title: Influence of alkaline co-contaminants on technetium mobility in vadose zone sediments.
abstract: Pertechnetate was slowly reduced in a natural, untreated arid sediment under anaerobic conditions (0.02 nmolg(-1)h(-1)), which could occur in low permeability zones in the field, most of which was quickly oxidized. A small portion of the surface Tc may be incorporated into slowly dissolving surface phases, so was not readily oxidized/remobilized into pore water. In contrast, pertechnetate reduction in an anaerobic sediment containing adsorbed ferrous iron as the reductant was rapid (15-600 nmolg(-1)h(-1)), and nearly all (96-98%) was rapidly oxidized/remobilized (2.6-6.8 nmolg(-1)h(-1)) within hours. Tc reduction in an anaerobic sediment containing 0.5-10mM sulfide showed a relatively slow reduction rate (0.01-0.03 nmolg(-1)h(-1)) that was similar to observations in the natural sediment. Pertechnetate infiltration into sediment with a highly alkaline water resulted in rapid reduction (0.07-0.2 nmolg(-1)h(-1)) from ferrous iron released during biotite or magnetite dissolution. Oxidation of NaOH-treated sediments resulted in slow Tc oxidation (∼0.05 nmolg(-1)h(-1)) of a small fraction of the surface Tc (13-23%). The Tc remaining on the surface was Tc(IV) (by XANES), and autoradiography and elemental maps of Tc (by electron microprobe) showed Tc was present associated with specific minerals, rather than being evenly distributed on the surface. Dissolution of quartz, montmorillonite, muscovite, and kaolinite also occurred in the alkaline water, resulting in significant aqueous silica and aluminum. Over time, aluminosilicates, cancrinite, zeolite and sodalite were precipitating. These precipitates may be coating surface Tc(IV) phases, limiting reoxidation.
authors.affiliation: Pacific Northwest National Laboratory, P.O. Box 999, MSIN K3-61, Richland, WA 99354, USA. Electronic address: jim.szecsody@pnnl.gov.
authors.forename: Jim E
authors.initials: JE
authors.lastname: Szecsody
authors.affiliation: Washington State Department of Ecology, Yakima, WA, USA. Electronic address: daja461@ecy.wa.gov.
authors.forename: Danielle P
authors.initials: DP
authors.lastname: Jansik
authors.affiliation: Pacific Northwest National Laboratory, P.O. Box 999, MSIN K3-61, Richland, WA 99354, USA. Electronic address: james.mckinley@pnnl.gov.
authors.forename: James P
authors.initials: JP
authors.lastname: McKinley
authors.affiliation: Pacific Northwest National Laboratory, P.O. Box 999, MSIN K3-61, Richland, WA 99354, USA. Electronic address: nancy.hess@pnnl.gov.
authors.forename: Nancy J
authors.initials: NJ
authors.lastname: Hess
mesh_terms: D000327:Adsorption; D019015:Geologic Sediments / Q000737:chemistry*; D013670:Sodium Pertechnetate Tc 99m / Q000737:chemistry; D013667:Technetium / Q000737:chemistry*
chemical_list: D013667:Technetium; D013670:Sodium Pertechnetate Tc 99m
keywords: Alkaline dissolution/precipitation; Pertechnetate reduction; Subsurface contamination; Technetium