Chapter 1

Dynamic Processes Occurring at the Cr^III_aq – Manganite (γ-MnOOH) Interface: Simultaneous Adsorption, Microprecipitation, Oxidation/Reduction and Dissolution

The complex interaction between Cr^III_aq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10⁻⁴ to 10⁻² M CrOH²⁺_aq. Solution compositional changes during batch reactions were characterized by ICP and UVvis. The manganites were characterized before and after reaction with XPS, SEM, high-resolution FESEM, and EDS analysis. Fluid-cell AFM was used to follow these metal-mineral interactions in situ. The reactions are characterized by 1) sorption of Cr^III and the surface-catalyzed microprecipitation of Cr^III-hydroxy hydrate on manganite surfaces, 2) the acidic dissolution of the manganite, and 3) the simultaneous reductive dissolution of manganite coupled with the oxidation of Cr^III_aq to highly toxic Cr^VI_aq. Cr^III-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to faster acid-promoted and Mn-reduction- promoted dissolution. Due to direct redox coupling with Mn reduction, Cr oxidation was most rapid in the lower pH range. Neither Mn^II nor Cr^VI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, Cr^III_aq was effectively removed from solution to form Cr^III-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and Cr^VI_aq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals, and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites.

Chapter 2

Comparison of the Reactivity of Various Mn-Oxides with Cr^III_aq: Microscopic and Spectroscopic Observations of Dissolution, Cr-sorption and Cr and Mn Redox Interactions

The interaction between Cr^III_aq and seven different Mn-oxides (6 monomineralic, 1 synthetic) have been observed in pH ~4.4 HNO₃ and pH ~4.4 ~10⁴ M Cr^III_aq solutions. For each mineral-solution interaction, the aqueous chemical concentrations (e.g. [Mn]_aq, [Cr]_aq, [Cr^VI_aq]) were measured with time. Reacted samples were examined by XPS to determine if, and to what extent, the surface chemical states of Cr, Mn and O had changed. Microscopic observations of the reacted surfaces were obtained using AFM and high-resolution, low-voltage FESEM. The solubility of the Mn-oxides in the acidic, non-Cr bearing solutions varied inversely with the average Mn valence, but did not show systematic behavior with respect to the mineral structure type (e.g. tunnel, layer, framework). This trend was interpreted as resulting from the relative ability of an adsorbed proton to polarize surface Mn-O bonds, with the polarizability being in the order Mn²⁺-O > Mn³⁺-O > Mn⁴⁺-O. For samples reacted with Cr^III_aq, the rate and extent of reductive dissolution was always greater than for acidic dissolution during the initial time period. The measured ratios of the [Mn]_aq : [Cr^VI]_aq were approximately in agreement with the values expected from the proposed stoichiometric reactions. Cr-uptake was observed to occur in undersaturated solutions as a result of adsorption, absorption and surface catalyzed precipitation. The chromium as detected by XPS was predominately Cr^III, however pyrolusite contained both Cr^III and Cr^VI. Previous studies have implicated a chromium surface precipitate to be responsible for the cessation of the Cr^III_aq oxidation reaction. Our surface sensitive FESEM and AFM observations tend to suggest that Cr-uptake is by isolated site binding, very small (<30 nm) surface clusters or monolayer scale films. Cr-uptake was followed by slow Cr-release on several of the solids (particularly the layered solids) after a substantial portion of the total aqueous Cr had been converted to Cr^VI_aq.

The oxidizing ability of the different Mn-oxides for Cr^III_aq is evaluated with regards to the energy level of the redox couple (i.e. the redox potential) as compared with the Fermi energy level of the Mn-oxide. Although these energies were calculated rather than directly measured, the results indicate that electrons originating from adsorbed Cr^III ions may be transferred into the conduction band or more likely, into available surface states. The presence of an initial limited quantity of electron accepting surface states likely explains the observation of a rapid initial Cr^III-oxidation followed by much slower oxidation. The Mn-oxides that exhibited the greatest and longest lasting Cr^III-oxidizing power were the Mn-oxides containing Mn⁺, and in particular those containing Mn³⁺ and Mn⁺. It is believed that the combined presence of a reducible Mn ion (e.g. Mn³⁺) and a highly soluble Mn⁺ ion facilitates a sustained Cr^III-oxidation reaction because fresh surface is exposed during the reaction.