R. Jeffrey Serne

Sorption of Cs+ to micaceous subsurface sediments from the Hanford site, USA

The sorption of Cs+ was investigated over a large concentration range (10−9−10−2 mol/L) on subsurface sediments from a United States nuclear materials site (Hanford) where high-level nuclear wastes (HLW) have been accidentally released to the vadose zone. The sediment sorbs large amounts of radiocesium, but expedited migration has been observed when HLW (a NaNO3 brine) is the carrier. Cs+ sorption was measured on homoionic sediments (Na+, K+, Ca2+) with electrolyte concentrations ranging from 0.01 to 1.0 mol/L. In Na+ electrolyte, concentrations were extended to near saturation with NaNO3(s) (7.0 mol/L). The sediment contained nonexpansible (biotite, muscovite) and expansible (vermiculite, smectite) phyllosilicates. The sorption data were interpreted according to the frayed edge-planar site conceptual model. A four-parameter, two-site (high- and low-affinity) numeric ion exchange model was effective in describing the sorption data. The high-affinity sites were ascribed to wedge zones on the micas where particle edges have partially expanded due to the removal of interlayer cations during weathering, and the low-affinity ones to planar sites on the expansible clays. The electrolyte cations competed with Cs+ for both high- and low-affinity sites according to the trend K+ >> Na+ ≥ Ca2+. At high salt concentration, Cs+ adsorption occurred only on high-affinity sites. Na+ was an effective competitor for the high-affinity sites at high salt concentrations. In select experiments, silver-thiourea (AgTU) was used as a blocking agent to further isolate and characterize the high-affinity sites, but the method was found to be problematic. Mica particles were handpicked from the sediment, contacted with Cs+(aq), and analyzed by electron microprobe to identify phases and features important to Cs+ sorption. The microprobe study implied that biotite was the primary contributor of high-affinity sites because of its weathered periphery. The poly-phase sediment exhibited close similarity in ion selectivity to illite, which has been well studied, although its proportion of high-affinity sites relative to the cation exchange capacity (CEC) was lower than that of illite. Important insights are provided on how Na+ in HLW and indigenous K+ displaced from the sediments may act to expedite the migration of strongly sorbing Cs+ in subsurface environments.

Geochemical Factors Affecting the Behavior of Antimony, Cobalt, Europium, Technetium, and Uranium in Vadose Zone Sediments

In developing the Field Investigation Report (FIR) for the Waste Management Area (WMA) S-SX at the Hanford Site, cesium-137 was the only gamma emitting radionuclide of concern (Knepp 2002). However, in WMA B-BX-BY, the spectral gamma logging data identify seven gamma emitting radionuclides, cesium-137, antimony-125, europium-152 and -154, cobalt-60, uranium-235 and -238 (DOE-GJPO 1998). The geochemical behaviors of several of these radionuclides, antimony-125 and the two europium isotopes, have not been extensively investigated at the Hanford Site. This task was initiated to assure that our understanding of the geochemical properties affecting the environmental behavior of these radionuclides reflects the current state of knowledge. A literature review was conducted to assess the important oxidation/reduction, aqueous speciation, solubility, and adsorption processes affecting the environmental behavior of antimony, cobalt, europium, technetium, and uranium in vadose zone sediments with low-organic matter content in semi-arid environments such as those at the Hanford Site. Technetium-99 was included in this task because of its importance in the long-term risk calculations. This report presents the results of this literature review.

Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation

During the nuclear waste vitrification process volatilized (99)Tc will be trapped by melter off-gas scrubbers and then washed out into caustic solutions, and plans are currently being contemplated for the disposal of such secondary waste. Solutions containing pertechnetate [(99)Tc(VII)O(4)(-)] were mixed with precipitating goethite and dissolved Fe(II) to determine if an iron (oxy)hydroxide-based waste form can reduce Tc(VII) and isolate Tc(IV) from oxygen. The results of these experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media. Identification of the phases, goethite + magnetite, was performed using XRD, SEM and TEM methods. Analyses of the Tc-bearing solid products by XAFS indicate that all of the Tc(VII) was reduced to Tc(IV) and that the latter is incorporated into goethite or magnetite as octahedral Tc(IV). Batch dissolution experiments, conducted under ambient oxidizing conditions for more than 180 days, demonstrated a very limited release of Tc to solution (2-7 μg Tc/g solid). Incorporation of Tc(IV) into the goethite lattice thus provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.

Hanford Contaminant Distribution Coefficient Database and Users Guide

This report compiles in a single source the Kd values measured with Hanford sediment for radionuclides and toxic compounds that have the greatest potential for driving risk to human health and safety in the vadose zone and groundwater at the Hanford Site.

Limited Field Investigation Report for Uranium Contamination in the 300 Area, 300-FF-5 Operable Unit, Hanford Site, Washington

Four new CERCLA groundwater monitoring wells were installed in the 300-FF-5 Operable Unit in FY 2006 to fulfill commitments for well installations proposed in the Hanford Federal Facility Agreement and Consent Order Milestone M-24-57. Wells were installed to collect data to determine the distribution of process uranium and other contaminants of potential concern in groundwater. These data will also support uranium contaminant transport simulations and the wells will supplement the water quality monitoring network for the 300-FF-5 OU. This report supplies the information obtained during drilling, characterization, and installation of the new groundwater monitoring wells. This document also provides a compilation of hydrogeologic, geochemical, and well construction information obtained during drilling, well development, and sample collection/analysis activities.

Vadose zone infiltration rate at Hanford, Washington, inferred from Sr isotope measurements

[i] Sr isotope ratios were measured in the pore water, acid extracts, and sediments of a 70-m vadose zone core to obtain estimates of the long-term infiltration flux for a site in the Hanford/DOE complex in eastern Washington State. The 8 7 Sr/ 8 6 Sr values for the pore waters decrease systematically with depth, from a high value of 0.721 near the surface toward the bulk sediment average value of 0.711. Estimates of the bulk weathering rate combined with Sr isotopic data were used to constrain the long-term (century to millenial scale) natural diffuse infiltration flux for the site given both steady state and nonsteady state conditions. The models suggest that the infiltration flux for the site is 7 ′ 3 mm/yr. The method shows potential for providing long-term in situ estimates of infiltration rates for deep heterogeneous vadose zones.

Characterization of Vadose Zone Sediment: Uncontaminated RCRA Borehole Core Samples and Composite Samples

This report was revised in September 2008 to remove acid-extractable sodium data from Tables 4.14, 4.16, 5.20, 5.22, 5.43, and 5.45. The sodium data was removed due to potential contamination introduced during the acid extraction process. The rest of the text remains unchanged from the original report issued in February 2002. The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from Resource Conservation and Recovery Act (RCRA) borehole bore samples and composite samples.

Sorption and transport behavior of radionuclides in the proposed low-level radioactive waste disposal facility at the Hanford site, Washington

Abstract A series of batch sorption and column experiments was conducted to investigate sorption and transport behavior of 99Tc, 129I, 79Se, and 90Sr on and through borehole sediments collected from the proposed low-level radioactive waste disposal facility at the Hanford Site (200 East Area). Batch sorption experiments were conducted on Hanford sediment using uncontaminated Hanford groundwater and simulated glass leachates spiked with individual radionuclides. Strongest sorption occurred for 90Sr, while 79Se sorption was intermediate, and 129I and 99Tc showed the least sorption affinities on Hanford sediment among these radionuclides studied. The results of column experiments that measured transport behavior of these radionuclides through Hanford sediment were similar to the mobility that can be calculated from the batch sorption results, that is high mobility for 99Tc and 129I compared to the intermediate and strong retardation for 79Se and 90Sr, respectively. These contaminant sorption data on sediments from below the proposed disposal facility, especially the tests using simulated glass leachate, corroborate values obtained for sediments collected in the past from near by locations and for generic solutions such as regional groundwater. These new data should provide more technical defensibility for past performance assessment predictions that did not use site-specific sediments and leachates. Further, the new data will be incorporated into future performance assessment activities that will update and improve past predictions.

Characterization of Vadose Zone Sediment: Borehole 299-E33-45 Near BX-102 in the B-BX-BY Waste Management Area

This report was revised in September 2008 to remove acid-extractable sodium data from Table 4.22. The data was removed due to potential contamination introduced during the acid extraction process. The remaining text is unchanged from the original report issued in 2002. The overall goal of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc., asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediments from within Waste Management Area B-BX-BY. This report is the first in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from borehole 299-E33-45 installed northeast of tank BX-102.

Geochemical evolution of highly alkaline and saline tank waste plumes during seepage through vadose zone sediments

Abstract Leakage of highly saline and alkaline radioactive waste from storage tanks into underlying sediments is a serious environmental problem at the Hanford Site in Washington State. This study focuses on geochemical evolution of tank waste plumes resulting from interactions between the waste solution and sediment. A synthetic tank waste solution was infused into unsaturated Hanford sediment columns (0.2, 0.6, and 2 m) maintained at 70°C to simulate the field contamination process. Spatially and temporally resolved geochemical profiles of the waste plume were obtained. Thorough OH − neutralization (from an initial pH 14 down to 6.3) was observed. Three broad zones of pore solutions were identified to categorize the dominant geochemical reactions: the silicate dissolution zone (pH > 10), pH-neutralized zone (pH 10 to 6.5), and displaced native sediment pore water (pH 6.5 to 8). Elevated concentrations of Si, Fe, and K in plume fluids and their depleted concentrations in plume sediments reflected dissolution of primary minerals within the silicate dissolution zone. The very high Na concentrations in the waste solution resulted in rapid and complete cation exchange, reflected in high concentrations of Ca and Mg at the plume front. The plume-sediment profiles also showed deposition of hydrated solids and carbonates. Fair correspondence was obtained between these results and analyses of field borehole samples from a waste plume at the Hanford Site. Results of this study provide a well-defined framework for understanding waste plumes in the more complex field setting and for understanding geochemical factors controlling transport of contaminant species carried in waste solutions that leaked from single-shell storage tanks in the past.