P. Evan Dresel

Review: Technical and Policy Challenges in Deep Vadose Zone Remediation of Metals and Radionuclides

Contamination in deep vadose zone environments is isolated from exposure so direct contact is not a factor in its risk to human health and the environment. Instead, movement of contamination to the groundwater creates the potential for exposure and risk to receptors. Limiting flux from contaminated vadose zone is key for protection of groundwater resources, thus the deep vadose zone is not necessarily considered a resource requiring restoration. Contaminant discharge to the groundwater must be maintained low enough by natural attenuation (e.g., adsorption processes or radioactive decay) or through remedial actions (e.g., contaminant mass reduction or mobility reduction) to meet the groundwater concentration goals. This paper reviews the major processes for deep vadose zone metal and radionuclide remediation that form the practical constraints on remedial actions. Remediation of metal and radionuclide contamination in the deep vadose zone is complicated by heterogeneous contaminant distribution and the saturation-dependent preferential flow in heterogeneous sediments. Thus, efforts to remove contaminants have generally been unsuccessful although partial removal may reduce downward flux. Contaminant mobility may be reduced through abiotic and biotic reactions or through physical encapsulation. Hydraulic controls may limit aqueous transport. Delivering amendments to the contaminated zone and verifying performance are challenges for remediation.

Chromium transport in an acidic waste contaminated subsurface medium: the role of reduction.

A series of wet chemical extractions and column experiments, combined with electron microprobe analysis (EMPA) and X-ray photoelectron spectroscopy (XPS) measurements, were conducted to estimate the extent of Cr(VI) desorption and determine the mechanism(s) of Cr(VI) attenuation in contaminated and naturally aged (decades) Hanford sediments which were exposed to dichromate and acidic waste solutions. Results from wet extractions demonstrated that contaminated sediments contained a relatively large fraction of tightly-bound Cr. Results from column experiments showed that effluent Cr concentrations were low and only a small percentage of the total Cr inventory was removed from the sediments. EMPA inspections indicated that Cr contamination was spread throughout sediment matrix and high-concentrated Cr spots were absent. XPS analyses confirmed that most surface Cr occurred as reduced Cr(III), which was spatially associated with Fe(III). Collectively, the results from macroscopic experiments and microprobe and spectroscopic measurements demonstrated that reduction of Cr(VI) have occurred in these sediments, limiting dramatically the mass flux from this contaminated source. The most likely mechanism of Cr(VI) reduction is the acid promoted dissolution of Fe(II)-bearing soil minerals and/or their surface coatings, release of Fe(II) in the aqueous phase, abiotic homogeneous and/or heterogeneous Cr(VI) reduction by aqueous, sorbed and/or structural Fe(II), and subsequently, formation of insoluble Cr(III) phases or [Cr(III) Fe(III)] solid solutions. The results from this study will improve our fundamental understanding of Cr(VI) behavior in natural heterogeneous subsurface media and may be used as a basis for developing or selecting potential remedial measures.

Geochemical Characterization of Chromate Contamination in the 100 Area Vadose Zone at the Hanford Site - Part 2

At the Hanford Site, chromate was used throughout the 100 Areas (100-B, 100-C, 100-D/DR, 100-F, 100-H, and 100 K) as a corrosion inhibitor in reactor cooling water. Chromate was delivered in rail cars, tanker trucks, barrels, and local pipelines as dichromate granular solid or stock solution. In many occasions, chromate was inevitably discharged to surface or near-surface ground through spills during handling, pipeline leaks, or during disposal to cribs. The composition of the liquids that were discharged is not known and it is quite possible that Cr(VI) fate and transport in the contaminated sediments would be a function of the chemical composition of the waste fluids. The major objectives of this investigation which was limited in scope by the financial resources available, were to 1) determine the leaching characteristics of hexavalent chromium [Cr(VI)] from contaminated sediments collected from 100-D 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 macroscopic leaching studies, and 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 that can be used for developing options for environmental remediation. The information gathered from this research effort will help to further improve our understanding of Cr(VI) behavior in the vadose zone and will also help in accelerating the 100 Area Columbia River Corridor cleanup by providing valuable information to develop remedial action based on a fundamental understanding of Cr(VI) vadose zone geochemistry. A series of column experiments were conducted with contaminated sediments to study Cr(VI) desorption patterns. Column experiments used the field size fraction of the sediment samples and a simulated Hanford Site 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. Sediments were characterized for the spatial and mineralogical associations of the contamination using some microscale techniques such as X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Mossbauer spectroscopy.

Investigation of Isotopic Signatures for Sources of Groundwater Contamination at the Hanford Site

The Hanford Site Groundwater Monitoring Project at Pacific Northwest National Laboratory (PNNL) investigated selected isotopic signature techniques to aid interpretation of contaminant plumes in Hanford Site groundwater. The main approach was to select groundwater samples expected to exhibit a variety of contaminant characteristics and then develop inductively coupled plasma mass spectrometry (ICP-MS) analytical methods for the groundwater matrix. Initial broad scans were used to identify interferences and to focus the method development on isotopes showing the greatest promise of practical application. In addition, earlier work characterizing chlorine-36 in Hanford Site groundwater by accelerator mass spectrometry (AMS) will be discussed.

Measurement of Helium-3/Helium-4 Ratios in Soil Gas at the 618-11 Burial Ground

Seventy soil gas-sampling points were installed around the perimeter of the 618-11 Burial Ground, approximately 400 feet downgradient of well 699-13-3A, and in four transects downgradient of the burial ground to a maximum distance of 3,100 feet. Soil gas samples were collected and analyzed for helium-3/helium-4 ratios from these 70 points. Helium-3/helium-4 ratios determined from the soil gas sampling points showed significant enrichments, relative to ambient air helium-3 concentrations. The highest concentrations were located along the northern perimeter of the burial ground. Helium-3/helium-4 ratios (normalized to the abundances in ambient air) ranged from 1.0 to 62 around the burial ground. The helium-3/helium-4 ratios from the 4 transect downgradient of the burial ground ranged from 0.988 to 1.68. The helium-3/helium-4 ratios from around the burial ground suggest there is a vadose zone source of tritium along the north side of the burial ground.

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

99 Tc is a contaminant of interest at numerous nuclear facilities because it is quite mobile in sub-surface environments and is a key contributor to long-term risk. However, as a mono-isotopic fission product, 99Tc is limited in its use as a signature to differentiate between different waste disposal pathways that could have contributed to sub-surface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, their large fission yields, and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samples and water extracts of vadose zone sediments. Samples were analyzed directly on a PerkinElmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100–200 mesh hydronium-based cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng ml−1 or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. Aqueous concentrations of 96Mo and 96Zr, two potential interferents to the analysis of total ruthenium concentration, were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with mass correction to quantitatively analyze samples containing up to two orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural versus fission-product) in aqueous matrixes.

Geochemical Processes Data Package for the Vadose Zone in the Single-Shell Tank Waste Management Areas at the Hanford Site

This data package discusses the geochemistry of vadose zone sediments beneath the single-shell tank farms at the U.S. Department of Energy’s (DOE’s) Hanford Site. The purpose of the report is to provide a review of the most recent and relevant geochemical process information available for the vadose zone beneath the single-shell tank farms and the Integrated Disposal Facility. Two companion reports to this one were recently published which discuss the geology of the farms (Reidel and Chamness 2007) and groundwater flow and contamination beneath the farms (Horton 2007).

Remediation of Deep Vadose Zone Radionuclide and Metal Contamination: Status and Issues

This report documents the results of a PNNL literature review to report on the state of maturity of deep vadose zone remediation technologies for metal contaminants including some radionuclides. Its recommendations feed into decisionmakers need for scientific information and cost-effective in situ remediation technlogies needed under DOEs Environmental Management initiative Enhanced Remediation Methods: Scientific & Technical Basis for In Stu Treatment Systems for Metals and Radionuclides.

Measurement of Tritium in Gas Phase Soil Moisture and Helium-3 in Soil Gas at the Hanford Townsite and 100 K Area

In 1999, soil gas samples for helium-3 measurements were collected at two locations on the Hanford Site. Eight soil gas sampling points ranging in depth from 1.5 to 9.8 m (4.9 to 32 ft) below ground surface (bgs) in two clusters were installed adjacent to well 699-41-1, south of the Hanford Townsite. Fifteen soil gas sampling points, ranging in depth from 2.1 to 3.2 m (7 to 10.4 ft) bgs, were installed to the north and east of the 100 KE Reactor. Gas phase soil moisture samples were collected using silica gel traps from all eight sampling locations adjacent to well 699-41-1 and eight locations at the 100 K Area. No detectable tritium (<240 pCi/L) was found in the soil moisture samples from either the Hanford Townsite or 100 K Area sampling points. This suggests that tritiated moisture from groundwater is not migrating upward to the sampling points and there are no large vadose zone sources of tritium at either location. Helium-3 analyses of the soil gas samples showed significant enrichments relative to ambient air helium-3 concentrations with a depth dependence consistent with a groundwater source from decay of tritium. Helium-3/helium-4 ratios (normalized to the abundances in ambient air) at the Hanford Townsite ranged from 1.012 at 1.5 m (5 ft) bgs to 2.157 at 9.8 m (32 ft) bgs. Helium-3/helium-4 ratios at the 100 K Area ranged from 0.972 to 1.131. Based on results from the 100 K Area, the authors believe that a major tritium plume does not lie within that study area. The data also suggest there may be a tritium groundwater plume or a source of helium-3 to the southeast of the study area. They recommend that the study be continued by placing additional soil gas sampling points along the perimeter road to the west and to the south of the initial study area.

Evaluation of Elevated Tritium Levels in Groundwater Downgradient from the 618-11 Burial Ground Phase I Investigations

This report describes the results of the preliminary investigation of elevated tritium in groundwater discovered near the 618-11 burial ground, located in the eastern part of the Hanford Site.