Donaldo P. Mendoza

Demonstration of combined zero-valent iron and electrical resistance heating for in situ trichloroethene remediation.

The effectiveness of in situ treatment using zero-valent iron (ZVI) for nonaqueous phase or significant sediment-associated contaminant mass can be limited by relatively low rates of mass transfer to bring contaminants in contact with the reactive media. For a field test in a trichloroethene (TCE) source area, combining moderate-temperature subsurface electrical resistance heating with in situ ZVI treatment was shown to accelerate TCE treatment by a factor of about 4 based on organic daughter products and a factor about 8 based on chloride concentrations. A mass-discharge-based analysis was used to evaluate reaction, dissolution, and volatilization processes at ambient groundwater temperature (~10 °C) and as temperature was increased up to about 50 °C. Increased reaction and contaminant dissolution were observed with increased temperature, but vapor- or aqueous-phase migration of TCE out of the treatment zone was minimal during the test because reactions maintained low aqueous-phase TCE concentrations.

Development of an Electronic Seepage Chamber for Extended Use in a River

Seepage chambers have been used to characterize the flux of water across the water-sediment interface in a variety of settings. In this work, an electronic seepage chamber was developed specifically for long-term use in a large river where hydraulic gradient reversals occur frequently with river-stage variations. A bidirectional electronic flowmeter coupled with a seepage chamber was used to measure temporal changes in the magnitude and direction of water flux across the water-sediment interface over an 8-week period. The specific discharge measured from the seepage chamber compared favorably with measurements of vertical hydraulic gradient and previous specific discharge calculations. This, as well as other supporting data, demonstrates the effectiveness of the electronic seepage chamber to accurately quantify water flux in two directions over a multimonth period in this setting. The ability to conduct multimonth measurements of water flux at a subhourly frequency in a river system is a critical capability for a seepage chamber in a system where hydraulic gradients change on a daily and seasonal basis.

300 Area Uranium Stabilization Through Polyphosphate Injection: Final Report

The objective of the treatability test was to evaluate the efficacy of using polyphosphate injections to treat uranium-contaminated groundwater in situ. A test site consisting of an injection well and 15 monitoring wells was installed in the 300 Area near the process trenches that had previously received uranium-bearing effluents. This report summarizes the work on the polyphosphate injection project, including bench-scale laboratory studies, a field injection test, and the subsequent analysis and interpretation of the results. Previous laboratory tests have demonstrated that when a soluble form of polyphosphate is injected into uranium-bearing saturated porous media, immobilization of uranium occurs due to formation of an insoluble uranyl phosphate, autunite [Ca(UO2)2(PO4)2•nH2O]. These tests were conducted at conditions expected for the aquifer and used Hanford soils and groundwater containing very low concentrations of uranium (10-6 M). Because autunite sequesters uranium in the oxidized form U(VI) rather than forcing reduction to U(IV), the possibility of re-oxidation and subsequent re-mobilization is negated. Extensive testing demonstrated the very low solubility and slow dissolution kinetics of autunite. In addition to autunite, excess phosphorous may result in apatite mineral formation, which provides a long-term source of treatment capacity. Phosphate arrival response data indicate that, under site conditions, the polyphosphate amendment could be effectively distributed over a relatively large lateral extent, with wells located at a radial distance of 23 m (75 ft) reaching from between 40% and 60% of the injection concentration. Given these phosphate transport characteristics, direct treatment of uranium through the formation of uranyl-phosphate mineral phases (i.e., autunite) could likely be effectively implemented at full field scale. However, formation of calcium-phosphate mineral phases using the selected three-phase approach was problematic. Although amendment arrival response data indicate some degree of overlap between the reactive species and thus potential for the formation of calcium-phosphate mineral phases (i.e., apatite formation), the efficiency of this treatment approach was relatively poor. In general, uranium performance monitoring results support the hypothesis that limited long-term treatment capacity (i.e., apatite formation) was established during the injection test. Two separate overarching issues affect the efficacy of apatite remediation for uranium sequestration within the 300 Area: 1) the efficacy of apatite for sequestering uranium under the present geochemical and hydrodynamic conditions, and 2) the formation and emplacement of apatite via polyphosphate technology. In addition, the long-term stability of uranium sequestered via apatite is dependent on the chemical speciation of uranium, surface speciation of apatite, and the mechanism of retention, which is highly susceptible to dynamic geochemical conditions. It was expected that uranium sequestration in the presence of hydroxyapatite would occur by sorption and/or surface complexation until all surface sites have been depleted, but that the high carbonate concentrations in the 300 Area would act to inhibit the transformation of sorbed uranium to chernikovite and/or autunite. Adsorption of uranium by apatite was never considered a viable approach for in situ uranium sequestration in and of itself, because by definition, this is a reversible reaction. The efficacy of uranium sequestration by apatite assumes that the adsorbed uranium would subsequently convert to autunite, or other stable uranium phases. Because this appears to not be the case in the 300 Area aquifer, even in locations near the river, apatite may have limited efficacy for the retention and long-term immobilization of uranium at the 300 Area site..

Interim Report: 100-NR-2 Apatite Treatability Test: Low Concentration Calcium Citrate-Phosphate Solution Injection for In Situ Strontium-90 Immobilization

Following an evaluation of potential Sr-90 treatment technologies and their applicability under 100-NR-2 hydrogeologic conditions, U.S. Department of Energy, Fluor Hanford, Inc., Pacific Northwest National Laboratory, and the Washington Department of Ecology agreed that the long-term strategy for groundwater remediation at 100-N Area will include apatite sequestration as the primary treatment, followed by a secondary treatment if necessary (most likely phytoremediation). Since then, the agencies have worked together to agree on which apatite sequestration technology has the greatest chance of reducing Sr-90 flux to the river at a reasonable cost. In July 2005, aqueous injection, (i.e., the introduction of apatite-forming chemicals into the subsurface) was endorsed as the interim remedy and selected for field testing. Studies are in progress to assess the efficacy of in situ apatite formation by aqueous solution injection to address both the vadose zone and the shallow aquifer along the 300 ft of shoreline where Sr-90 concentrations are highest. This report describes the field testing of the shallow aquifer treatment.

Results of Performance Evaluation Testing of Electrical Leak-Detection Methods at the Hanford Mock Tank Site--FY 2002-2003

Application of two electrical resistivity methods at the Hanford Site Mock Tank during 2002, indicate the viability of the methods as possible leak-detection tools for SST retrieval operations. Electrical Resistivity Tomography and High-Resolution Resistivity were used over a 109-day period to detect leakage of a waste simulant beneath the tank. The results of the test indicate that both of these two methods, and subset methods may be applicable to SST leak detection.

Noble gas migration experiment to support the detection of underground nuclear explosions

A Noble Gas Migration Experiment injected 127Xe, 37Ar, and sulfur hexafluoride into a former underground nuclear explosion shot cavity. These tracer gases were allowed to migrate from the cavity to near-surface and surface sampling locations and were detected in soil gas samples collected using various on-site inspection sampling approaches. Based on this experiment we came to the following conclusions: (1) SF6 was enriched in all of the samples relative to both 37Ar and 127Xe. (2) There were no significant differences in the 127Xe to 37Ar ratio in the samples relative to the ratio injected into the cavity. (3) The migratory behavior of the chemical and radiotracers did not fit typical diffusion modeling scenarios.

Treatability Test Plan for 300 Area Uranium Stabilization through Polyphosphate Injection

The U.S. Department of Energy has initiated a study into possible options for stabilizing uranium at the 300 Area using polyphosphate injection. As part of this effort, PNNL will perform bench- and field-scale treatability testing designed to evaluate the efficacy of using polyphosphate injections to reduced uranium concentrations in the groundwater to meet drinking water standards (30 ug/L) in situ. This technology works by forming phosphate minerals (autunite and apatite) in the aquifer that directly sequester the existing aqueous uranium in autunite minerals and precipitates apatite minerals for sorption and long term treatment of uranium migrating into the treatment zone, thus reducing current and future aqueous uranium concentrations. Polyphosphate injection was selected for testing based on technology screening as part of the 300-FF-5 Phase III Feasibility Study for treatment of uranium in the 300-Area.

Methods for Assessing the Relative Amounts of Groundwater Discharge into the Columbia River and Measurement of Columbia River Gradients at the Hanford Site’s 300 Area

This report summarizes FY08 activities conducted under the Remediation and Closure Sciences Project.

Investigation of the Strontium-90 Contaminant Plume along the Shoreline of the Columbia River at the 100-N Area of the Hanford Site

Efforts are underway to remediate strontium-laden groundwater to the Columbia River at the 100-N Area of the Hanford Site. Past practices of the 100-N reactor liquid waste disposal sites has left strontium-90 sorbed onto sediments which is a continuing source of contaminant discharge to the river. The Remediation Task of the Science and Technology Project assessed the interaction of groundwater and river water at the hyporheic zone. Limited data have been obtained at this interface of contaminant concentrations, geology, groundwater chemistry, affects of river stage and other variables that may affect strontium-90 release. Efforts were also undertaken to determine the extent, both laterally and horizontally, of the strontium-90 plume along the shoreline and to potentially find an alternative constituent to monitor strontium-90 that would be more cost effective and could possibly be done under real time conditions. A baseline of strontium-90 concentrations along the shoreline was developed to help assess remediation technologies.

Hanford 100-D Area Biostimulation Treatability Test Results

Pacific Northwest National Laboratory conducted a treatability test designed to demonstrate that in situ biostimulation can be applied to help meet cleanup goals in the Hanford Site 100-D Area. In situ biostimulation has been extensively researched and applied for aquifer remediation over the last 20 years for various contaminants. In situ biostimulation, in the context of this project, is the process of amending an aquifer with a substrate that induces growth and/or activity of indigenous bacteria for the purpose of inducing a desired reaction. For application at the 100-D Area, the purpose of biostimulation is to induce reduction of chromate, nitrate, and oxygen to remove these compounds from the groundwater. The in situ biostimulation technology is intended to provide supplemental treatment upgradient of the In Situ Redox Manipulation (ISRM) barrier previously installed in the Hanford 100-D Area and thereby increase the longevity of the ISRM barrier. Substrates for the treatability test were selected to provide information about two general approaches for establishing and maintaining an in situ permeable reactive barrier based on biological reactions, i.e., a biobarrier. These approaches included 1) use of a soluble (miscible) substrate that is relatively easy to distribute over a large areal extent, is inexpensive, and is expected to have moderate longevity; and 2) use of an immiscible substrate that can be distributed over a reasonable areal extent at a moderate cost and is expected to have increased longevity.