Experiments were carried out on the solidification of iron-manganese alloys containing sulphur and carbon. The alloys were solidified under controlled conditions in a travelling furnace constructed especially for the investigation. Qualitative and quantitative metallography and electron-probe microanalysis were used to determine the solidification structure, dendrite arm spacings, solute concentration profiles and inclusion compositions. The results were interpreted in the light of existing knowledge and concepts especially developed for the purpose of this investigation. / Thesis / Doctor of Philosophy (PhD)

New evidence shows iron(II) oxidation is strongly coupled to nitrate reduction under anaerobic conditions in freshwater sediments and agricultural soils. However, the contribution of iron(II) oxidation to nitrate reduction is unknown. Furthermore, oxidation of manganese(II) by nitrate has been largely overlooked. This study investigated nitrate-dependent iron(II) and manganese(II) oxidation in an agricultural soil (Sadler silt loam) using stirred-batch kinetic techniques with native soil organic carbon (SOC) as the electron donor and included addition of amendments (hydrogen gas and wheat residue). In the presence of native SOC, nitrate-dependent Fe(II) and Mn(II) oxidation occurred at early stages of the reaction while organic carbon participated at longer times. Contributions of iron(II) and manganese(II) oxidation to nitrate reduction were 19% and 25%, respectively. This is significant in light of excess SOC relative to total Fe and Mn in the Sadler soil. Addition of hydrogen gas lowered the contribution of iron(II) oxidation to nitrate reduction to 10%, while addition of plant residue raised this value to approximately 55%. Manganese(II) oxidation contributed 50% to nitrate reduction under hydrogen amended conditions. These coupled processes involving Fe(II) and Mn(II) oxidation are an underappreciated aspect of the nitrogen cycle and merit consideration in future studies.

The presented thesis includes investigations to fully characterize the electronic structure and magnetic properties ofselected manganese containing high-spin molecules by means of various X-ray spectroscopic, magnetic and theoretical methods. The investigations on the Mn4 star-shaped molecule havelead to a number of interesting results. Magneto-chemical studies exhibit very weak exchange coupling constantsbetween the four Mn(II) ions, leading to complicated low lying states in which the ground state is not well separated, resulting from a dominant weak ferromagnetic coupling and a giant moment of up to 20 µB/f.u. XMCD measurements revealed that almost the completemagnetic moment is located around the Mn(II) ions.This is in agreement with only a few charge transfer states foundwithin the detailed X-ray absorption spectroscopic study. The electronic structure and detailed magnetic properties of the star-shaped heteronuclear CrIIIMnII3 complex have been precisely investigated.With XPS the homovalency of Mn and Cr have been verified. The XA-spectra of the manganese and chromium L edges were measured and compared to earlier investigated Mn4 spectra.The combination high-magnetic field magnetic measurements and element selective XMCD of Mn and Cr L edges and quantum model calculations lead to a complete analysis of the magnetic structure of the CrMn3 magnetic core. The III valence state of the manganese ions in MnIII6O2Salox has been verified. From X-ray diffraction, typical Jahn-Teller distorted oxygen octahedra have been found for Mn(III) ions. Comparisons of XPS and XAS spectra of the complex to corresponding spectraof maganite and tetranuclear manganese(II) cluster it was definitely possible to identify MnIII6O2Salox as a pure Mn(III) compound.