There are currently multiple U.S. Department of Energy sites with significant quantities of technetium-99 stored under a variety of conditions. While it is known that Tc in the VII oxidation state has a very high rate of envi- ronmental migration, little is known about the chemistry of the IV oxidation state, expected to occur under anoxic conditions. In this work, the binding of Tc(IV) with humic acid (HA) of varying sizes was studied using ultracentri- fugation and total organic carbon analysis. A constant ratio HA-bound Tc(IV):HA concentration was observed for the 10-1,000 nm HA size range and it is independent of pH, ionic strength, background electrolyte and HA origin. HA zeta potentials were determined; the largest HA size frac- tion had a considerably less negative zeta potential than the smaller size fractions; the zeta potential of the colloidal size fraction (10-1,000 nm) was independent of solution conditions. 13 C cross polarization magic angle spinning and attenuated total reflectance-Fourier transform infrared spectroscopy results indicate that solid filtrates of HA from two different origins have distinct spectra that were not altered with changes in solution conditions. This work shows that we are able to use zeta potential measurements to describe binding characteristics of HA with Tc(IV).
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