Project Work Plan Chromium Vadose Zone Characterization and Geochemistry

The major objectives of the proposed study are to 1) determine the leaching characteristics of Cr(VI) from contaminated sediments collected from 100 area spill sites, 2) elucidate possible Cr(VI) mineral and/or chemical associations that may be responsible for Cr(VI) retention in the Hanford site 100 areas through the use of i) macroscopic solubility studies and ii) microscale characterization of contaminated sediments, and 3) from these data construct a conceptual model of Cr(VI) geochemistry in the Hanford 100 area vadose zone. These objectives are based on locating and obtaining contaminated sediment with depth and at varying Cr(VI) concentrations as we hypothesize that mineral/chemical-Cr(VI) associations should be related to the total Cr concentration and other master geochemical variables (e.g., pH, counter-cation type and concentration, and water content). In addressing these objectives, additional benefits accrued will be (1) a fuller understanding of Cr(VI) entrained in the vadose zone that will that can be utilized in modeling potential Cr(VI) source terms, and 2) accelerating the Columbia River 100 area corridor cleanup by developing remedial action based on a fundamental understanding of Cr(VI) vadose zone geochemistry

Project Work Plan 100-N Area Strontium-90 Treatability Demonstration Project: Phytoremediation Along the 100-N Columbia River Riparian Zone

The 100-N Area Innovative Treatment and Remediation Demonstration (ITRD) identified phyto¬remediation as a potential technology both for the removal of 90Sr from the soil of the riparian zone and as a filter for groundwater along the Columbia River. Recent greenhouse and growth chamber studies have demonstrated the viability of phytoextraction to remove 90Sr from this area’s soil/water; in conjunction with monitored natural attenuation and an apatite barrier the process would make an effective treatment for remediation of the 100-N Area 90Sr plume. All activities associated with the 100-NR-1 and 100-NR-2 Operable Units of the Hanford 100-N Area have had, and continue to have, significant regulatory and stakeholder participation. Beginning in 1998 with the ITRD process, presentations to the ITRD TAG were heavily attended by EPA, Washington State Department of Ecology, and stakeholders. In addition, three workshops have been held to receive regulatory and stakeholder feedback on monitored natural attenuation, the apatite barrier, and phytoremediation; these were held in Richland in August 2003, December 2004, and August 2005. The apatite injection treatability test plan (DOE 2005) describes phytoremediation as a technology to be evaluated during the March 2008 evaluation milestone as described in the Tri-Party Agreement change request (M-16-06-01 Change Control Form). If, during this evaluation milestone, phytoremediation is favorably evaluated it would be incorporated into the treatability test plan. The phytoremediation treatability test described in this proposal is strongly supported by the Washington State Department of Ecology

Quinoline Sorption on Na-Montmorillonite: Contributions of the Protonated and Neutral Species

Dilute aqueous solutions of quinoline were contacted with Na-montmorillonite to elucidate the sorption process of the neutral and protonated species. Sorption occurs via a combination of ion exchange and molecular adsorption and yields S-type isotherms. Exchange between the quinolinium ion (QH+ and Na can be described by means of Vanselow selectivity coefficients and a thermodynamic exchange constant (Kex). Due to the apparent adsorption of the neutral species at high mole fractions (x) of the solid phase, the thermodynamic standard state was defined as 0.5 mole fraction. The selectivity at pH ~4.95 of the QH+ species over Na (at XQH+ 0.5) was determined to be Kv = 340. At pH ≥ 5.5 surface mole fractions of 0.5 could not he obtained without adsorption of the neutral species. This study suggests that at dilute solution concentrations quinoline is sorbed preferentially as the cation even at pHs \u3e\u3e pKa. A critical surface-solution concentration is apparently necessary for adsorption of the neutral species

Sorption of Binary Mixtures of Aromatic Nitrogen Heterocyclic Compounds on Subsurface Materials

Single and binary solute sorption of pyridine, quinoline, and acridine has been investigated on two low organic carbon subsurface materials with similar properties but different equilibrium pH when saturated with water. Single solute sorption for all compounds is higher in the acidic soil as compared to the basic soil, reflecting stronger sorption of the protonated organic cations. The protonated species exhibit high selectivity for the exchange complex at low aqueous concentration with selectivity increasing with ring number. Binary sorption experiments with quinoline/pyridine and quinoline/acridine demonstrate that competitive sorption occurs between compounds in the acidic subsoil where the protonated compound species predominate in solution. In contrast, competition is minimal in the basic subsoil when the compounds are neutral. The competition between compounds is consistent with their measured single solute sorption and suggests mass action on a common set of high-affinity surface sites. A simplified model based on ideal adsorbed solution theory (IAS) is used to provide simulations of binary solute sorption that are in good qualitative agreement with experimental results. It is suggested that competition between ionized solutes may significantly influence transport of organic mixtures when the groundwater pH is near the pKa of the compounds

Geochemical Characterization of Chromate Contamination in the 100 Area Vadose Zone at the Hanford Site

The major objectives of the proposed study were to: 1.) determine the leaching characteristics of hexavalent chromium [Cr(VI)] from contaminated sediments collected from 100 Area spill sites; 2.) elucidate possible Cr(VI) mineral and/or chemical associations that may be responsible for Cr(VI) retention in the Hanford Site 100 Areas through the use of i.) macroscopic leaching studies and ii.) microscale characterization of contaminated sediments; and 3.) provide information to construct a conceptual model of Cr(VI) geochemistry in the Hanford 100 Area vadose zone. In addressing these objectives, additional benefits accrued were: (1) a fuller understanding of Cr(VI) entrained in the vadose zone that will that can be utilized in modeling potential Cr(VI) source terms, and (2) accelerating the Columbia River 100 Area corridor cleanup by providing valuable information to develop remedial action based on a fundamental understanding of Cr(VI) vadose zone geochemistry. A series of macroscopic column experiments were conducted with contaminated and uncontaminated sediments to study Cr(VI) desorption patterns in aged and freshly contaminated sediments, evaluate the transport characteristics of dichromate liquid retrieved from old pipelines of the 100 Area; and estimate the effect of strongly reducing liquid on the reduction and transport of Cr(VI). Column experiments used the < 2 mm fraction of the sediment samples and simulated Hanford groundwater solution. Periodic stop-flow events were applied to evaluate the change in elemental concentration during time periods of no flow and greater fluid residence time. The results were fit using a two-site, one dimensional reactive transport model. Sediments were characterized for the spatial and mineralogical associations of the contamination using an array of microscale techniques such as XRD, SEM, EDS, XPS, XMP, and XANES. The following are important conclusions and implications. Results from column experiments indicated that most of contaminant Cr travels fast through the sediments and appears as Cr(VI) in the effluents. The significance of this for groundwater concentrations would, however, depend on the mass flux of recharge to the water table. adsorption of Cr(VI) to sediments from spiked Cr(VI) solution is low; calculated retardation coefficients are close to one. Calcium polysulfide solutions readily reduced Cr(VI) to Cr(III) in column experiments. However a significant amount of the Cr(VI) was mobilized ahead of the polysulfide solution front. This has significant implications for in-situ reductive remediation techniques. The experiments suggest that it would be difficult to design a remedial measure using infiltration of liquid phase reductants without increasing transport of Cr(VI) toward the water table. The microscopic characterization results are consistent with the column studies. Cr(VI) is found as ubiquitous coatings on sediment grain surfaces. Small, higher concentration, chromium sites are associated with secondary clay mineral inclusions, with occasional barium chromate minerals, and reduced to Cr(III) in association with iron oxides that are most likely magnetite primary minerals. Within the restricted access domains of sediment matrix, ferrous iron could also diffuse from in situ, high-surface-area minerals to cause the reductive immobilization of chromate. This process may be favored at microscale geochemical zones where ferrous iron could be supplied. Once nucleated, micrometer-scale precipitates are favored as growing locales for further accumulation, causing the formation of discrete zones of Cr(III)

Characterization of Vadose Zone Sediment: Slant Borehole SX-108 in the S-SX Waste Management Area

This report was revised in September 2008 to remove acid-extractable sodium data from Table 4.17. 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 the fourth 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 a slant borehole installed beneath tank SX-108 (or simply SX-108 slant borehole)

Characterization of Vadose Zone Sediment: Borehole 41-09-39 in the S-SX Waste Management Area

This report was revised in September 2008 to remove acid-extractable sodium data from Table 5.15. 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 borehole 41-09-39 installed adjacent to tank SX-109

Transformation of 1-Aminonapththalene At The Surface of Smectite Clays

One-aminonaphthalene is sorbed onto the Na-saturated smectite clays, montmorillonite and hectorite, by cation exchange. In the presence of Fe3+ either in the clay structure or on the clay surface, sorption is followed by the formation of a blue-colored complex, with the continuous disappearance of aminonaphthalene from solution and the clay surface. The rate of aminonaphthalene disappearance decreases as pH increases. With time, four major products that appear to be structural isomers of N(4- aminonaphthyl)-1-naphthylamine are produced. A simplified model of this transformation is suggested to be the oxidation by Fe3+ of sorbed aminonaphthalene forming a radical cation-clay complex. A subsequent reaction between the radical-cation and a neutral aminonaphthalene molecule takes place, with the products being strongly sorbed to the clay surface