Human exposure to arsenic in groundwater is a global concern, and arsenic mobility in groundwater is often controlled by Fe mineral dissolution and precipitation. Additionally, Fe(II)-catalyzed recrystallization of Fe oxides has been shown to enable trace element release from and incorporation into Fe oxides. However, the effect of As(V) on the Fe(II)-catalyzed recrystallization of Fe oxides such as goethite, magnetite, and ferrihydrite remains unclear. Here, we measured the extent of Fe atom exchange between aqueous Fe(II) and magnetite, goethite, or ferrihydrite in the presence of As(V) by reacting isotopically "normal" Fe oxides with 57Fe-enriched aqueous Fe(II). At lower levels of adsorption (≤13.3 μM), As(V) had little influence on the rate or extent of Fe(II)-catalyzed Fe atom exchange in goethite or magnetite. However, Fe atom exchange was increasingly inhibited as As(V) concentration increased above 100 μM. Additionally, adsorbed As(V) may be incorporated into magnetite over time in the presence and absence of added aqueous Fe(II) as indicated by X-ray absorption spectroscopy (XAS) and chemical extraction data, with more rapid incorporation in the absence of added Fe(II). XAS and chemical extraction data are also consistent with the incorporation of As(V) during goethite and magnetite precipitation. Additionally, atom exchange data indicated that low levels of As(V) coprecipitation (As:Fe = 0.0005-0.0155) had little influence on the rate or extent of Fe(II)-catalyzed Fe atom exchange in goethite or magnetite. Atom exchange data indicated that ferrihydrite likely transforms via a dissolution-reprecipitation mechanism both to lepidocrocite at 0.2 mM Fe(II) and to magnetite at 5 mM Fe(II). The presence of 206 μM As(V) slowed the transformation of ferrihydrite to more crystalline iron minerals and slowed the rate of atom exchange between aqueous Fe(II) and ferrihydrite. However, the degree of atom exchange did not directly correlate with the amount of ferrihydrite transformed. In summary, Fe oxide recrystallization processes may affect As(V) uptake and release in the environment, and As(V) may inhibit Fe(II)-catalyzed Fe oxide recrystallization.

Metal oxide-facilitated transformation is likely an important degradation pathway of antibacterial agents at soil-water interfaces. Phenolic disinfectants (triclosan and chlorophene), fluoroquinolones (FQs), and aromatic N-oxides are of particular concern due to their widespread usage, potential toxicity and frequent detection in the environment. Results of the present study show that the above antibacterial agents are highly susceptible to metal oxide-facilitated oxidation. The interfacial reactions exhibit complex reaction kinetics, which are affected by solution pH, the presence of co-solutes, surface properties of metal oxides, and structural characteristics of antibacterial agents. Adsorption of the antibacterial agents to Mn and Fe oxide surfaces generally proceeds faster than oxidation reactions of these compounds by Mn and Fe oxides, especially in the case of Fe oxides. Reaction intermediates and end products are identified by GC/MS, LC/MS and/or FTIR. Structurally-related model compounds are examined to facilitate reaction site and mechanism elucidation. On the basis of experimental results and literature, reaction schemes are proposed. In general, the antibacterial agent is adsorbed to the oxide surface, forming a precursor complex. Electrons are transferred within the precursor complex from the antibacterial agent to the oxide, followed by releasing of the radical intermediates which undergo further reactions to generate oxidation products. The precursor complex formation and electron transfer are likely rate-limiting. For triclosan, phenoxy radicals are critical intermediates to form oxidation products through three pathways (i.e., radical coupling, further oxidation of the radical, and breakdown of an ether bond within the radical). The first two pathways are also operative in the oxidation of chlorophene. For FQs, oxidation generates radical intermediates that are most likely centered on the inner N in the piperazine ring. The radical intermediates then undergo three major pathways (i.e., radical coupling, N-dealkylation, and hydroxylation) to yield a variety of products. For aromatic N-oxides, a N-oxide radical intermediate is generated upon oxidation by MnO2, followed by the loss of oxygen from the N-oxide moiety and the formation of a hydroxyl group at the C-atom adjacent to the N-oxide moiety. Overall, a fundamental understanding of the reaction mechanisms between three classes of antibacterial agents and metal oxides has been obtained.

Samli Fe-oxide (+Cu&plusmn / Au) deposit is hosted by Samli pluton and rocks of Karakaya Complex in western Anatolia. The pluton consists of both mafic and felsic phases showing magma mixing textures. 40Ar/39Ar geochronology yielded an age range of 23.2&plusmn / 0.5 to 22.42&plusmn / 0.11 Ma for the Samli pluton, overlapping with 40Ar/39Ar age of 22.33&plusmn / 0.59 Ma and U-Pb age of 23.34&plusmn / 0.19 Ma from alterations. Sr-Nd isotope data are suggestive of a metasomatized subcontinental lithospheric mantle (SCLM) source for the magma. Alteration-mineralization pattern is defined by a series of overlapping halos characterized by sodic-calcic (plagioclase-pyroxene&plusmn / scapolite), calcic (garnet-pyroxene&plusmn / epidote), potassic (biotite+magnetite+chalcopyrite), hematite-limonite, and late stage (chalcedony-calcite+native Cu) alterations. Stable (&delta / 18O, &delta / 34S) and radiogenic (87Sr/86Sr,143Nd/144Nd) isotope compositions suggest a magmatic source for the fluids responsible for alteration-mineralization. Given the spatial-temporal association of alteration- mineralization with magmatic rocks, the hydrothermal system that controls mineralization in Samli appears to be linked with emplacement and cooling of Samli pluton. Samli Fe-oxide (+Cu&plusmn / Au) deposit has features characteristic for both skarn- and Iron-Oxide-Copper-Gold (IOCG) type deposits. The spatial and temporal association with a porphyritic intrusion, widespread calc-silicate assemblage, metal content (abundant Fe-oxide with high copper content) are similar to calcic Fe-Cu skarns, whereas low-Ti (&le / 0.05% TiO2) magnetite/hematite, low-S sulfides (chalcopyrite&gt / pyrite), high Cu (up to 6.78%) and moderate Au (up to 8.82 ppm) grades, local structural control in alteration-mineralization, and the derivation of the causative magma from a SCLM resembles the features pertinent to IOCG type mineralization. Therefore, Samli deposit is defined as a skarn type Fe-Cu mineralization with a potential for IOCG type deposit.

Diese Arbeit untersucht Fe-Oxid-Systeme mit Hilfe einer Kombination aus Mikroskopie (LEEM, Röntgen PEEMs), Beugung (LEED) und Spektroskopie (XPS) und berichtet über die elektronenoptische Entwicklung adaptiver Optiken und Aberrationskorrekturen für einen elektrostatischen abbildenden Energieanalysator. Experimentell untersuchten wir Magnetit und Hämatit Dünnschichten. Ihre Kristallstruktur, Stöchiometrie sowie deren Oberflächenterminierung können durch spezielle Herstellungsverfahren eingestellt werden. Unter Ausnutzung der Echtzeit-Beobachtung mit Mikroskopie, Beugung und Spektroskopie untersuchten wir (a) die Oberflächenmodifikationen von Fe3O4 und α-Fe2O3-Dünnschichten durch Fe Ablagerung; (b) die reversible Phasenumwandlung Fe3O4 ↔ α-Fe2O3 unter verschiedenen Oxidationsbedingungen; (c) die Bildung der metastabilen γ-Fe2O3-Phase und (d) die Wechselwirkung von Fe3O4 und α-Fe2O3 Oberflächen mit unterstützten Pt-Nanopartikeln. Es wurde ein Algorithmus entwickelt, um den LEEM Bildkontrast für inhomogene 2D Oberflächen zu simulieren. Abschließend wird das Design eines Energiefilter-System vorgestellt, das in ein PEEM/LEEM Mikroskop der neuen Generation eingebaut werden wird. Das System basiert auf dem gleichen Abbildungsprinzip wie der magnetische Ω-Filter, der erfolgreich im aktuellen SMART Mikroskop eingesetzt wird. Das neue Instrument zielt auf die Verbesserung der Orts- und Energieauflösung im XPEEM (5 nm und 70 meV). Die Mehrzahl der möglichen Aberrationen zweiter Ordnung wird durch die intrinsische Symmetrie selbstkompensiert. Die Wirkung der anderen Aberrationen wird durch ein geeignetes Design der Verzögerungs- und Beschleunigungsoptiken kombiniert mit einer optimierten Passenergie reduziert. Darüber hinaus kompensieren zusätzliche Hexapole die restlichen dominierenden Aberrationen, wodurch eine Orts- und Energieauflösung besser als 2 nm bzw. 75 meV erreicht wird. / This work presents the investigation of Fe-oxide systems, combining microscopy (LEEM, X-PEEM), diffraction (LEED) and spectroscopy (XPS), and the electron-optical development of adaptive optics and aberration corrections for an electrostatic imaging energy analyzer. Experimentally, we studied magnetite (Fe3O4) and hematite (α-Fe2O3) thin films. Their crystal structure, stoichiometry as well as their surface termination can be tuned by special preparation procedures. Taking advantage of real time observation with microscopy, diffraction and spectroscopy, we investigated (a) the surface modifications of Fe3O4 and α-Fe2O3 thin films by Fe deposition; (b) the reversible phase transformation Fe3O4 ↔ α-Fe2O3 under different oxidation conditions; (c) the formation of the metastable γ-Fe2O3 phase and (d) the interaction of Fe3O4 and α-Fe2O3 surfaces with supported Pt nanoparticles . An algorithm was developed to simulate the LEEM image contrast for inhomogeneous 2D surfaces. The possible application to experimental data and the limitation will be discussed. Finally, the design of an energy filtering system is presented, which will be implemented in a new generation PEEM/LEEM microscope. The system bases on the same imaging principle as the magnetic Ω-filter, successfully implemented in the actual SMART microscope. The new instrument aims for the improvement of lateral and energy resolution in X-PEEM (5 nm and 70 meV, respectively). The majority of the possible second order aberrations are self-compensated by intrinsic symmetry. The effect of the other aberrations is reduced by an adequate design for the deceleration-acceleration optics in combination with optimized pass energy. Furthermore, additional hexapole multipoles compensate for the residual dominating aberrations, yielding in the lateral resolution and energy resolution better than 2 nm and 75 meV, respectively.