There is a global need to find a permanent and readily implemented solution to the problem of heavy metal pollution in aqueous environments. A dithiol compound, benzene-1,3-diamidoethanethiol (BDETH2), also known as N,N'-bis(2-mercaptoethyl) isophthalamide or N,N'-bis(2-mercaptoethyl)-1,3-benzenedicarboxamide, capable of binding divalent metal ions, has been synthesized and characterized. A broad range of BDET-metal compounds, spanning the periodic chart, has been prepared and characterized by IR, MS, EA, Raman, XAFS and TGA. The characteristics of the BDET-M compounds were determined through secondary reactions. In an effort to derivatize BDET-M compounds through alkylalumination a new cyclic compound, 1,3- bis(4,5-dihydrothiazolo)benzene, has been synthesized by refluxing BDETH2 in the presence of AlMe3. Mineral coating studies have been performed and it was found that coating with BDET prevents metal leaching. XPS studies indicated that covalent bonds exist between BDET and metals at the mineral surfaces. BDETH2 is not water soluble and must be used as an ethanolic solution to precipitate metals from water. In an effort to find similar ligands that are water-soluble another dithiol compound, N,N'-bis(2-mercaptoethyl)oxalamide (MOA), and a monothiol compound, N-mercaptoethyl-furoylamide (MFA), have been synthesized. Each was found to precipitate Cd, Hg and Pb from water, to varying degrees. Some metal compounds of MOA, MFA and dithiothreitol (DTT), a watersoluble dithiol compound have been prepared and characterized. These compounds provide insight into the properties of the BDET-M compounds. For example, it was shown that insolubility in water is a common feature of thiol compounds and is not unique to BDET-M compounds.

Historic mine tailings pose a significant health risk to surrounding ecosystems and communities because of high residual concentrations of contaminant metals. The initial tailings mineral assemblage, metal sulfides, silicates, and carbonates are unstable at earth surface conditions and undergo oxidative and proton-promoted weathering. The weathering of metal sulfides generally produces acid that, if not balanced by protonconsuming dissolution of silicates and carbonates, leads to progressive acidification. The Klondyke State Superfund Site in Graham County, Arizona contains high concentrations of Pb (up to 13 g kg⁻¹) and Zn (up to 6 g kg⁻¹), and remains unvegetated 50 years after mining cessation. Field-scale investigation revealed a wide range of pH (2.5-8.0) and plant-available (DTPA-extractable) metals in the near surface of the tailings pile. Four samples were chosen for in-depth characterization ranging in pH, as denoted by subscript, from 2.6 to 5.4. The mineral transformations occurring in these four samples were investigated using a variety of techniques and the data indicated an increase in tailings weathering extent with increasing acidification (decreasing pH). Lead speciation, studied by a combination of chemical sequential extraction and X-ray absorption fine structure (XAFS) spectroscopy, was found to vary with tailings depth. The principle lead-bearing mineral was plumbojarosite (PbFe₆(SO₄)₄(OH)₁₂), with smaller amounts of anglesite (PbSO₄) and lead-sorbed iron-oxide. Anglesite, the most bioavailable mineral form of Pb in the tailings, was found to accumulate at the tailings surface, which has important implications for health risks. Total Zn content decreased by an order of magnitude (from 6 to 0.4 g kg⁻¹) and showed a change in molecular speciation with decreasing pH. Zinc-rich phyllosilicates and Zn-containing manganese oxides predominate at high pH, whereas low pH samples contained principally Zn-sorbed iron oxides. One of the overarching goals of the project is to remediate the Klondyke site using phytostabilization to keep contaminant metals from eroding offsite either by wind or water transport mechanisms. However, the impacts of plant growth on metal bonding environment are unknown. To address that gap in knowledge, we have developed a technique for the study of root-microbe-mineral-metal interactions that occur in the rhizosphere, the volume of soil surrounding, and affected by, plant roots. This technique involves the conjunctive use of fluorescence in-situ hybridization, X-ray fluorescence elemental mapping, XAFS and Raman micro-spectroscopies, and electron microscopy on single roots. Manganese and iron root plaques collocalized with elevated Pb, Zn, and Cr demonstrate that the rhizosphere can affect metal speciation. Metal speciation is an important factor in determining metal bioavailability, and thus is critical for understanding the health risk associated with mine tailings. The results of this research provides site-specific information about Pb and Zn speciation, which will be used to evaluate the effectiveness of site remediation within the context of metal toxicity.

The magnetic and physical properties of oxide-free, ligand passivated, iron nanoparticles were studied using superconducting quantum interference device (SQUID) magnetometry and synchrotron based X-ray radiation. Particles used for this study ranged in diameter between 2 and 10 nm, which made it possible to distinguish between bulk and surface effects in the nanoparticles’ properties. Additionally, the effects of two different weakly interacting ligands (2,4-pentanedione and hexaethylene glycol monododecylether) on the nanoparticles’ behavior were studied. The results of this study were compared to theoretical predictions of magnetic transition metal behavior in both thin films and nanoparticles, as well as experimental results from measurements of transition metal clusters formed in an inert carrier gas and measured with a Stern-Gerlach magnet. Magnetometry revealed that the iron nanoparticles have a magnetocrystalline anisotropy an order of magnitude greater than bulk iron. At the same time, these particles exhibit a saturation mass magnetization up to 209 Am2/kg, which is only slightly lower than bulk iron. The structural properties of these particles were characterized using high energy X-ray diffraction analyzed using the atomic pair distribution function method (PDF). The PDF analysis indicates that the Fe particles have a distorted and expanded form of the bcc lattice, which could, at least in part, explain the magnetocrystalline anisotropy of these nanoparticles. X-ray absorption fine structure (XAFS) was used to study the surface properties of the iron nanoparticles and further characterize their structural properties. XAFS showed that oxidized species of iron exist at the nanoparticles’ surface and can be attributed to iron/ligand interactions. The percentage of oxidized species scales with the surface to volume ratio of the nanoparticles, and therefore appears limited to the nanoparticle surface. The layer of Fe(II) species present at the nanoparticles’ surface accounts for the reduction in saturation mass magnetization values (when compared to bulk iron) observed in these particles. XAFS analysis also provided further confirmation of the nanoparticles’ expanded crystalline lattice. / text

Widespread arsenic contamination with adverse effects to human health is a global problem. Most previous studies on arsenic contamination in natural environments and those associated with mining and agricultural activities focused largely on arsenic-rich minerals such as arsenates, arsenites, sulfarsenides, and sulfides. Rock-forming minerals generally contain only minor or trace amounts of arsenic but, owing to their sheer abundances, are potentially important (and sometimes dominant) sources of this metalloid and can play significant roles in the attenuation and sequestration of arsenic in various environments. However, there remains a significant gap in my knowledge about the uptake and speciation of arsenic in rock-forming minerals. This thesis research is intended to bridge this gap by investigating the uptake and speciation of arsenic in selected rock-forming sulfate and phosphate minerals (i.e., gypsum, struvite and newberyite). Gypsum (CaSO4•2H2O) is a major by-product of mining and milling processes of borate, phosphate and uranium deposits worldwide and, therefore, potentially plays an important role in the stability and bioavailability of heavy metalloids, including As, in tailings and surrounding areas. Gypsum containing 1,900 and 185 ppm As, synthesized with Na2HAsO4•7H2O and NaAsO2 in the starting materials, respectively, has been investigated by synchrotron X-ray absorption spectroscopy (XAS), single-crystal electron paramagnetic resonance spectroscopy (EPR), and pulsed electron nuclear double resonance spectroscopy (ENDOR). Quantitative analyses of As K edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra show that arsenic occurs in both +3 and +5 oxidation states and the As3+/As5+ value varies from 0.35 to 0.79. Single-crystal EPR spectra of gamma-ray-irradiated gypsum reveal two types of arsenic-associated oxyradicals: [AsO3]2− and an [AsO2]2−. The [AsO3]2− center is characterized by principal 75As hyperfine coupling constants of A1 = 1952.0(2) MHz, A2 = 1492.6(2) MHz and A3 = 1488.7(2) MHz, with the unique A axis along the S-O1 bond direction, and contains complex 1H superhyperfine structures that have been determined by pulsed ENDOR. These results suggest that the [AsO3]2− center formed from electron trapping on the central As5+ ion of a substitutional (AsO4)3− group after removal of an O1 atom. The [AsO2]2− center is characterized by its unique A(75As) axis approximately perpendicular to the O1-S-O2 plane and the A2 axis along the S-O2 bond direction, consistent with electron trapping on the central As3+ ion of a substitutional (AsO3)3− group after removal of an O2 atom. These results confirm lattice-bound As5+ and As3+ in gypsum and point to potential application of this mineral for immobilization and removal of arsenic pollution. EPR spectra show that another sulfate boussingaultite is also sequestering both As5+ and As3+ at its S site. Synthesis experiments at pH from 2 to 14 also show that arsenic uptake in gypsum is pH dependent. Struvite and newberyite, common biominerals and increasingly important green fertilizers recovered from wastewater treatment plants, are capable of sequestering a wide range of heavy metals and metalloids, including arsenic. Inductively coupled plasma mass spectrometric (ICPMS) analyses show that struvite formed under ambient conditions contains up to 547±15 ppm As and that the uptake of As is controlled by pH. Synchrotron As K-edge XANES spectra measured at 20 K show that As5+ is the predominant oxidation state in struvite, irrespective of Na2HAsO4•7H2O or NaAsO2 as the source for As. Modeling of As K-edge EXAFS data suggest that local structural distortion associated with the substitution of As5+ for P5+ in struvite reaches up to 3.75 Å. Single-crystal electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated struvite disclose five [AsO3]2- radicals and one [AsO4]2- radical. These arsenic-centered oxyradicals are all readily attributed to form from diamagnetic [AsO4]3- precursors during irradiation, providing further support for exclusive incorporation and local structural expansion beyond the first shell of As5+ at the P site in struvite. Arsenic doped newberyite (MgHPO4•3H2O) obtained from the gel diffusion method has investigated by synchrotron XAS at the As K-edge (11,867 eV) at 8 K and single-crystal EPR spectroscopy at room temperature. XANES data show that As5+ is dominant and EXAFS analysis reveals a local environment typical of the arsenate species as well. Single-crystal EPR spectra of gamma-ray-irradiated newberyite contain two arsenic-associated oxyradicals: [AsO3]2− and [AsO2]2− derived from As5+ and As3+, respectively, at the P site in the newberyite structure. Elevated concentrations of arsenic have also been observed in natural newberyite from guano deposits and reflect the accumulation of this metalloid in the food chain. Therefore, struvite and newberyite can both sequester significant amounts of arsenic, and their direct use as fertilizers (irrespective of origins from guano deposits or wastewaters) is a potential source of arsenic contamination. On the other hand, the capacities of struvite and newberyite for accommodating significant amounts of arsenic in crystal lattices coupled with their simple chemistry and crystallization under ambient conditions make them attractive materials for immobilization and removal of arsenic contamination in aqueous environments.

京都大学 / 0048 / 新制・論文博士 / 博士(工学) / 乙第12929号 / 論工博第4122号 / 新制||工||1626(附属図書館) / 32139 / (主査)教授 田中 庸裕, 教授 田中 勝久, 教授 佐藤 啓文 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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京都大学 / 新制・論文博士 / 博士(工学) / 乙第13403号 / 論工博第4189号 / 新制||工||1761(附属図書館) / (主査)教授 田中 庸裕, 教授 江口 浩一, 教授 阿部 竜 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

This dissertation describes preparation and characterization of Ni₂P catalysts and their application in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN). The work carried out includes synthesis of Ni₂P on different siliceous supports, SiO2 and MCM-41. It also includes characterization of these catalytic materials using X-ray diffraction (XRD), temperature-programmed reduction (TPR), Fourier transform infrared (FTIR) spectroscopy and X-ray absorbance fine structure (XAFS) spectroscopy. In situ FTIR was employed to study the acidity of Ni₂P/SiO₂ and probe the catalytic sites involved in the HDN of pyridine. Transient and steady-state kinetics of a surface intermediate that is formed upon pyridine adsorption and reaction was studied to elucidate the mechanism of HDN over Ni₂P/SiO₂. Additionally, in situ FTIR and X-ray absorption near edge structure (XANES) spectroscopy was utilized to probe the bonding, mechanism and kinetics of thiophene HDS over a novel MCM-41-supported Ni₂P catalyst. The use of these techniques allowed for better understanding of the surface intermediates, mechanisms and the nature of the active sites involved in HDN and HDS. / Ph. D.

L'élucidation du mécanisme de formation de divers verres naturels peut aider à comprendre la dynamique de la Terre car ces matériaux retiennent l'état de formation dans leurs structures. La spectroscopie XAFS appliquée aux matériaux amorphes issue des météorites fournit des informations sur les changements structuraux locaux des éléments présents. En effectuant des analyses dans la phase de verre des météorites et dans les verres issus de l'impact météoritiques des informations sur les conditions de formation des ces matériaux peuvent être obtenues. Dans cette thèse, l'analyse de la structure locale d’éléments de transition (Ti, Zr) dans les minéraux et les verres naturels a été réalisée par la XAFS. Des expériences de chauffage au laser à haute température et de flux gazeux sur zircon ont également été effectuées pour observer les changements structuraux à haute température dans les phases cristallines qui accompagnent le verre météoritique. La structure locale de ces matériaux est semblable à celle du Zr dans les sédiments de la limite Crétacé – Paléogène (K-Pg). Ce dernier ne montre aucune influence de diagenèse ou d'altération, ce qui suggère que les sédiments Cependant, l'abondance de Zr dans les sédiments n'est pas toujours suffisante pour obtenir des informations fiables sur la structure locale du Zr. Nous nous sommes ainsi intéressés à la structure local du Ti, qui appartient au même groupe que le Zr. Les conditions d'impact des météorites sur Mars et du passage des météorites à travers l'atmosphère peuvent être estimées par l'analyse de la structure locale de Zr dans la partie vitrifiée des météorites. L'analyse de la structure locale du Zr dans la météorite martienne de Tissint montre la croûte de fusion de cette météorite est semblable à celle des tectites et du verre d'impact qui les accompagne, alors que la partie intérieure vitreuse de Tissint est similaire à celle de la baddeleyite et de la fulgurite. Cette dernière aurait subi une vitrification pendant le passage à travers l'atmosphère. Afin de confirmer le changement structurel de Zr à haute température, nous avons effectué des expériences de chauffage du zircon, ainsi qu’une expérience de diffraction des rayons X sur poudre pendant le chauffage. L'analyse chimique dans le MEB a montré l'évaporation de la composante SiO2. Nous avons aussi obtenu un nouveau digramme de phase ZrO2-SiO2 dans lequel la région d’immiscibilité liquide proposée auparavant n’a pas pu être confirmée / Elucidation of the formation mechanism of various natural glasses can help to understand the dynamics of the Earth because these materials record the formation condition in their structures. XAFS applied to natural meteorite-related glasses provides information about the local structural changes of elements therein. By performing high-accuracy XAFS analyses for trace elements and their local structure in sedimentary rocks, in the glass phase of meteorites and in the meteorite impact-related glasses such as tektite and impact glass, information on the formation condition of these materials can be obtained. We have performed local structure analysis of IVb transition metal elements (Ti, Zr) in natural minerals and glasses K-edge XANES and EXAFS as well as high-temperature laser heating and gas flow experiments on zircon, to observe structural changes at high temperature in the crystalline phases that accompany the meteoric glass. The local structure of these materials is similar to that of of Zr in K-Pg sediments, which do not show any influence from diagenesis and weathering, suggesting that K-Pg sediments maintain the thermal quenching history of the meteorite impact. However, the low abundance of Zr in sediments prompted us to study Ti, which belongs to the same group as Zr and is much more abundant. Combination of the information about the local structures of Ti and Zr allows a higher reliability for the estimation of meteorite impact event. The local structure of Zr in the fusion crust and inner glassy part of the Martian meteorite of Tissint are similar, respectively, to that in tektite and accompanying impact glass and to that in baddeleyite and fulgurite. The latter was likely vitrified part during the passage through the atmosphere. It should be possible to estimate the conditions of meteorite impact on Mars and the passage of meteorites through the Earth’s atmosphere through the analysis of the local structure of Zr in the glassy part of meteorites. In order to confirm this hypothesis, we performed heating experiments of zircon with in-situ powder X-ray diffraction experiment was performed for ZrSiO4 and ZrO2. SEM analysis confirmed evaporation of the SiO2 component. We have obtained a new ZrO2-SiO2 phase diagram where the liquid-immiscible region proposed earlier does not appear.