Publication Date

2008

Document Type

Dissertation

Committee Members

Udo Becker (Committee Member), G. Allen Burton (Committee Member), Cindy K. Carney (Committee Member), Songlin Cheng (Committee Member), Steven R. Higgins (Advisor), Audrey E. Mcgowin (Committee Member)

Degree Name

Doctor of Philosophy (PhD)

Abstract

Dissolution as a function of solution undersaturation (Ω) was studied on both celestite and barite (001) by the aid of atomic force microscopy (AFM). Both the sulfates exhibited non-linear reactivity trends showing increasing dissolution rates with decreasing Ω. In the case of celestite, the dissolution rate non linearity was attributed to a changeover in reaction mechanism. At higher undersaturations below a critical saturation state of Ωcrit ~ 0.1, dissolution occurred both along the existing step edges and also via the creation of new steps. At conditions near saturation states dissolution took place exclusively by removal of ions from existing step edges. On the other hand dissolution rate nonlinearity in the case of barite was controlled by changes in step speeds with Ω. Similar dissolution rate behavior also evident on powdered barite in mixed flow reactor system establishes the dissolution rate non-linearity in terms Ω to be the characteristic property of barite. Celestite (001) dissolution was also studied in terms of Sr:SO4 by AFM to examine the mineral's reactivity under nonstoichiometric solute conditions. At Ω = 0.63, reaction kinetics were investigated by measuring <010> and <120> step speeds. Application of a theoretical model, describing step speed as a function of Sr:SO4 indicated that both step speeds reached maxima at Sr:SO4 = 1. This implied that the rate of SO42- ion attachment was equal to that of the Sr2+ ion to the kink sites. Laboratory experiments on barite dissolution in the presence of CrO42-(aq) exhibited substantial lowering in dissolution rates due to adsorption of CrO42- onto surface reactive sites. AFM studies on barite (001) at 70°C showed dissolution rates ~ 2.3 times lower at 1000 μM CrO42- and MFR experiments on powdered barite at 25°C quantified ~ 2 times lowering in dissolution rates at 5 μM CrO42-. Transport of aqueous CrO42- (4mM) through powdered barite in one dimensional plug flow reactor showed delayed chromate peak arrival times compared to that of a tracer (Na+) at all flow rates. The efficiency of barite being able to retain aqueous chromate appears to be a possible means to clean chromate contaminated waste waters.

Page Count

293

Department or Program

Department of Earth and Environmental Sciences

Year Degree Awarded

2008

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