Anthropogenic activities and natural processes over time have led to the release of toxic heavy metal contaminants into the environment. As a consequence, there is an increasing number of illnesses caused by the exposure of humans to heavy metals and metalloids. The dissertation work presented here focused on the synthesis, characterization, and understanding of the surface chemistry, as well as the photo-reactivity, of a variety of iron (oxyhydr)oxide nano-materials that have relevance for the remediation of heavy metal contaminants, such as arsenic and chromium in aqueous environments. The research focused on the photo-induced reductive dissolution of a nano-dimensioned iron oxyhydroxide, ferrihydrite, in the presence of oxalate, the photo-induced arsenite oxidation, and the simultaneous redox transformation of arsenite and chromate in the presence of ferrihydrite and another environmentally relevant iron oxyhydroxide, goethite. The photo-reductive dissolution of ferrihydrite (using simulated solar radiation) in the presence of oxalic acid was investigated with surface sensitive in situ and ex situ techniques that included attenuated total reflectance Fourier transform infrared spectroscopy. Ferrihydrite at a solution pH of 4.5 exhibited an induction period where the rate of Fe(II) release was limited by a low concentration of adsorbed oxalate due to the site-blocking of carbonate that was intrinsic to the surface of the ferrihydrite starting material. The photo-induced decarboxylation of adsorbed oxalate also ultimately led to the appearance of carbonate reaction product (distinct from carbonate intrinsic to the starting material) on the surface. Ferrihydrite that was prepared under carbonate free condition showed a rapid release of Fe(II) upon irradiation and no induction period was observed. Arsenite [As(III)] oxidation in the presence of ferrihydrite and goethite was also investigated. Ferrihydrite or goethite when exposed to As(III) in the dark led to no change in the oxidation state of As(III) reactant. However, exposure of As(III) in the presence of ferrihydrite or goethite to simulated solar light resulted in the oxidation of As(III) and a reduction of surface Fe(III) leading to an overall increase in the total As removal. At a solution pH of 5, this conversion of As(III) to As(V) on ferrihydrite resulted in the partitioning of a stoichiometric amount of Fe(II) into the aqueous phase and the majority of the As(V) product remained bound to the ferrihydrite surface. In contrast, the As(III)/goethite system showed a different photochemical behavior in the absence or presence of dissolved oxygen. Under oxic conditions, in contrast to ferrihydrite, the majority of the As(V) product was in the aqueous phase and the relative amount of aqueous Fe(II) was significantly less than in the ferrihydrite circumstance. Experimental observations suggested that in the oxic environment, Fe(II) on the goethite surface was heterogeneously oxidized to Fe(III) by dissolved oxygen resulting in the formation of reactive oxygen species that led to the further oxidation of As(III) in solution. Similarly, various experimental investigations were conducted to test the simultaneous removal of As(III) and Cr(VI) from solution. Our results suggested that a surface mediated spontaneous electron transfer between As(III) and Cr(VI) occurred in the presence of Fe- and Al-(oxy)hydroxides. Both infrared and x-ray absorption spectroscopies were conducted to get more insight into the charge transfer reaction and mechanism of electron transfer reaction. In summary, the research discussed here should help to understand the details of oxidation/reduction reactions occurring at mineral-water interfaces. Perhaps more importantly, the methodologies discussed in this dissertation could potentially be novel and eco-friendly approaches for arsenite as well as hexavalent chromium remediation. / Chemistry

Important reactions in the environment often occur at the interface between a mineral surface and aqueous phase. Reactions occurring at this interface often control the uptake or release of harmful components resulting in the geochemical cycling of elements in the environment. Additionally, minerals are commonly used in the remediation of contaminated areas, where similar chemistry occurs at their interfaces. Thus, studies of the chemistry of these interfaces are essential to our understanding of complex environments. Many of these processes are controlled by electron transfer reactions between adsorbates and the mineral interface, and it is here where this research presented will concentrate. The studies in this thesis key in on redox chemistry on various environmentally relevant iron minerals, including ferrihydrite, pyrite, and amorphous iron sulfide. A large portion of this body of work is dedicated to the understanding of the surface mediated reaction between chromate (Cr(VI)) and arsenite (As(III)). Both of these species are present in the environment and are detrimental to human health. Using in- and ex-situ experiments we have monitored the coupled redox transformation of Cr(VI) and As(III) to chromite (Cr(III)) and arsenate (As(V)). Quantum mechanical modeling was used to support the experimental studies of this novel redox chemistry. The reaction was monitored in situ, using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), on the surface of the iron oxyhydroxide, ferrihydrite, at various solution pH values by following vibrational modes unique to Cr(VI), As(III), and As(V). At pH < 9 we observed an initial growth of Cr(VI) vibrational modes due to adsorption, followed by the simultaneous decrease in Cr(VI) vibrational modes and increase in As(V) vibrational modes. Ex situ analysis of the reaction products via X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) indicated that there was an increase in the percentage of reaction products as the pH decreased. Quantum mechanical calculations were completed to model the reaction of Cr(VI) and As(III) on the ferrihydrite surface by analyzing differences in geometric and electronic structural changes and thermodynamic preferences. The results indicate that Cr(VI) and As(III) adsorbed physically separated from each other is not only thermodynamically favorable but results in changes in As(III)-Fe and Cr(VI)-Fe atomic distances, towards those characteristic of As(V)-Fe and Cr(III)-Fe. Thus a mechanism where electron transport occurs through bulk states is plausible. Additionally, natural bond order analysis reveals a redistribution of electron density away from the Cr(VI) atomic center upon adsorption, indicating probable changes in Cr(VI) reduction potential. The electrochemical reduction of Cr(VI) on three surfaces, ferrihydrite, titanium dioxide, and aluminum oxides, indicate that Cr(VI) reduction potential is surface dependent, an observation that has significance for redox chemistry in the environment. The interaction of ferric, Fe(III), with iron sulfide surfaces (during and after coal mining activities) contributes to the detrimental environmental problem known as acid mine drainage (AMD). We investigated whether Fe(III) chelating siderophores could be used to suppress the oxidation of iron sulfide surfaces and the resulting AMD chemistry. The exposure of the iron sulfide, pyrite, to the siderophore, desferrioxamine B (DFOB) at initial pH values of 3, 6, and 8 under oxic conditions showed a significant decrease in the rate of dissolution of pyrite: decreases of 43.7%, 37.5% and 78.4%, respectively. An even greater decrease in pyrite oxidation was observed when DFOB was present in anoxic conditions, specifically 56.1%, 74.4% and 91.5%, at pH 3, 6 and 8, respectively. We further compared the rate of dissolution between DFOB and another siderophore, enterobactin, which is a stronger chelator of Fe(III). The presence of enterobactin suppressed pyrite oxidation more than DFOB, consistent with the contention that inhibiting the interaction of Fe(III) with pyrite will decrease the oxidation of the mineral. We also analyzed the exposure of the pyrite surface to DFOB using ATR-FTIR, to determine if any surface chelation occurs. We found that when Fe(III) is present on the pyrite surface, DFOB adsorbs to the surface via hydroxamate groups, similar to the aqueous phase spectra of DFOB-Fe(III) complex. In contrast the spectra do not exhibit hydroxamate vibrational modes when Fe(III) was not initially present on the pyrite surface and in this circumstance the spectra resembled that of aqueous phase unchelated DFOB. Taken together the results showed that siderophore inhibited pyrite oxidation by chelating Fe(III) present on the pyrite surface and in solution. Finally, the reduction of NO(g) to NH3/NH4+ with amorphous iron sulfide (FeS) was studied. The exposure of NO gas to a suspension of FeS solid resulted in the conversion of 2.3% NO(g) to the reaction product ammonia (NH3), which was found to grow over time, while the exposure of NO(g) to water (in the absence of mineral) resulted in no NH3 formation. Additionally, we completed in situ analysis of NO exposure to FeS as a function of water concentration using ATR-FTIR. The exposure of NO to an aqueous paste of FeS or a FeS film (with adsorbed H2O), resulted in the adsorption of NO to the FeS surface and the subsequent production of NH3, as indicated by N-H vibrational modes. In contrast, the removal of all water, via thermal desorption from the film, resulted in the adsorption of NO but did not show vibrational modes consistent with the formation of NH3. We conclude that the presence of H2O, as a source of protons, and a FeS surface, as a source of electrons, results in the transformation of NO to NH3 via a heterogeneous reaction. This result has important implications towards remediation of NOx gases and mechanisms of prebiotic synthesis of NH3. In summary, the research presented expands our understanding of redox reactions at mineral interfaces in the environment. The work herein aims to inform and aid in the development of remediation methods for arsenic and chromium, the formulation of methods to inhibit the production of acid mine drainage, and develop our understanding of toxic NOx gas reduction on surfaces. / Chemistry

Thesis. 1975. Ph.D.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Vita. / Bibliography: leaves 289-308. / by Frank E. Huggins. / Ph.D.

Magnetic resonance imaging (MRI) is regularly used to obtain anatomical images, greatly advancing biomedical research and clinical health care today, but its full potential in providing functional, physiological, and molecular information is only beginning to emerge. The goal of magnetic resonance molecular imaging is to utilize MRI to acquire information on the molecular level. This dissertation is focused on ways to increase the use of MRI for molecular imaging using superparamagnetic iron oxide (SPIO) nanoparticle induced MRI contrast. This work is divided into three main sections: <B>1)<I> Elucidation of the contribution of size and coating properties to magnetic nanoparticle induced proton relaxation.</I></B> To maximize contrast generated without increasing particle size, new methods to increase effects on relaxivity must be developed. Experimental data obtained on a new class of biocompatible particles are presented, along with simulated data. The effects of coating size, proton exchange, and altered diffusion are examined. Simulations are presented confirming the effect of particle coatings on clustering-induced relaxivity changes, and an experimental system demonstrating the clustering effect is presented. <B>2)<I> Development of a diffusion-dependent, off-resonance imaging protocol for magnetic nanoparticles.</I></B> This work demonstrates an alternative approach, off-resonance saturation (ORS), for generating contrast sensitive to SPIO nanoparticles. This method leads to a calculated contrast that increases with SPIO concentration. Experimental data and a mathematical model demonstrate and characterize this diffusion-dependent, off-resonance effect. Dependence on off-resonance frequency and power are also investigated. <B>3)<I> Development of a genetic MRI marker via in vivo magnetic nanoparticle synthesis.</I></B> This work seeks to provide a gene expression marker for MRI based on bacterial magnetosomes, tiny magnets produced by naturally occurring magnetotactic bacteria. Here, <I>magA</I> is expressed in a commonly used human cell line, 293FT, resulting in the production of magnetic, iron oxide nanoparticles by these cells. MRI shows these particles can be formed <I>in vivo</I> utilizing endogenous iron and can be used to visualize cells positive for <I>magA</I>. These results demonstrate <I>magA</I> alone is sufficient to produce magnetic nanoparticles and that it is an appropriate candidate for an MRI reporter gene.

Flow accelerated corrosion (FAC) is a major concern in the power industry as it causes thinning of the pipes by the dissolution of the passive oxide layer formed on the pipe surface. Present research deals with comparing the protection offered by the magnetite (Fe3O4) versus maghemite (γ-Fe2O3) phases thickness loss measurements. Fourier transform infrared spectroscopy (FTIR) is used in distinguishing these two elusive phases of iron oxides. Representative pipes are collected from high pressure steam extraction line of the secondary cycle of unit 2 of Comanche Peak Steam Electric Station (CPSES). Environmental scanning electron microscopy (ESEM) is used for morphological analysis. FTIR and X-ray diffraction (XRD) are used for phase analysis. Morphological analysis showed the presence of porous oxide surfaces with octahedral crystals, scallops and "chimney" like vents. FTIR revealed the predominance of maghemite at the most of the pipe sections. Results of thickness measurements indicate severe thickness loss at the bend areas (extrados) of the pipes.

Algumas indicações morfológicas sugerem que as superfícies de paisagem tropicais onde encontram-se os duricrusts ferruginosos, podem apresentar idades que variam desde o Quaternário até o Cretáceo, e que a laterização sobre estas superfícies pode ter sido iniciada simultaneamente ou não, estabelecendo-se uma sequência cronológica de formação escalonada de acordo com a elevação, em função da evolução geomorfológica das superfícies. Sabendo-se que no Planalto de Diamantina na Serra do Espinhaço Meridional (SdEM) são reconhecidos três níveis geomorfológicos correlatos aos ciclos de aplainamento da plataforma Sul-americana, o objetivo deste trabalho foi estudar as variações mineralógicas, geoquímicas e morfológicas de duricrusts ferruginosos da Serra do Espinhaço Meridional buscando entender os processos genéticos envolvidos e as implicações disto sobre a distribuição e evolução da paisagem regional e suas relações com os ciclos de aplainamento do continente Sul-americano. Para atingir estes objetivos, foram realizadas análises de difratometria de raios X, suscetibilidade magnética, microscopia eletrônica de varredura com sistema de energia dispersiva acoplado e análise elementar a partir da dissolução total dos minerais constituintes. Os resultados mostraram que no Planalto de Diamantina na SdEM coexistem níveis de ferricretes e lateritas na superfície correspondente ao ciclo erosivo Pós-Gondwanico. As superfícies lateríticas são provavelmente as formações supérgenas mais antigas da paisagem regional, originadas durante os processos denudacionais que ocorreram ao longo do ciclo erosivo Pós-Gondwanico. A erosão parcial de seu perfil laterítico constituíram o material fonte de Fe e Al para a gênese dos ferricretes distribuídos em superfícies elevadas (> 1200 m), especialmente aqueles em superfícies em torno de 1400 m de altitude. As variações paleoclimáticas do ciclo Pós-Gondwanico também proporcionaram ciclos erosivos alternados que resultaram no subescalonamento desta superfície, criando condições geomorfológicas favoráveis à gênese de ferricretes mais recentes (1200 - 1400 m). Além disso, os duricrusts ferruginosos do Planalto Diamantina (SdEM) sob influência do maciço quartzítico do Supergrupo Espinhaço e situados superfícies erosivas elevadas (> 1200 m), além de policíclicos, também podem apresentar características poligenéticas. / Some morphological indications suggest that the tropical landscape surfaces where the iron-rich duricrust are present may have ages varying from the Quaternary to the Cretaceous, and that the laterization on these surfaces may have been initiated simultaneously or not, establishing a sequence chronological formation according to the elevation, according to the geomorphological evolution of the surfaces. Three geomorphological levels correlated to the South American platform planing cycles are known on the Diamantina Plateau, for this the objective of this work was to study the mineralogical, geochemical and morphological variations of the iron-rich duricrust of the SdEM, trying to understand the genetic processes involved and the implications of this on the distribution and evolution of the regional landscape and its relations with the planning cycles of the South American continent. In order to reach these objectives, X-ray diffraction, magnetic susceptibility, scanning electron microscopy with dispersive energy system coupled and elemental analysis carried out from the total dissolution of the constituent minerals. The results showed that in the Diamantina Plateau at the SdEM, coexist levels of ferricretes and laterites on the surface corresponding to the Post-Gondwanic erosive cycle. The laterite surfaces are probably the oldest surviving formations of the regional landscape, originated during the denudation processes that occurred along the Post-Gondwanic erosive cycle. Partial erosion of its lateritic profile was source material of Fe and Al for the genesis of ferricretes distributed on high surfaces (> 1200 m), especially those on surfaces at 1400 m of altitude. The paleoclimatic variations of the Post-Gondwanic cycle also provided alternating erosive cycles that resulted in sub-scaling of this surface, creating geomorphological conditions favorable for genesis of earlier ferricretes (1200 - 1400 m). In addition, the ferricretes of the Diamantina Plateau (SdEM) under influence of the Quartzite massif of the Espinhaço Supergroup and located in elevated erosive surfaces (> 1200 m), besides polycyclics, may also present polygenetic characteristics.

Submitted by DEISE CRISTINA SANTOS NOGUEIRA null (deise17nogueira@hotmail.com) on 2017-03-08T13:15:38Z No. of bitstreams: 1 Dissertação.pdf: 858288 bytes, checksum: 84d43bc8161733904a29be8fd6a0e023 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-03-13T13:13:26Z (GMT) No. of bitstreams: 1 nogueira_dcs_me_jabo.pdf: 858288 bytes, checksum: 84d43bc8161733904a29be8fd6a0e023 (MD5) / Made available in DSpace on 2017-03-13T13:13:26Z (GMT). No. of bitstreams: 1 nogueira_dcs_me_jabo.pdf: 858288 bytes, checksum: 84d43bc8161733904a29be8fd6a0e023 (MD5) Previous issue date: 2017-02-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Nos solos brasileiros, a caulinita, os óxidos de ferro e os hidróxidos de alumínio são alguns dos minerais encontrados na fração argila influenciando o comportamento dos atributos físicos do solo. O objetivo do presente trabalho foi avaliar a influência dos minerais da fração argila nos atributos físicos de um Argissolo Amarelo, submetido a dois tipos de preparo e cultivado com cana-de-açúcar. As amostras deformadas e indeformadas de solo foram coletadas após oito meses do plantio da cana-de-açúcar, em quatro camadas (0,00-0,10, 0,10-0,20, 0,20-0,40 e 0,40-0,60 m) na linha e entrelinha de plantio nas áreas submetidas à escarificação em área total e escarificação na linha da cultura. Através das amostras deformadas determinou-se a textura do solo, ferro extraído por ditionito-citrato-bicarbonato (FeDCB), ferro extraído por oxalato ácido de amônio (FeOAA) e razão caulinita/(caulinita+gibbsita) [(Ct/(Ct+Gb)]. Com as amostras indeformadas determinou-se a densidade do solo (Ds) e a resistência do solo à penetração (RP). Os resultados apresentados pela estatística descritiva demostraram que houve uma separação das áreas de estudo devido à diferença mineralógica encontrada nessas áreas, sendo a primeira área caracterizada pela maior razão Ct/(Ct+Gb) e a segunda área caracterizada pelos maiores teores de ferro extraído por ditionito-citrato-bicarbonato (FeDCB). Pela análise de componentes principais foi possível observar que o FeDCB apresentou correlação inversa com a Ds e a RP, a razão Ct/(Ct+Gb) apresentou correlação direta com os atributos físicos Ds e RP. A mineralogia influenciou o comportamento da densidade do solo e resistência do solo à penetração. A área com maior razão caulinita apresentou maiores valores de densidade do solo e de resistência do solo à penetração e a área com maiores teores de óxidos de ferro apresentou menores valores de densidade do solo e de resistência do solo á penetração. O preparo do solo não influenciou o comportamento da densidade do solo e da resistência do solo à penetração. / In Brazilian soils, kaolinite, iron oxides and aluminium hydroxides are some of the minerals found in the clay fraction influencing the behavior of the soil physical attributes. The objective of the present work was to evaluate the influence of minerals of the clay fraction on the physical attributes of a yellow Ultisol under two tillage and sugar cane cultivation. The disturbed and undisturbed samples of soil were collected in the row and interrow in the areas with chiselling in the total area and chiselling in the planting row in four layers (0,00-0,10, 010-0,20, 0,20-0,40, 0,40-0,60 m) eight months later the sugar cane cultivation. The soil texture, citrate/bicarbonate/dithionite extractable Fe, oxalate/acid/ammonium extractable Fe (FeOAA) and Ct / (Ct+ Gb) ratio were evaluated from disturbed samples and bulk density (Bd) and soil penetration resistance (SPR) were evaluated from undisturbed samples. The results presented by the descriptive statistics showed that there was a separation of the study areas due to the mineralogical difference found in these areas, being the first area characterized by the higher ratio Ct / (Ct + Gb) and the second area characterized by the higher citrate/bicarbonate/dithionite extractable Fe (FeDCB). In the principal component analysis, it was observed that the FeDCB showed an inverse correlation between Bd and SPR. It was also observed that the Ct / (Ct + Gb) ratio showed a direct correlation with the physical attributes Bd and SRP. The mineralogy influenced the behavior of the Bd and SPR. The area with higher Ct/ (Ct+Gb) ratio, showed higher values of Bd and SRP and The area with higher content of iron oxides had lower values of Bd and SRP. The soil tillage didn’t influence the behavior of Bd and SPR. / FAPESP: 2014/14490-2

Algumas indicações morfológicas sugerem que as superfícies de paisagem tropicais onde encontram-se os duricrusts ferruginosos, podem apresentar idades que variam desde o Quaternário até o Cretáceo, e que a laterização sobre estas superfícies pode ter sido iniciada simultaneamente ou não, estabelecendo-se uma sequência cronológica de formação escalonada de acordo com a elevação, em função da evolução geomorfológica das superfícies. Sabendo-se que no Planalto de Diamantina na Serra do Espinhaço Meridional (SdEM) são reconhecidos três níveis geomorfológicos correlatos aos ciclos de aplainamento da plataforma Sul-americana, o objetivo deste trabalho foi estudar as variações mineralógicas, geoquímicas e morfológicas de duricrusts ferruginosos da Serra do Espinhaço Meridional buscando entender os processos genéticos envolvidos e as implicações disto sobre a distribuição e evolução da paisagem regional e suas relações com os ciclos de aplainamento do continente Sul-americano. Para atingir estes objetivos, foram realizadas análises de difratometria de raios X, suscetibilidade magnética, microscopia eletrônica de varredura com sistema de energia dispersiva acoplado e análise elementar a partir da dissolução total dos minerais constituintes. Os resultados mostraram que no Planalto de Diamantina na SdEM coexistem níveis de ferricretes e lateritas na superfície correspondente ao ciclo erosivo Pós-Gondwanico. As superfícies lateríticas são provavelmente as formações supérgenas mais antigas da paisagem regional, originadas durante os processos denudacionais que ocorreram ao longo do ciclo erosivo Pós-Gondwanico. A erosão parcial de seu perfil laterítico constituíram o material fonte de Fe e Al para a gênese dos ferricretes distribuídos em superfícies elevadas (> 1200 m), especialmente aqueles em superfícies em torno de 1400 m de altitude. As variações paleoclimáticas do ciclo Pós-Gondwanico também proporcionaram ciclos erosivos alternados que resultaram no subescalonamento desta superfície, criando condições geomorfológicas favoráveis à gênese de ferricretes mais recentes (1200 - 1400 m). Além disso, os duricrusts ferruginosos do Planalto Diamantina (SdEM) sob influência do maciço quartzítico do Supergrupo Espinhaço e situados superfícies erosivas elevadas (> 1200 m), além de policíclicos, também podem apresentar características poligenéticas. / Some morphological indications suggest that the tropical landscape surfaces where the iron-rich duricrust are present may have ages varying from the Quaternary to the Cretaceous, and that the laterization on these surfaces may have been initiated simultaneously or not, establishing a sequence chronological formation according to the elevation, according to the geomorphological evolution of the surfaces. Three geomorphological levels correlated to the South American platform planing cycles are known on the Diamantina Plateau, for this the objective of this work was to study the mineralogical, geochemical and morphological variations of the iron-rich duricrust of the SdEM, trying to understand the genetic processes involved and the implications of this on the distribution and evolution of the regional landscape and its relations with the planning cycles of the South American continent. In order to reach these objectives, X-ray diffraction, magnetic susceptibility, scanning electron microscopy with dispersive energy system coupled and elemental analysis carried out from the total dissolution of the constituent minerals. The results showed that in the Diamantina Plateau at the SdEM, coexist levels of ferricretes and laterites on the surface corresponding to the Post-Gondwanic erosive cycle. The laterite surfaces are probably the oldest surviving formations of the regional landscape, originated during the denudation processes that occurred along the Post-Gondwanic erosive cycle. Partial erosion of its lateritic profile was source material of Fe and Al for the genesis of ferricretes distributed on high surfaces (> 1200 m), especially those on surfaces at 1400 m of altitude. The paleoclimatic variations of the Post-Gondwanic cycle also provided alternating erosive cycles that resulted in sub-scaling of this surface, creating geomorphological conditions favorable for genesis of earlier ferricretes (1200 - 1400 m). In addition, the ferricretes of the Diamantina Plateau (SdEM) under influence of the Quartzite massif of the Espinhaço Supergroup and located in elevated erosive surfaces (> 1200 m), besides polycyclics, may also present polygenetic characteristics.

Reactions of aqueous Fe(II) with Fe and Mn oxides influence heavy metal mobility, transformation of trace organics, and important elemental cycles as Fe precipitates form or dissolve, and as electrons move between aqueous and solid phases. Our objective was to characterize reactions of Fe(II) with important metal oxides, using a suite of complementary tools to investigate the extent and underlying mechanisms of Fe(II)-metal oxide redox activity. Nanoscale materials (1-100 nm) may have fundamentally different surface or electronic properties than larger solids. Goethite was synthesized with primary particle dimensions above or below the nanoscale. Despite large differences in particle surface area, goethite nanorods and microrods had similar net Fe(II) sorption and electron transfer properties. Experimental evidence suggested particle aggregation resulted in particle complexes of a similar size, meaning considerations of available reactive surface area could explain our results. Kinetics and extent of Fe(II)-Fe(III) redox reactions between aqueous Fe(II) and goethite were examined using a stable isotope tracer approach. Aqueous Fe(II) that had been enriched in 57Fe was mixed with isotopically-normal goethite. Convergence of Fe isotope ratios in aqueous and solid phases to values predicted by complete Fe atom exchange provided evidence that all goethite Fe(III) atoms could eventually react with Fe(II), despite no evidence for complete atom exchange from bulk measurements of the aqueous or solid phase. Fe isotope data at different experimental conditions was combined with theoretical considerations governing electron transfer in goethite to provide evidence for redox-driven atom exchange involving bulk conduction of electrons between spatially distinct Fe(II) sorption and release sites. Procedures for stable Fe isotope tracer studies have been adapted to investigate redox transformations of magnetite solids with different divalent cation content. Evolution of aqueous Fe(II)-Mn(IV) redox reactions was examined using complementary techniques. After pyrolusite particles were exposed to aqueous Fe(II), aqueous Fe and Mn were analyzed, and X-ray diffraction was utilized with electron microscopy to assess solid phase evolution during continued exposure to Fe(II). Selective use of Fe isotopes during Fe(II) resuspensions allowed us to track chemical changes occurring to one particular Fe addition using 57Fe Mössbauer spectroscopy.

Iron (Fe) minerals and ferrous iron (Fe(II)) play an important role in the several natural elemental cycles, including the carbon cycle, nutrient cycles, and the cycling of metals. In this work we have characterized the reactivity structural Fe(II) in several Fe minerals and in natural soil with uranium. We have studied the reactivity of Fe(II) in solution with the Fe oxide goethite conditions relevant to many natural systems. Green rusts are widely recognized as an intermediate phase in the Fe cycle. Here we investigate the reactivity of green rusts containing different structural anions with uraniumVI (UVI). We have also investigated the effect of aqueous bicarbonate on UVI sorption and reduction by green rusts. Our findings indicate that green rusts reduce UVI to UIV, and that environmentally relevant carbonate concentrations have little effect the rate and extent on this reaction. We have also investigated UVI reduction by structural Fe(II) in magnetite. Magnetite with varying stoichiometry (x = Fe2+/Fe3+) was reacted with UVI. Results from x-ray absorption spectroscopy indicate that the redox properties of magnetite dictate whether magnetite reduces UVI. In addition, magnetite reactivity can be "recharged" by electron transfer from aqueous Fe(II). There is little evidence of the reactivity of structural Fe(II) towards UVI in natural materials. We have characterized a naturally reduced soil and found it contains structural Fe(II) in clay minerals and a possible green rust-like phase. When this soil is exposed to UVI we find that Fe(II) reduces a portion of the U added. Our work highlights the potential for abiotic reduction of UVI by Fe(II) in reduced, Fe-rich environments. We have used 57Fe Mössbauer spectroscopy to study redox reactions of Fe(II) with goethite under biogeochemical conditions relevant to natural systems. When Fe(III) in goethite is substituted with aluminum or anions such as phosphate, silicate, carbonate, and natural organic matter are sorbed onto the surface of goethite, interfacial electron transfer occurs between sorbed Fe(II) and goethite. These results indicate that electron transfer between Fe(II) and Fe oxides occurs under environmentally relevant conditions. Electron transfer was blocked by phospholipids, however, suggesting electron transfer may be inhibited under eutrophic conditions.