Nicolas Perdrial

Strontium and Cesium Release Mechanisms during Unsaturated Flow through Waste-Weathered Hanford Sediments

Leaching behavior of Sr and Cs in the vadose zone of Hanford site (Washington) was studied with laboratory-weathered sediments mimicking realistic conditions beneath the leaking radioactive waste storage tanks. Unsaturated column leaching experiments were conducted using background Hanford pore water focused on first 200 pore volumes. The weathered sediments were prepared by 6 months reaction with a synthetic Hanford tank waste leachate containing Sr and Cs (10(-5) and 10(-3) molal representative of LO- and HI-sediment, respectively) as surrogates for (90)Sr and (137)Cs. The mineral composition of the weathered sediments showed that zeolite (chabazite-type) and feldspathoid (sodalite-type) were the major byproducts but different contents depending on the weathering conditions. Reactive transport modeling indicated that Cs leaching was controlled by ion-exchange, while Sr release was affected primarily by dissolution of the secondary minerals. The later release of K, Al, and Si from the HI-column indicated the additional dissolution of a more crystalline mineral (cancrinite-type). A two-site ion-exchange model successfully simulated the Cs release from the LO-column. However, a three-site ion-exchange model was needed for the HI-column. The study implied that the weathering conditions greatly impact the speciation of the secondary minerals and leaching behavior of sequestrated Sr and Cs.

Contaminant Desorption during Long-Term Leaching of Hydroxide-Weathered Hanford Sediments

Mineral sorption/coprecipitation is thought to be a principal sequestration mechanism for radioactive (90)Sr and (137)Cs in sediments impacted by hyperalkaline, high-level radioactive waste (HLRW) at the DOEs Hanford site. However, the long-term persistence of neo-formed, contaminant bearing phases after removal of the HLRW source is unknown. We subjected pristine Hanford sediments to hyperalkaline Na-AI-NO(3)-OH solutions containing Sr, Cs, and I at 10(-5), 10(-5), and 10(-7) molal, respectively, for 182 days with either <10 ppmv or 385 ppmv pCO(2). This resulted in the formation of feldspathoid minerals. We leached these weathered sediments with dilute, neutral-pH solutions. After 500 pore volumes (PVs), effluent Sr, Cs, NO(3), Al, Si, and pH reached a steady-state with concentrations elevated above those of feedwater. Reactive transport modeling suggests that even after 500 PV, Cs desorption can be explained by ion exchange reactions, whereas Sr desorption is best described by dissolution of Sr-substituted, neo-formed minerals. While, pCO(2) had no effect on Sr or Cs sorption, sediments weathered at <10 ppmv pCO(2) did desorb more Sr (66% vs 28%) and Cs (13% vs 8%) during leaching than those weathered at 385 ppmv pCO(2). Thus, the dissolution of neo-formed aluminosilicates may represent a long-term, low-level supply of (90)Sr at the Hanford site.

Enrichment of Cesium and Rubidium in Weathered Micaceous Materials at the Savannah River Site, South Carolina

The enrichment of Cs and Rb relative to Ba, Sr, and K in three soils representing a range of soil maturities was determined to investigate the long-term sorption behavior of these elements in upland soils of the Savannah River Site (SRS). Elemental mass fractions normalized to upper continental crust (UCC) decreased in the order Cs > Rb > Ba > K > Sr in the soil fine fractions. Only the UCC-normalized amount of Cs was greater than unity. The UCC-normalized amounts in strong-acid extracts decreased as Cs > Rb > Ba > K ≈ Sr. In all three soil cores, the trends of the UCC-normalized amounts of acid-extractable metals were similar to trends of cation-exchange capacity (CEC) calculated from synchrotron-X-ray diffractometry measurements of soil mineralogy. Consequently, the relative enrichment of Cs and Rb is largely controlled by selective sorption to micaceous minerals, including hydroxy-interlayered vermiculite, that dominate the CEC. Where high clay content had caused retention of soil solution, amounts of acid extractable K, Sr, and Ba were enhanced. The retention of natural Cs by these three soils, which developed over many thousands of years, is a strong indicator that radiocesium will likewise be retained in SRS soils.

Cesium and strontium incorporation into zeolite-type phases during homogeneous nucleation from caustic solutions

Abstract Formation of faujasite- and sodalite/cancrinite-type phases associated with caustic waste reactions in the environment may structurally incorporate contaminant species such as radioactive Sr2+ and Cs+, and thus provide a mechanism of attenuation. To investigate mineral evolution and structural incorporation of cations in simplified experiments, aluminosilicate solids were precipitated homogeneously at room temperature from batch solutions containing a 1:1 molal ratio of Si to Al and 10-3 molal Sr and/or Cs, and aged for 30 or 548 days. Syntheses were done with solutions in equilibrium with atmospheric CO2 and with gas-purged solutions. Experimental products were characterized by bulk chemical analyses, chemical extractions, XRD, SEM/TEM, TGA, solid-state 27Al NMR, and Sr EXAFS. Chemical analysis showed that solids had a 1:1 Al:Si molar ratio, and that Sr was sequestered at higher amounts than Cs. After 30 days of aging in purged solutions, XRD showed that zeolite X (faujasite-type) was the only crystalline product. After aging 30 and 548 days in solutions equilibrated with atmospheric CO2, a mixture of sodalite, cancrinite, and minor zeolite X were produced. Surface areas of solids at 30 days were much lower than published values for zeolite phases synthesized at high temperature, although particle aging produced more crystalline and less aggregated phases with higher bulk surface areas. Characterization of products by 27Al NMR indicated only tetrahedrally coordinated Al. Measured isotropic shifts of primary resonances did not change substantially with precipitate aging although the primary mineral phase changed from zeolite X to sodalite/cancrinite, indicating local ordering of Al-Si tetrahedra. Analysis of reaction products by Sr EXAFS suggested Sr bonding in hexagonal prisms and six-membered rings of the supercages of zeolite X that may be more site specific than those of monovalent cations. For samples aged for 548 days, interatomic distances from Sr-EXAFS are consistent with partial Sr dehydration and bonding to framework oxygen atoms in sodalite cages or in large channels in cancrinite. Incorporation of Sr into both faujasite and sodalite/cancrinite phases is favored over Cs during room-temperature synthesis, possibly because of increased cation site competition between Cs+ and Na+. Results of this study help to constrain cation incorporation into sodalite/cancrinite mineral assemblages that form at caustic waste-impacted field sites and may aid in the predictive modeling of contaminant release.

Tropical river suspended sediment and solute dynamics in storms during an extreme drought

Droughts, which can strongly affect both hydrologic and biogeochemical systems, are projected to become more prevalent in the tropics in the future. We assessed the effects of an extreme drought during 2015 on stream water composition in the Luquillo Mountains of Puerto Rico. We demonstrated that drought base flow in the months leading up to the study was sourced from trade-wind orographic rainfall, suggesting a resistance to the effects of an otherwise extreme drought. In two catchments (Mameyes and Icacos), we sampled a series of four rewetting events that partially alleviated the drought. We collected and analyzed dissolved constituents (major cations and anions, organic carbon, and nitrogen) and suspended sediment (inorganic and organic matter (particulate organic carbon and particulate nitrogen)). The rivers appeared to be resistant to extreme drought, recovering quickly upon rewetting, as (1) the concentration-discharge (C-Q) relationships deviated little from the long-term patterns; (2) “new water” dominated streamflow during the latter events; (3) suspended sediment sources had accumulated in the channel during the drought flushed out during the initial events; and (4) the severity of the drought, as measured by the US drought monitor, was reduced dramatically after the rewetting events. Through this interdisciplinary study, we were able to investigate the impact of extreme drought through rewetting events on the river biogeochemistry.

Quantifying particulate and colloidal release of radionuclides in waste-weathered hanford sediments

At the Hanford Site in the state of Washington, leakage of hyperalkaline, high ionic strength wastewater from underground storage tanks into the vadose zone has induced mineral transformations and changes in radionuclide speciation. Remediation of this wastewater will decrease the ionic strength of water infiltrating to the vadose zone and could affect the fate of the radionuclides. Although it was shown that radionuclide host phases are thermodynamically stable in the presence of waste fluids, a decrease in solution ionic strength and pH could alter aggregate stability and remobilize radionuclide-bearing colloids and particulate matter. We quantified the release of particulate, colloidal, and truly dissolved Sr, Cs, and I from hyperalkaline-weathered Hanford sediments during a low ionic strength pore water leach and characterized the released particles and colloids using electron microscopy and X-ray diffraction. Although most of the Sr, Cs, and I was released in dissolved form, between 3 and 30% of the Sr and 4 to 18% of the Cs was associated with a dominantly zeolitic mobile particulate fraction. Thus, the removal of hyperalkaline wastewater will likely induce Sr and Cs mobilization that will be augmented by particulate- and colloid-facilitated transport.

Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanfords cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.