Performance Optimization of Metallic Iron and Iron Oxide Nanomaterials for Treatment of Impaired Water Supplies

Iron nanomaterials including nanoscale zero valent iron (NZVI), NZVI-based bimetallic reductants (e.g., Pd/NZVI) and naturally occurring nanoscale iron mineral phases represent promising treatment tools for impaired water supplies. However, questions pertaining to fundamental and practical aspects of their reactivity may limit their performance during applications.For NZVI treatment of pollutant source zones, a major hurdle is its limited reactive lifetime. In Chapter 2, we report the longevity of NZVI towards 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) and hexavalent chromium [Cr(VI)] in oxygen-free systems with various anionic co-solutes (e.g., Cl-, SO2-, ClO-, HCO-, NO-). Trends in longevity provide evidence that surface-associated Fe(II) species are responsible for Cr(VI) reduction, whereas 1,1,1,2-TeCA reduction depends on the accessibility of Fe(0) at the NZVI particle surface. In Chapter 3, we show that dithionite, previously utilized for in situ redox manipulation, can restore the reducing capacity of passivated NZVI treatment systems. Air oxidation of NZVI at pH &ge 8 quickly exhausted reactivity despite a significant fraction of Fe(0) persisting in the particle core. Reduction of this passive layer by low dithionite concentrations restored suspension reactivity to levels of unaged NZVI, with multiple dithionite additions further improving pollutant removal.In Chapter 4, measurements of solvent kinetic isotope effects reveals that optimal Pd/NZVI reactivity results from accumulation of atomic hydrogen, which only occurs in NZVI-based systems due to their higher rates of corrosion. However, atomic hydrogen formation only occurs in aged Pd/NZVI suspensions for ~2 weeks, after which any reactivity enhancement likely results from galvanic corrosion of Fe(0). Finally, the activity of hybrid nanostructures consisting of multi-walled carbon nanotubes decorated with of hematite nanoparticles (&alpha-Fe2O3/MWCNT) is explored in Chapter 5. Sorption of Cu(II) and Cr(VI) is enhanced in hybrid nanostructure systems beyond what would be expected from simple additive sorption capacities of their building blocks. The enhanced sorption capacity is in part derived from the greater surface area of hematite nanoparticles immobilized on MWCNTs relative to aggregated hematite suspensions. The hybrid &alpha-Fe2O3/MWCNT may also exhibit unique surface chemistry, as supported by the tunable values of zeta potential measured as a function of the mass of &alpha-Fe2O3 deposited on the MWCNTs