Linearity and reversibility of iodide adsorption on sediments from Hanford, Washington under water saturated conditions.

A series of adsorption and desorption experiments were completed to determine the linearity and reversibility of iodide adsorption onto sediment at the Hanford Site in southeastern Washington. Adsorption experiments conducted with Hanford formation sediment and groundwater spiked with dissolved (125)I (as an analog tracer for (129)I) indicated that iodide adsorption was very low (0.2 mL/g) at pH 7.5 and could be represented by a linear isotherm up to a total concentration of 100 mg/L dissolved iodide. The results of desorption experiments revealed that up to 60% of adsorbed iodide was readily desorbed after 14 days by iodide-free groundwater. Because iodide adsorption was considered to be partially reversible, even though small amount of initial iodide is retarded by adsorption at mineral-water interfaces, the weak adsorption affinity results in release of iodide when iodide-free pore waters and uncontaminated groundwaters contact the contaminated sediments in the vadose zone and aquifer systems.

Molecular interfacial reactions between Pu(VI) and manganese oxide minerals manganite and hausmannite.

The sorption of Pu(VI) onto manganite (MnOOH) and hausmannite (Mn3O4) was studied as a function of time, solution pH, and initial plutonium concentration. Kinetic experiments indicate that the surface complexation of plutonium occurs over the first 24 h of contact with the mineral surface. The sorption increases with pH beginning at pH 3 until it reaches a maximum value of 100% at pH 8 (0.0011-0.84 micromol of Pu/m2 of manganite and 0.98-1.2 micromol of Pu/m2 of hausmannite) and then decreases over the pH range from 8 to 10. The ratio of solid to solution was 10 mg/mL for manganite experiments and 4 mg/mL for hausmannite samples. Carbonate was not excluded from the experiments. The amount of plutonium removed from the solution by the minerals is determined by a combination of factors including the plutonium solution species, the surface charge of the mineral, and the mineral surface area. X-ray absorption fine structure taken at the Pu L(III) edge were compared to plutonium standard spectra and showed that Pu(VI) was reduced to Pu(IV) after contact with the minerals. Plutonium sorption to the mineral surface is consistent with an inner-sphere configuration, and no evidence of PuO2 precipitation is observed. The reduction and complexation of Pu(VI) by manganese minerals has direct implications on possible migration of Pu(VI) species in the environment.

Distribution and retention of 137Cs in sediments at the Hanford Site, Washington.

137Cesium and other contaminants have leaked from single-shell storage tanks (SSTs) into coarse-textured, relatively unweathered unconsolidated sediments. Contaminated sediments were retrieved from beneath a leaky SST to investigate the distribution of adsorbed 137Cs+ across different sediment size fractions. All fractions contained mica (biotite, muscovite, vermiculatized biotite), quartz, and plagioclase along with smectite and kaolinite in the clay-size fraction. A phosphor-plate autoradiograph method was used to identify particular sediment particles responsible for retaining 137Cs+. The Cs-bearing particles were found to be individual mica flakes or agglomerated smectite, mica, quartz, and plagioclase. Of these, only the micaceous component was capable of sorbing Cs+ strongly. Sorbed 137Cs+ could not be significantly removed from sediments by leaching with dithionite citrate buffer or KOH, but a fraction of the sorbed 137Cs+ (5-22%) was desorbable with solutions containing an excess of Rb+. The small amount of 137Cs+ that might be mobilized by migrating fluids in the future would likely sorb to nearby micaceous clasts in downgradient sediments.