- Eisensulfid <Eisen(II)-sulfid> (1) (remove)
- The reactivity of ferric (hydr)oxides towards dissolved sulphide (2010)
- Ferric (hydr)oxides are ubiquitous with different characteristics such as stability, reactivity and surface properties and play an important role in redox reactions in many environments such as soils, marine sediments, lakes, and ground water. Under anoxic conditions, ferric (hydr)oxides are reduced by dissolved sulphide or by microorganisms. This reaction generates Fe(II) which may precipitate as iron hydroxide, adsorb to the ferric (hydr)oxide surfaces and transform the ferric (hydr)oxides into more stable minerals, or precipitate as iron sulphide. During the reductive dissolution adsorbed species like arsenic may be released from the oxide surfaces to solution. Furthermore, the generation of ferrous iron in ground water systems, their transport through the groundwater-surface water interface, and subsequent iron oxidation and precipitation contribute to the acidification of lakes or sediments as a result of both mining activities and natural processes. Hence, the redox reactions between dissolved sulphide and ferric (hydr)oxides are of fundamental importance for the elemental cycles of sulphur and iron and in particular for the carbon and electron flow in groundwater, soil, and lake systems. The overall chemical pathway of the reactions and their kinetics are reasonably understood. There is less knowledge on the transient stages and the electron transfer processes during the reactions which involve the formation of amorphous or disordered, as well as, nucleation of (metastable) crystalline phases at the reacting interface as a function of time. Furthermore, the interaction between dissolved sulphide and ferric (hydr)oxides can be regard as a key reaction ultimately leading to pyrite formation in both marine and freshwater sediments. However, the knowledge on the pathways and on the controlling factors of pyrite formation is still limited. Therefore this work focused on anoxic abiotic kinetic batch and flow-through experiments with various ferric (hydr)oxides and dissolved sulphide at pH 4 and pH 7. TEM, X-ray diffraction, Mössbauer spectroscopy, and wet chemistry were used to explore the nanocrystalline products which formed over time during the reaction. Furthermore, these experiments should be contribute to the elucidation of the role of Fe2+ regarding the iron sulphide formation and the transformation of Fe(III) oxides. The electron transfer reaction between dissolved sulphide and ferric (hydr)oxides and the deeper insight into the processes occurring at the ferric (hydr)oxides surfaces were investigated in chapter 2 and 3. Batch experiments with dissolved sulphide and ferrihydrite, lepidocrocite, and goethite were performed under well-defined conditions at pH 7 and at room temperature in a glove box with a special emphasis on the characterization of nanocrystalline products forming at different time steps over a reaction time of 14 days. The temporal evolution of the chemical species and the solid phases indicate that the reaction progress was highly dynamic. After two weeks we observed the formation of secondary minerals and pyrite in all experiments as a result of excess-Fe(II) formation. Ferrihydrite was transformed completely via dissolution-precipitation processes into more stable minerals such as magnetite, hematite, pyrite, and into minor amounts of goethite. In the experimental solution with lepidocrocite and goethite the host mineral remained and we detected only pyrite as new mineral. Small amounts of goethite were transformed to hematite while the pyrite formation in the experimental solution with lepidocrocite was accompanied by traces of magnetite. In chapter 4, the reaction kinetic of dissolved sulphide and ferric (hydr)oxides were studied under abiotic, anoxic, and flow-through conditions at pH 4 and 7 and at room temperature over a time period of 6 hours. Various synthetic Fe(III) (hydr)oxides with a broad range of crystallinity and different surface and bulk properties were used in order to assess how variations in these properties influence the kinetics of chemical Fe(III) (hydr)oxide reduction. These experiments showed, as well as, the batch experiments, that the formation of Fe(II) and S(0) was decoupled. In the presence of ferrihydrite and lepidocrocite the generated Fe(II) due to the reaction with dissolved sulphide adsorbed to their surfaces and was accompanied by an electron transfer which led to the formation of excess-Fe(II). These processes seem to be accelerating the reductive dissolution of ferrihydrite and lepidocrocite by dissolved sulphide. Goethite behaved differ: the adsorption of Fe(II) onto the goethite surface occurred without an electron transfer. Thus, the generated Fe(II) controls the reductive dissolution of various ferric (hydr)oxides by dissolved sulphide.