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At least 91 records · Page 5

Annual Closure Monitoring Report for Corrective Action Unit 98, Frenchman Flat, Underground Test Area, Nevada National Security Site, Nevada: (CY2017 January 2017–December 2017, Rev. 0)

Corrective Action Unit (CAU) 98: Frenchman Flat on the Nevada National Security Site was the location of 10 underground nuclear tests. CAU 98 underwent a series of investigations and actions in accordance with the Federal Facility Agreement and Consent Order to assess contamination of groundwater by radionuclides from the tests. A Closure Report completed that process in 2016 and called for long-term monitoring, use restrictions (URs), and institutional controls to protect the public and environment from potential exposure to contaminated groundwater. Three types of monitoring are performed for CAU 98: water quality, water level, and institutional control. These are monitored to determine whether the URs remain protective of human health and the environment, and to ensure that the regulatory boundary objectives are being met. Monitoring data will be used in the future, once multiple years of data are available, to evaluate consistency with the groundwater flow and contaminant transport models because the contaminant boundaries calculated with the models are the primary basis of the UR boundaries. Six wells were sampled for water-quality monitoring in 2017. Contaminants of concern were detected only in the two source/plume wells already known to contain contamination as a result of a radionuclide migration experiment. The 86,000-picocuries-per-liter (pCi/L) tritium concentration in one of the wells is about 12 percent higher than measured in 2016 but is over an order of magnitude less than the peak value measured in the well in 1980. The concentration in the other source/plume well is lower than measured in 2016. The water-level monitoring network includes 16 wells. Depth to water measured in 2017 is generally consistent with recent measurements for most wells. Water-level declines differing from long-term trends were observed in four wells. Three of these (WW-4, WW-4A, and WW-5B) are water-supply wells that experienced increases in pumping during the year. No definitive cause for the sharp decline in the fourth well (ER-5-3-2) in 2016 is known as yet. Institutional control monitoring confirmed the URs are recorded in U.S. Department of Energy and U.S. Air Force land management systems, and that no activities within Frenchman Flat basin are occurring that could potentially affect the contaminant boundaries. Survey of groundwater resources in basins surrounding Frenchman Flat similarly identify no current or pending development that would indicate the need to increase monitoring activities or would otherwise cause concern for the closure decision. The URs continue to prevent exposure of the public, workers, and the environment to contaminants of concern by preventing use of potentially contaminated groundwater.

54 ENVIRONMENTAL SCIENCES↗

Post-Closure Monitoring Report for Corrective Action Unit 98, Frenchman Flat, Underground Test Area, Nevada National Security Site, Nevada for Calendar Year 2016 (January 2016–December 2016), Revision 1

Corrective Action Unit (CAU) 98: Frenchman Flat on the Nevada National Security Site was the location of 10 underground nuclear tests. CAU 98 underwent a series of investigations and actions in accordance with the Federal Facility Agreement and Consent Order to assess contamination of groundwater by radionuclides from the tests. A Closure Report completed that process in 2016 and called for long-term monitoring, use restrictions (URs), and institutional controls to protect the public and environment from potential exposure to contaminated groundwater. Three types of monitoring are performed for CAU 98: water quality, water level, and institutional control. These are monitored to determine whether the UR boundaries remain protective of human health and the environment, and to ensure that the regulatory boundary objectives are being met. Monitoring data will be used in the future, once multiple years of data are available, to evaluate consistency with the groundwater flow and contaminant transport models because the contaminant boundaries calculated with the models are the primary basis of the UR boundaries. Six wells were sampled for water-quality monitoring in 2016. Contaminants of concern were detected only in the two source/plume wells already known to contain contamination as a result of a radionuclide migration experiment. The tritium concentration in both wells is slowly decreasing. The water-level monitoring network includes 16 wells. Depth to water measured in 2016 in all wells is consistent with recent measurements. Institutional control monitoring confirmed the URs are recorded in U.S. Department of Energy and U.S. Air Force land management systems, and that no activities within Frenchman Flat basin are occurring that could potentially affect the contaminant boundaries. Survey of groundwater resources in basins surrounding Frenchman Flat similarly identify no current or pending development that would indicate the need to increase monitoring activities or would otherwise cause concern for the closure decision. The URs continue to prevent exposure of the public, workers, and the environment to contaminants of concern by preventing use of potentially contaminated groundwater.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

CY2018 Annual Closure Monitoring Report for Corrective Action Unit 98, Frenchman Flat, Underground Test Area, Nevada National Security Site, Nevada (January 2018–December 2018, Revision 1)

Corrective Action Unit (CAU) 98: Frenchman Flat on the Nevada National Security Site was the location of 10 underground nuclear tests. CAU 98 underwent a series of investigations and actions in accordance with the Federal Facility Agreement and Consent Order to assess contamination of groundwater by radionuclides from the tests. A Closure Report completed that process in 2016 and called for long-term monitoring, use restrictions (URs), and institutional controls to protect the public and environment from potential exposure to contaminated groundwater. Three types of monitoring are performed for CAU 98: water quality, water level, and institutional control. These are monitored to determine whether the URs remain protective of human health and the environment, and to ensure that the regulatory boundary objectives are being met. Monitoring data will be used in the future, once multiple years of data are available, to evaluate consistency with the groundwater flow and contaminant transport models because the contaminant boundaries calculated with the models are the primary basis of the UR boundaries. Six wells were sampled for water-quality monitoring in 2018. Contaminants of concern were detected only in the two source/plume wells already known to contain contamination as a result of a radionuclide migration experiment. Tritium concentrations in both of these wells, RNM-2S and UE-5n, remain above the Safe Drinking Water Act maximum contaminant level of 20,000 picocuries per liter but declined in 2018 as compared to measurements in 2017. All other contaminants of concern are below the minimum detection level plus analytical error. The water-level monitoring network includes 16 wells. Depth to water measured in 2018 is generally consistent with recent measurements for all wells. Many wells continue to exhibit a long-term downward trend in water level, despite small increases in measured water levels in 2018. The sharp 2016 decline in water level in Well ER-5-3-2 remains unexplained, with the lower level persisting through 2018. Rising water-level trends continue to be observed in two relatively deep wells (ER-5-3 deep piezometer and ER-5-4-2), and also in former supply Well WW-5A. The current supply wells exhibit relatively erratic water levels associated with pumping activities. Institutional control monitoring confirmed the URs are recorded in U.S. Department of Energy and U.S. Air Force land management systems, and that no activities within Frenchman Flat basin are occurring that could potentially affect the contaminant boundaries. Survey of groundwater resources in basins surrounding Frenchman Flat similarly identify no current or pending development that would indicate the need to increase monitoring activities or would otherwise cause concern for the closure decision. The URs continue to prevent exposure of the public, workers, and the environment to contaminants of concern by preventing use of potentially contaminated groundwater.

54 ENVIRONMENTAL SCIENCES↗

A Critical Review of the Impacts of Leaking CO 2 Gas and Brine on Groundwater Quality

Geological carbon sequestration (GCS) is a global carbon emission reduction strategy involving the capture of CO 2 emitted from fossil fuel burning power plants, as well as the subsequent injection of the captured CO 2 gas into deep saline aquifers or depleted oil and gas reservoirs. A critical question that arises from the proposed GCS is the potential impacts of CO 2 injection on the quality of drinking-water systems overlying CO 2 sequestration storage sites. Although storage reservoirs are evaluated and selected based on their ability to safely and securely store emplaced fluids, leakage of CO 2 from storage reservoirs is a primary risk factor and potential barrier to the widespread acceptance of geologic CO 2 sequestration (OR Harvey et al. 2013; Y-S Jun et al. 2013; DOE 2007). Therefore, a systematic understanding of how CO 2 leakage would affect the geochemistry of potable aquifers, and subsequently control or affect elemental and contaminant release via sequential and/or simultaneous abiotic and biotic processes and reactions is vital.

54 ENVIRONMENTAL SCIENCES↗

Improving Long-term Monitoring of Contaminated Groundwater at Sites where Attenuation-based Remedies are Deployed

This study presents an effective approach to tackle the challenge of long-term monitoring of contaminated groundwater sites where remediation leaves residual contamination in the subsurface. Traditional long-term monitoring of contaminated groundwater sites focuses on measuring contaminant concentrations and is applicable to sites where contaminant mass is removed or degraded to a level below the regulatory standard. The traditional approach is less effective at sites where risk from metals or radionuclides continues to exist in the subsurface after remedial goals are achieved. We propose a long-term monitoring strategy for this type of waste site that focuses on measuring the hydrological and geochemical parameters that control attenuation or remobilization of contaminants while de-emphasizing contaminant-concentration measurements. Furthermore, we demonstrate how this approach would be more effective than traditional long-term monitoring, using a site in South Carolina, USA, where groundwater is contaminated by several radionuclides. A comprehensive enhanced attenuation remedy has been implemented at the site to minimize discharge of contamination to surface water. The immobilization of contaminants occurs in three locations by manipulation of hydrological and geochemical parameters, as well as by natural attenuation processes. Deployment of our proposed long-term monitoring strategy will combine subsurface and surface measurements using spectroscopic tools, geophysical tools, and sensors to monitor the parameters controlling contaminant attenuation. The advantage of this approach is that it will detect the potential for contaminant remobilization from engineered and natural attenuation zones, allowing potential adverse changes to be mitigated before contaminant attenuation is reversed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electrochemical Property Determination of Fission Product Elements in Molten Fluoride Salt

The fluoride salt-cooled high temperature reactor (FHR) is a developing nuclear reactor concept that combines many attractive features of previous reactor designs. The FHR concept is also a technological bridge between today's light water reactors (LWRs) which use solid fuel and water coolant, to future technologies that utilize liquid salt coolant and dissolved liquid fuel. The FHR concept incorporates low-pressure liquid fluoride salt, tri-structural isotropic (TRISO) coated particle fuel, and an entirely passive decay heat removal system. FHRs operating at very high temperatures increase the thermal energy transfer and subsequently thermal efficiency. Similar to LWRs, the FHR will feature a cleanup system that performs online processing of the primary coolant in order to mitigate contamination from leaking fuel and moisture. Due to its ionic liquid properties, molten salts can be controlled with various applications of electrochemical properties. Oak Ridge National Laboratory (ORNL) studied these applications greatly during the Molten Salt Reactor Experiment (MSRE) and the Molten Salt Breeder Reactor (MSBR) concept during the 1960's and 70's; however, many technology gaps exist in terms of online salt processing for the FHR. The purpose of this research is to identify the electrochemical properties of leaking fission products as well as contamination from moisture in the system. These properties have been thoroughly studied for molten chloride salts but not as much data is reported for behavior in fluoride salts. Before a cleanup system can be proposed for the FHR concept, these properties will need to be extensively investigated to generate a reliable source of electrochemical data. These results are gathered through an electrochemical system which probes the molten salt at high temperatures (up to 750 deg. C). (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Integrated systems-based approach to monitoring environmental remediation

The U.S. Department of Energy is responsible for risk reduction and cleanup of its nuclear weapons complex. Remediation strategies for some of the contamination may include techniques that mitigate risk, but leave contaminants in place. Monitoring to verify remedy performance and long-term mitigation of risk is key to implementing these strategies and can be a large portion of the total cost of remedy implementation. Especially in these situations, there is a need for innovative monitoring approaches that move away from the cost- and labor-intensive point-source monitoring. In this paper, alternative approaches for monitoring are presented for vadose zone, groundwater, groundwater/surface water interface, and surface water. To illustrate integrated, systems-based monitoring, this paper focuses on vadose zone contaminant remediation to mitigate impact to groundwater. In this context, vadose zone contamination is a source, or potential source, to groundwater plumes. The monitoring design uses a systems-based approach focused on developing a conceptual site model that highlights key features that control contaminant flux to groundwater. These features are derived considering the unsaturated flow and contaminant transport processes in the vadose zone and the nature of the waste discharge. Diagnostic properties and/or parameters related to both short- and long-term contaminant flux to groundwater can be identified and targeted for monitoring. The resolution of monitoring data needed to correspond to a functionally useful indicator of flux to groundwater can be estimated using quantitative analyses and the associated unsaturated flow properties relevant to the targeted site and vadose zone features. This monitoring design approach follows the process of developing a quantitative conceptual model suitable for supporting projections of future flux to groundwater. Support for such projections is important because it is likely that, in many cases, remediation decisions for the vadose zone will need to be made based all or in part on projected impacts to groundwater, and monitoring will then be applied to verify that remedy goals are being met. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Implementation of atomic layer etching of silicon: Scaling parameters, feasibility, and profile control

Atomic or layer by layer etching of silicon exploits temporally segregated self-limiting adsorption and material removal steps to mitigate the problems associated with continuous or quasicontinuous (pulsed) plasma processes: selectivity loss, damage, and profile control. Successful implementation of atomic layer etching requires careful choice of the plasma parameters for adsorption and desorption steps. This paper illustrates how process parameters can be arrived at through basic scaling exercises, modeling and simulation, and fundamental experimental tests of their predictions. Using chlorine and argon plasma in a radial line slot antenna plasma source as a platform, the authors illustrate how cycle time, ion energy, and radical to ion ratio can be manipulated to manage the deviation from ideality when cycle times are shortened or purges are incomplete. Cell based Monte Carlo feature scale modeling is used to illustrate profile outcomes. Experimental results of atomic layer etching processes are illustrated on silicon line and space structures such that iso-dense bias and aspect ratio dependent free profiles are produced. Experimental results also illustrate the profile control margin as processes move from atomic layer to multilayer by layer etching. The consequence of not controlling contamination (e.g., oxygen) is shown to result in deposition and roughness generation.

42 ENGINEERING↗

Subsurface Biogeochemical Research: Watershed System Science for Energy

The Subsurface Biogeochemical Research (SBR) program within the U.S. Department of Energy’s (DOE) Office of Biological and Environmental Research is strategically aligned with DOE’s mission to ensure U.S. security and prosperity through watershed system science. Water resources critical for energy production are under pressure from growing water demand, contamination, drought, flooding, and saltwater intrusion. Sustainable management of watershed systems and their coupling with the built environment rely on understanding the hydrological and biogeochemical processes that control watershed system dynamics and water availability and quality. Next-generation science-based models of watershed systems are needed to address many U.S. energy and environmental challenges, including contaminant cleanup, clean water availability, safe storage of energy and nuclear byproducts in the subsurface, nutrient availability for sustainable biofuel crops, and recovery of subsurface energy resources.

09 BIOMASS FUELS↗

Hydrogeological and multi-isotopic approach to define nitrate pollution and denitrification processes in a coastal aquifer (Sardinia, Italy)

Agricultural coastal areas are frequently affected by the superimposition of various processes, with a combination of anthropogenic and natural sources, which degrade groundwater quality. In the coastal multi-aquifer system of Arborea (Italy)—a reclaimed morass area identified as a nitrate vulnerable zone, according to Nitrate Directive 91/676/EEC—intensive agricultural and livestock activities contribute to substantial nitrate contamination. For this reason, the area can be considered a bench test for tuning an appropriate methodology aiming to trace the nitrate contamination in different conditions. An approach combining environmental isotopes, water quality and hydrogeological indicators was therefore used to understand the origins and attenuation mechanisms of nitrate pollution and to define the relationship between contaminant and groundwater flow dynamics through the multi-aquifer characterized by sandy (SHU), alluvial (AHU), and volcanic hydrogeological (VHU) units. Various groundwater chemical pathways were consistent with both different nitrogen sources and groundwater dynamics. Isotope composition suggests a mixed source for nitrate (organic and synthetic fertilizer), especially for the AHU and SHU groundwater. Moreover, marked heterotrophic denitrification and sulfate reduction processes were detected; although, for the contamination related to synthetic fertilizer, the attenuation was inefficient at removing NO{sub 3}{sup −} to less than the human consumption threshold of 50 mg/L. Various factors contributed to control the distribution of the redox processes, such as the availability of carbon sources (organic fertilizer and the presence of lagoon-deposited aquitards), well depth, and groundwater flow paths. The characterization of these processes supports water-resource management plans, future actions, and regulations, particularly in nitrate vulnerable zones.

54 ENVIRONMENTAL SCIENCES↗

Solubility controls on plutonium and americium release in subsurface environments exposed to acidic processing wastes

To identify the role of waste composition and sediment interactions in controlling Pu and Am mobility in contaminated sediments at Hanford, a legacy nuclear site, Pu and Am concentrations in solutions equilibrated with contaminated sediments from beneath the 216-Z-9 (Z-9) Trench were compared to the solubilities of PuO 2 materials, synthesized by methods representative of the disposed wastes, in the absence of sediments. Furthermore, this work shows that the solubilities of PuO 2 materials synthesized by different methods, and with varying particle sizes, agree with PuO 2 (am,hyd), although dissolution kinetics differed between materials. According to saturation index (SI) calculations, PuO 2 (am,hyd) is likely also controlling Pu release from sediments under conditions where phosphate concentrations are low. However, both Pu-phosphate and Am-phosphate phases, identified in SI calculations and by high resolution transmission electron microscopy, play roles in controlling release in low pH, high phosphate, shallow sediments just below the Z-9 Trench. The elevated phosphate is likely due to decomposition of tributyl phosphate from waste solutions over time. Sediments from deeper in the subsurface beneath the Z-9 Trench are less acidic and contain less phosphate, with Pu solubility likely controlled by PuO 2 (am,hyd) that precipitated following neutralization of the acidic waste stream. Controls on Am concentrations in deeper sediments are more complex and potentially involve sediment adsorption and/or release from Pu (1-x) Am x O 2 following Am in-growth. The concentrations of both Pu and Am were elevated in the colloidal fraction associated with shallow sediments, but not in PuO 2 experiments, suggesting the presence of Pu/Am pseudocolloids (e.g., Pu/Am associated with mineral colloids). However, Pu and Am association with the colloidal size fraction was not observed in deeper sediments, suggesting transport of Pu and Am to these depths beneath the Z-9 Trench was not due to colloidal transport.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Federal Facility Agreement and Consent Order: Nevada National Security Site Use Restriction Management Plan with ROTC 1

This Use Restriction Management Plan (URMP) provides the information needed to create, modify, and manage use restrictions (URs) for sites on the Nevada National Security Site (NNSS), and sites accessed through the NNSS main gate, that were closed using the corrective action alternative (CAA) of closure in place under the Federal Facility Agreement and Consent Order (FFACO) (1996, as amended). (Note: This pertains to those FFACO sites not managed by the U.S. Department of Energy [DOE], Legacy Management.) The closure in place alternative is used for sites closed with residual contamination at levels requiring corrective action as determined using the FFACO process. The URs contain and control all requirements for long-term monitoring. This URMP also serves as the single repository of the URs implemented under the FFACO that identify use restricted areas and contain the current requirements for inspections, maintenance, and monitoring of the UR. The requirements in these URs replace all requirements listed in previous documentation. This consolidates post-closure monitoring requirements into a single source that ensures completeness and consistency of UR requirements and information. Standardized UR forms were developed to clearly document post-closure requirements that are consistent with current protocols and to ensure consistent information is contained in the URs. Standard notification, summary, and site controls statements were developed for all URs with provisions to insert site-specific options in the text. Current protocols for Industrial Sites and Soils URs are defined in this document and in the Soils Risk-Based Corrective Action (RBCA) Evaluation Process (DOE/EMNV, 2018). The standardized UR forms that have been approved to date are listed in Appendix A. Additional UR forms will be added once the review and approval process has been completed.

54 ENVIRONMENTAL SCIENCES↗

Non Accountable Sealed Radioactive Sources

Presentation describes investigation into defective 10 uCi Cs-137 "button" sources and response to potential contamination, to include radiological control measures, notifications, and awareness reports. Effort involves benchmarking of EFCOG member processes for use and handling of non-accountable sources.

61 RADIATION PROTECTION AND DOSIMETRY↗

Molten Salt Sampling Techniques and Analytical Approaches

Recent global interest in pyroprocessing and molten salt reactors has brought salt sampling methods and techniques back to the forefront of nuclear safeguards concerns. Issues with uranium supplies have also encouraged various countries to pursue advanced nuclear fuel cycles. Tracking nuclear material in molten salt has proven to be a challenge and updating molten salt sampling will greatly help in this endeavor. Molten salt is problematic to sample due to salt stratification, lack of homogeneity, solids, and difficulty with hot cell adaptations. Various salt sampling techniques have been used since before the 1960s including surface, spoon/spatula, and bar solidification. Since then, new types of sampling techniques have been developed to improve sampling results. These include rod/dip, pipet, suction, filtered sampling along with devices such as the Valve Core Sampler and the Multi-Level Sampler. These different approaches are being analyzed and improved upon along with developing requirements for an improved salt sampling device. Work continues to develop salt samplers that are more robust, easier to segment, collect at a specific depth, can work with filters, and can collect fines. Sampling parameters are also being narrowed in terms of stirring, settling time, filtration, depth, etc. In the future, we hope to address deficiencies for process control and nuclear material accountancy control by determining the best way to collect samples that minimizes contaminants and is representative. A compilation of salt sampling approaches, analyses techniques, and an evaluation of findings will be presented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Persistence of uranium groundwater plumes: Contrasting mechanisms at two DOE sites in the groundwater-river interaction zone

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and that are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 µg/L or 0.126 µmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (< one pore volume). At the Rifle site, slow oxidation of naturally reduced, contaminant U(IV) in the saturated zone and a continuous influx of U(VI) from natural, up-gradient sources influences plume persistence. Rate-limited mass transfer and surface complexation also control U(VI) migration velocity in the sub-oxic Rifle groundwater. Flux of U(VI) from the vadose zone at the Rifle site may be locally important, but it is not the dominant process that sustains the plume. A wide range in microbiologic functional diversity exists at both sites. Strains of Geobacter and other metal reducing bacteria are present at low natural abundance that are capable of enzymatic U(VI) reduction in localized zones of accumulated detrital organic carbon or after organic carbon amendment. Major differences between the sites include the geochemical nature of residual, contaminant U; the rates of current kinetic processes (both biotic and abiotic) influencing U(VI) solid-liquid distribution; the presence of detrital organic matter and the resulting spatial heterogeneity in microbially-driven redox properties; and the magnitude of groundwater hydrologic dynamics controlled by river-stage fluctuations, geologic structures, and aquifer hydraulic properties. The comparative analysis of these sites provides important guidance to the characterization, understanding, modeling, and remediation of groundwater contaminant plumes influenced by surface water interaction that are common world-wide.

Environmental Molecular Sciences Laboratory↗

On silica's roles in controlling americium migration in contaminated sediments

Two studies in the early 1980s described the leaching behavior of americium (Am) disposed as part of acidic high-salt processing wastes from the Hanford Site’s Plutonium Finishing Plant to nearby ground sediments. Here these batch leach experiments showed that the Am concentrations followed a linear log [Am] versus pH relationship with a slope of –1. Column leach experiments in the second study, however, did not follow this relationship and only ~30% of the americium desorbed even after extensive column leaching. Here, the 1980s research is re-examined along with previously unpublished information and, in light of recent published work, a plausible mechanism is proposed to explain these phenomena. Amorphous silica in the contaminated sediments is postulated to be the substrate responsible for both the exchangeable Am available for leaching and the retained low-leachable Am made evident in the column leach experiments. The exchangeable Am 3+ in the contaminated sediment leach experiments behaves with pH dependence similar to that observed for uptake onto amorphous silica of sodium (Na + ), calcium (Ca 2+ ), barium (Ba 2+ ), cadmium (Cd 2+ ), uranyl (UO 2 2+ ), ferric (Fe 3+ ), chromic (Cr 3+ ), cupric (Cu 2+ ), plumbous (Pb 2+ ), uranium(IV) (U 4+ ), plutonium(IV) (Pu 4+ ), zirconium (Zr 4+ ), analogue lanthanide (gadolinium, Gd 3+ , europium, Eu 3+ , and lutetium, Lu 3+ ) and curium (Cm 3+ ) ions as well as other studies with Am 3+ . Correspondingly, the residual low-leachable Am 3+ revealed in the column leach experiments is attributed to incorporation of Am 3+ within amorphous silica by dynamic Am 3+ sorption and silica precipitation processes.

58 GEOSCIENCES↗

Colloidal metal transport in soils developing on historic coal mine spoil

Chemical weathering of pyrite via oxidative dissolution is well-known for generating Fe(III)-bearing colloids at acid mine drainage (AMD) sites; however, the potential for physical weathering of pyrite-bearing materials and subsequent release and transport of colloidal pyrite and associated trace metals has not been studied. Here, we monitored the colloidal metal transport in soil developing on abandoned coal mine spoil with a history of AMD generation to systematically study the contribution of colloids to base and trace metal transport and determine the elemental and mineralogical composition of colloids. Additionally, we collected soil pore water using lysimeters with a pore size of approximately 1.3 μm and centrifugation was used to separate the colloids from aqueous fractions. Metal concentrations of Na, Ca, Mg, K, Si, Al, Mn, Fe, Cu, and Zn were analyzed. Our results show only 14% of the total Al and Cu were present in colloidal fractions whereas 23%, 43%, and 54% of Fe, Mn, and Zn were transported in the colloidal phase, respectively. In contrast, all base metals were primarily present in the aqueous concentration with a small fraction (<10%) present in the colloidal phase. The colloidal fractions of the base metals were inferred to be associated with the concentration of clay colloids. The release of colloids exhibited possible sensitivity toward weather conditions such as alternating high temperatures and rainfall during summer (May–July) compared to fall (August–November). The morphology, elemental, and mineral composition of colloids were determined by a scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Colloids were dominated by phyllosilicates (biotite, muscovite, and kaolinite) with minor quartz and feldspars. Other minerals phases identified in colloidal fractions were hematite, goethite, arsenopyrite, and chalcopyrite. Colloids consisting of Fe, S, and O with structures resembling framboidal pyrite were identified, which is consistent with the non-silicates minerals identified by XRD. Our study suggests that the physical weathering of pyrite in the mine spoil can generate colloidal pyrite, which is mobilized and transported by soil pore water. Our results also indicate that these pyritic colloids are associated with toxic trace metals including Cu, Mn, and Zn. Colloid mobilization is also impacted by changes in temperature and precipitation, where clay mobilization afer rain events is favored. Further, sudden spikes in aqueous and/or colloidal concentrations may be the result of local heterogeneity within soils developing on mine spoil, indicating that further field-based work is necessary to better characterize pore-scale processes that control aqueous and colloid transport at similar sites to have a better understanding of potential contaminant transport from mine spoil systems.

58 GEOSCIENCES↗

Biochemical Mechanisms and Energy Strategies of Geobacter Sulfurreducens

To provide the scientific understanding required to allow DOE sites to incorporate relevant biological, chemical, and physical processes into decisions concerning environmental remediation, a fundamental understanding of the controls on micro-organism growth in the subsurface is necessary. Specifically, mobility of metals in the environment, including chromium, technetium and uranium, is greatly affected by the process of dissimilatory metal reduction (DMR), which has been shown to be an important biological activity controlling contaminant mobility in the subsurface at many DOE sites. Long-term maintenance of DMR at constant rates must rely upon steady fluxes of electron donors to provide the maintenance energy needed by organisms such as Geobacter sulfurreducens to maintain steady state populations in the subsurface.

09 BIOMASS FUELS↗