraser University, 1976. / Includes bibliographical references (leaves 85-93).

Thesis (Ph. D.)--Florida State University, 2004. / Advisors: Eric A. Smith and Paul H. Ruscher (co-chairs) , Florida State University, College of Arts and Sciences, Dept. of Meteorology. Title and description from dissertation home page (viewed Feb. 7. 2006). Document formatted into pages; contains xiii, 131 pages. Includes bibliographical references.

Thesis (M.S.)--University of Missouri-Columbia, 2004. / Typescript. Includes bibliographical references (leaves 92-98). Also available on the Internet.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1971. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--Oregon State University, 2006. / Printout. Includes bibliographical references (leaves 142-152). Also available on the World Wide Web.

Thesis (Ph. D.)--Oregon State University, 2007. / Printout. Includes bibliographical references (leaves 158-169). Also available on the World Wide Web.

Biogeochemical processes in the marine biosphere are important in global element cycling and greatly influence the gas composition of the Earth’s atmosphere. The nitrogen cycle is a key component of marine biogeochemical cycles. Nitrogen is an essential constituent of living organisms, but bioavailable nitrogen is often short in supply thus limiting primary production. The largest input of nitrogen to the marine environment is by N2-fixation, the transformation of inert N2 gas into bioavailable ammonium by a distinct group of microbes. Hence, N2-fixation bypasses nitrogen limitation and stimulates productivity in oligotrophic regions of the marine biosphere. Extensive blooms of N2-fixing cyanobacteria occur regularly during summer in the Baltic Sea. N2-fixation during these blooms adds several hundred kilotons of new nitrogen into the Baltic Proper, which is similar in magnitude to the annual nitrogen load by riverine discharge and more than twice the atmospheric nitrogen deposition in this area. N2-fixing cyanobacteria are therefore a critical constituent of nitrogen cycling in the Baltic Sea. In this thesis N2 fixation of common cyanobacteria in the Baltic Sea and the direct fate of newly fixed nitrogen in otherwise nitrogen-impoverished waters were investigated. Initially, the commonly used 15N-stable isotope assay for N2-fixation measurements was evaluated and optimized in terms of reliability and practicality (Paper I), and later applied for N2-fixation assessments (Paper II–IV). N2 fixation in surface waters of the Baltic Sea was restricted to large filamentous heterocystous cyanobacteria (Aphanizomenon sp., Nodularia spumigena, Dolichospermum spp.) and absent in smaller filamentous cyanobacteria such as Pseudanabaena sp., and unicellular and colonial picocyanobacteria (Paper II-III). Most of the N2-fixation in the Northern Baltic Proper was contributed by Aphanizomenon sp. due to its high abundance throughout the summer and similar rates of specific N2-fixation as Dolichospermum spp. and N. spumigena. Specific N2 fixation was substantially higher near the coast than in an offshore region (Paper II). Half of the fixed nitrogen was released as ammonium at the site near the coast and taken up by non-N2-fixing organisms including phototrophic and heterotrophic, prokaryotic and eukaryotic planktonic organisms. Newly fixed nitrogen was thereby rapidly turned-over in the nitrogen-depleted waters (Paper III). In colonies of N. spumigena even the potential for a complete nitrogen cycle condensed to a microcosm of a few millimeters could be demonstrated (Paper IV). Cyanobacterial colonies can therefore be hot-spots of nitrogen transformation processes potentially including nitrogen gain, recycling and loss processes. In conclusion, blooms of cyanobacteria are instrumental for productivity and CO2 sequestration in the Baltic Sea. These findings advance our understanding of biogeochemical cycles and ecosystem functioning in relation to cyanobacterial blooms in the Baltic Sea with relevance for both ecosystem-based management in the Baltic Sea, and N2-fixation and nitrogen cycling in the global ocean. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.</p>

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.