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At least 505 records · Page 28

Decommissioning an Active Historical Reactor Facility at the Savannah River Site - 13453

The Savannah River Site (SRS) is an 802 square-kilometer United States Department of Energy (US DOE) nuclear facility located along the Savannah River near Aiken, South Carolina, where Management and Operations are performed by Savannah River Nuclear Solutions (SRNS). In 2004, DOE recognized SRS as structure within the Cold War Historic District of national, state and local significance composed of the first generation of facilities constructed and operated from 1950 through 1989 to produce plutonium and tritium for our nation's defense. DOE agreed to manage the SRS 105-C Reactor Facility as a potentially historic property due to its significance in supporting the U.S. Cold War Mission and for potential for future interpretation. This reactor has five primary areas within it, including a Disassembly Basin (DB) that received irradiated materials from the reactor, cooled them and prepared the components for loading and transport to a Separation Canyon for processing. The 6,317 square meter area was divided into numerous work/storage areas. The walls between the individual basin compartments have narrow vertical openings called 'slots' that permit the transfer of material from one section to another. Data indicated there was over 830 curies of radioactivity associated with the basin sediments and approximately 9.1 M liters of contaminated water, not including a large quantity of activated reactor equipment, scrap metal, and debris on the basin floor. The need for an action was identified in 2010 to reduce risks to personnel in the facility and to eliminate the possible release of contaminants into the environment. The release of DB water could potentially migrate to the aquifer and contaminate groundwater. DOE, its regulators [U. S. Environmental Protection Agency (USEPA)-Region 4 and the South Carolina Department of Health and Environmental Control (SCDHEC)] and the SC Historical Preservation Office (SHPO) agreed/concurred to perform a non-time critical removal action for the In Situ Decommissioning (ISD) of the 105-C Disassembly Basin. ISD consisted of stabilization/isolation of remaining contaminated water, sediment, activated reactor equipment, and scrap metal by filling the DB with underwater non-structural grout to the appropriate (-4.877 meter) grade-level, thence with dry area non-structural grout to the final -10 centimeter level. The roof over the DB was preserved due to its potential historical significance and to prevent the infiltration of precipitation. Forced evaporation was the form of treatment implemented to remove the approximately 9.1 M liters of contaminated basin water. Using specially formulated grouts, irradiated materials and sediment were treated by solidification/isolation thus reducing their mobility, reducing radiation exposure and creating an engineered barrier thereby preventing access to the contaminants. Grouting provided a low permeability barrier to minimize any potential transport of contaminants to the aquifer. Efforts were made to preserve the historical significance of the Reactor in accordance with the National Historic Preservation Act. ISD provides a cost effective means to isolate and contain residual radioactivity from past nuclear operations allowing natural radioactive decay to reduce hazards to manageable levels. This method limits release of radiological contamination to the environment, minimizes radiation exposure to workers, prevents human/animal access to the hazardous substances, and allows for ongoing monitoring of the decommissioned facility. Field construction was initiated in August 2011; evaporator operations commenced January 2012 and ended July 2012 with over 9 M liters of water treated/removed. Over 8,525 cubic meters of grout were placed, completing in August 2012. The project completed with an excellent safety record, on schedule and under budget. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

INTERPRETING THE UNRESOLVED INTENSITY OF COSMOLOGICALLY REDSHIFTED LINE RADIATION

Intensity mapping experiments survey the spectrum of diffuse line radiation rather than detect individual objects at high signal-to-noise ratio. Spectral maps of unresolved atomic and molecular line radiation contain three-dimensional information about the density and environments of emitting gas and efficiently probe cosmological volumes out to high redshift. Intensity mapping survey volumes also contain all other sources of radiation at the frequencies of interest. Continuum foregrounds are typically ∼10{sup 2}–10{sup 3} times brighter than the cosmological signal. The instrumental response to bright foregrounds will produce new spectral degrees of freedom that are not known in advance, nor necessarily spectrally smooth. The intrinsic spectra of foregrounds may also not be well known in advance. We describe a general class of quadratic estimators to analyze data from single-dish intensity mapping experiments and determine contaminated spectral modes from the data themselves. The key attribute of foregrounds is not that they are spectrally smooth, but instead that they have fewer bright spectral degrees of freedom than the cosmological signal. Spurious correlations between the signal and foregrounds produce additional bias. Compensation for signal attenuation must estimate and correct this bias. A successful intensity mapping experiment will control instrumental systematics that spread variance into new modes, and it must observe a large enough volume that contaminant modes can be determined independently from the signal on scales of interest.

79 ASTRONOMY AND ASTROPHYSICS↗

Implications of an Improvised Nuclear Device Detonation on Command and Control for Surrounding Regions at the Local, State and Federal Levels

This paper discusses command and control issues relating to the operation of Incident Command Posts (ICPs) and Emergency Operations Centers (EOCs) in the surrounding area jurisdictions following the detonation of an Improvised Nuclear Device (IND). Although many aspects of command and control will be similar to what is considered to be normal operations using the Incident Command System (ICS) and the National Incident Management System (NIMS), the IND response will require many new procedures and associations in order to design and implement a successful response. The scope of this white paper is to address the following questions: • Would the current command and control framework change in the face of an IND incident? • What would the management of operations look like as the event unfolded? • How do neighboring and/or affected jurisdictions coordinate with the state? • If the target area’s command and control infrastructure is destroyed or disabled, how could neighboring jurisdictions assist with command and control of the targeted jurisdiction? • How would public health and medical services fit into the command and control structure? • How can pre-planning and common policies improve coordination and response effectiveness? • Where can public health officials get federal guidance on radiation, contamination and other health and safety issues for IND response planning and operations?

command and control, Incident Command Post, ICP, E↗

Decommissioning, Decontamination, and Disposal of LLW-LL, and ILW-LL at a Former Rare Earths Processing Facility in Malaysia - 19087

Geosyntec Consultants, Inc. (Geosyntec) was the design-build Contractor for a project involving the remediation and disposal of low level (LLW-LL and ILW-LL) NORM and TENORM wastes at a former rare earth processing facility in Malaysia. These sites were associated with a plant that extracted rare earth elements from local tin ores. Because of the naturally occurring radioactivity contained in the raw materials, these productions resulted in by-products and residues containing LLW-LL and ILW-LL thorium hydroxide and uranium hydroxide. The total mass of uranium (∼120 tons) and thorium (∼1,200 tons) managed in a single repository required the project design incorporate requirements related to inventory, security and safeguards around nuclear precursor materials. The requirement to consider a performance over a period of more than 10,000 years led to significant challenges in design and modeling of the disposal facility as this disposal facility was purposely designed and permitted as a final disposal for the LLW-LL and ILW-LL. The first phase of the project was the decommissioning, decontamination, and demolition of the 14- acre former rare earth processing plant and excavation of contaminated soils, construction of an engineered cell at the repository for waste disposal, and transportation and disposal of the waste materials into the cell. Final status surveys were carried out to allow the site to be successfully released by the Malaysian regulatory authorities as a clean site for re-development as common industrial use. Over 11,000 loads of material, including approximately 75,000 cubic meters of excavated soils and plant debris, were transported in specially designed steel transport boxes on public roads for disposal in the engineered cell. The second phase of the project included the design and construction of a second engineered cell, enhanced with protective barrier systems and a final cover system constructed of natural materials. Ancillary facilities such as substations, offices, processing buildings, and wastewater treatment plants were constructed to support retrieval and processing of the materials from more than 87,000 individual drums using a semi-automated process. The drums, waste packages, and other materials in the storage facility were systematically extracted, sorted, inventoried, solidified using Portland cement, transported, and disposed in the cell. All temporary facilities were decontaminated, demolished, and disposed in the cell. Radiological inventory and radiation safety programs were implemented to quantify the waste activity and to control exposure to workers and the public during the project. The total mass of radioactive contaminated waste disposed in the two projects is nearly 200,000 tons. The projects were carried out under a high level of scrutiny from Malaysian and international regulatory bodies. Between 2014 and 2017, performance monitoring and modeling activities were carried out to demonstrate that the disposal facility was performing in accordance with design requirements established by regulatory agencies. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Morphological and crystallographic controls in the replacement of calcite and aragonite by cerussite and otavite

Mineral replacement reactions are essential solid-fluid interactions in natural and industrial processes including metasomatism, diagenesis, and metamorphism, and sequestration of metal toxins from polluted water. In this paper, we explore the morphological evolution of aragonite and calcite (polymorphs of CaCO 3 ) during their replacement by cerussite (PbCO 3 , an isomorph of aragonite) and otavite (CdCO 3 , an isomorph of calcite) in acidic aqueous solutions (with initial pH 3 to 4). Observations using scanning electron and synchrotron-based transmission X-ray microscopies reveal the formation of pseudomorphic shells (~5 to 10 µm thick) of cerussite and otavite when Pb 2+ is reacted with either calcite or aragonite and when Cd 2+ is reacted with aragonite. The formation of pore space at the substrate-precipitate interface and within the precipitate is found to be key in promoting chemical exchange between the dissolving phase and the solution. In contrast, minimal reactivity is observed when Cd 2+ is reacted with calcite. These results demonstrate that the lack of substrate-precipitate epitaxy (either because of inconsistent symmetries or due to large lattice constant mismatch) is a critical factor that enables replacement of primary CaCO 3 minerals by Pb- or Cd-bearing secondary minerals while the presence of epitaxial relationships inhibit those reactions. When calcite and aragonite coexist, the replacement of aragonite by cerussite and otavite occurs preferentially over calcite. We postulate that the relative reactivity of calcite and aragonite to Pb 2+ and Cd 2+ can be determined by interplay between morphological and crystallographic properties of CaCO 3 materials as well as solution chemistry. Our results demonstrate that coupled dissolution-precipitation processes of carbonate minerals play an important role in controlling mobility and bioavailability of lead and cadmium in environments where acidic metal-contaminated water interacts with carbonate-rich rocks and soils.

58 GEOSCIENCES↗

Numerical study of groundwater flow cycling controlled by seawater/freshwater interaction in Woodville Karst Plain

Seawater intrusion due to sea level rise and climate change could significantly contaminate coastal groundwater resources, particularly in Florida, the flat low-land state in the United States. Based on the field investigation and hydrological measurements, a three-dimensional SEAWAT model is developed to evaluate the groundwater flow cycling and seawater intrusion to freshwater system in the Woodville Karst Plain (WKP), a typical karst groundwater system in the Floridan aquifer. The karst conduit network in the aquifer acts as fast flow pathway for groundwater flow and solute transport, so seawater could deeply intrude into the aquifer. Wakulla Spring, an inland spring 17 km from the coast and a coastal submarine spring, Spring Creek Spring Complex are connected through the conduit network. The flow direction between the two springs switches under various rainfall conditions in this region, thus the discharges at two karst springs are used to estimate the location of seawater/freshwater mixing interface. The SEAWAT modeling results indicate that the mixing interface, defined as 2 PSU (Practical Salinity Unit), intrudes 3 to 5 km through the subsurface karst conduit during the dry season and severely contaminates nearly 1 km width of groundwater around the conduit. The salinity distribution and the distance of seawater intrusion through the conduit system are very sensitive to precipitation variation and the sea level boundary condition. Furthermore, predictions are made for seawater intrusion to the aquifer under various sea level rise, precipitation scenarios and water pumping. The results show that the seawater intrusion could reach and contaminate inland freshwater systems if sea level rises 1.0 m or during a long-term no-precipitation season. Finally, this study provides insights for modeling and predicting the vulnerability of a coastal karst aquifer through the simulation of variable-density flow.

58 GEOSCIENCES↗

In situ Infrared Spectroelectrochemistry for Understanding Structural Transformations of Precisely Defined Ions at Electrochemical Interfaces

Understanding the intrinsic properties of electroactive species at electrode-electrolyte interfaces (EEIs) is essential to the rational design of high-performance solid-state energy conversion and storage systems. In situ spectroscopy combined with cyclic voltammetry (CV) provides insights into structural changes of electroactive species at functioning EEIs. Ion soft-landing enables precisely-controlled deposition of massand charge-selected ions onto electrode surfaces thereby avoiding the contamination inherent with conventional electrode preparation techniques. In this contribution, we describe a new approach for the simultaneous electrochemical and spectroscopic characterization of soft-landed ions at operating solid-state EEIs. The technique exploits a specially-fabricated three-electrode cell that is compatible with in situ infrared reflection absorption spectroscopy (IRRAS) characterization of the softlanded ions. Keggin polyoxometalate (POM) anions, PW12O40 3-, were selected as a model system for these experiments due to their multielectron redox activity, structural stability, and well-characterized IRRAS spectrum. In situ CV measurements indicated continuous multielectron transfer processes of the soft-landed PW12O40 3- anions over a large potential range of -2.1 to -0.3 V. A distinct shift in the wavenumber of the terminal W=Ot stretching vibration in the IRRAS spectra was observed during the multielectron reduction process. The results demonstrate the capabilities of the in situ spectroelectrochemical approach for examining structural changes of well-defined electroactive species during electron transfer processes at operating solid-state EEIs.

Su, Pei↗

Ranking Coal Ash Materials for Their Potential to Leach Arsenic and Selenium: Relative Importance of Ash Chemistry and Site Biogeochemistry

The chemical composition of coal ash is highly heterogeneous and dependent on the origin of the source coal, combustion parameters, and type and configuration of air pollution control devices. This heterogeneity results in uncertainty in the evaluation of leaching potential of contaminants from coal ash. The goal of this work was to identify whether a single leaching protocol could roughly group high-leaching potential coal ash from low-leaching potential coal ash, with respect to arsenic (As) and selenium (Se). We used four different leaching tests, including the Toxicity Characteristic Leaching Protocol (TCLP), natural pH, aerobic sediment microcosms, and anaerobic sediment microcosms on 10 different coal ash materials, including fly ash, lime-treated ash, and flue gas desulfurization materials. Leaching tests showed promise in categorizing high and low-leaching potential ash materials, indicating that a single point test could act as a first screening measure to identify high-risk ash materials. However, the amount of contaminant leached varied widely across tests, reflecting the importance of ambient conditions (pH, redox state) on leaching. These results demonstrate that on-site geochemical conditions play a critical role in As and Se mobilization from coal ash, underscoring the need to develop a situation-based risk assessment framework for contamination by coal ash pollutants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pajarito models

Pajarito models are developed to perform various types of model analyses related to the LANL-site groundwater contamination problems. Pajarito models include several models representing the LANL Chromium (Cr) and RDX sites. Pajarito models also include a model that is at the scale of the Pajarito Plateau. The models are designed to perform model prediction of groundwater flow and contaminant transport. The models are bundled in repositories. The model repositories include scripts, input control files, and drivers. A detailed description of the various files included in the repositories is provided in electronic form within the repositories.

Vesselinov, Velimir↗

Aging of Iodine-Loaded Silver Mordenite in NO2

Used nuclear fuel facilities need to control and minimize radioactive emissions. Off-gas systems are designed to remove radioactive contaminants, such as 85Kr, 14C, 3H, and 129I. In an off-gas system, any capture material will be exposed to a gas stream for months at a time. This gas stream may be at elevated temperature and could contain water, NOx gas, or a variety of other constituents comprising the dissolver off-gas stream in a nuclear fuel reprocessing plant. For this reason, it is important to evaluate the effects of long-term exposure, or aging, on proposed capture materials. One material under consideration is reduced silver mordenite (Ag0Z), which is recognized for its efficient iodine capture properties. Iodine is immobilized on Ag0Z as AgI, a solid with low volatility (m.p. ≥ 500°C). The aim of this study was to determine whether extended aging at elevated temperature in a nominally 2% NO2 environment would result in a loss of immobilized iodine from this material due to either physical or chemical changes that might occur during aging. Charges of iodine-loaded reduced silver mordenite (I2-Ag0Z) were exposed to a 2% NO2 environment for 1, 2, 3, and 4 months at 150°C, then analyzed for iodine losses The aging study was completed successfully. The material did not visibly change color or form. The results demonstrate that no significant iodine loss was observed over the course of 4 months of 2% NO2 aging of I2-Ag0Z at elevated temperature within the margin of error and the variability (~10%) in the loading along the beds. This provides assurance that iodine will remain immobilized on Ag0Z during extended online use in an off-gas capture treatment system. Future tests should expose I2-Ag0Z to progressively more complex feed gases in an effort to accurately replicate the conditions expected in a reprocessing facility.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Occurrence and Stabilization of Colloidal and Nanoparticulate Mercury Sulfides (Final Technical Report)

Mercury contaminates the soils at several DOE sites, including facilities at Oak Ridge, Hanford, and the Savannah River site. This contamination poses a hazard to surrounding ecosystems because the metal continuously leaches to local streams and rivers and is converted to methylmercury, a neurotoxic and highly bioaccumulative form of mercury. Anaerobic microorganisms such as sulfate-reducing and iron-reducing bacteria are primarily responsible for methylmercury production in the environment. The remediation of mercury-contaminated ecosystems is difficult because we lack a poor understanding of the factors that control mercury mobilization and methylation in sediments. The objective of this project was to investigate the forms of mercury that are bioavailable to methylating bacteria. This project specifically focused on mercury-sulfide-organic matter geochemistry and the persistence of nanoparticulate HgS that are intermediates of metal sulfide precipitation reactions occurring in the presence of natural organic matter (NOM). This work involved two specific aims: 1) Investigate environmental processes that facilitate the occurrence and stabilization of nanoparticulate HgS and other metal sulfides; and (2) Investigate the occurrence of nanoparticulate HgS in sediments of the East Fork Poplar Creek, located in near a DOE facility in Oak Ridge, TN. For specific aim #1, laboratory experiments were performed to simulate metal sulfide precipitation processes in environmental systems. A key experimental variable was the type and concentration of NOM that was used in the experiments simulating metal sulfide precipitation. The characteristics of the metal sulfide nanoparticles were analyzed using a suite of analytical techniques that included X-ray based methods at DOE synchrotron facilities (National Synchrotron Light Source and Advanced Photon Source). Field sampling in Oak Ridge was performed in collaboration with colleague at the Oak Ridge National Laboratory. The experimental results demonstrated that a combination of photon scattering and spectroscopic tools can be used to characterize nanoscale structures that form during heterogeneous metal-sulfide-NOM precipitation. ZnS precipitation experiments with a low molecular weight thiol indicated the importance of specific metal-ligand binding for altering the kinetics of ZnS nanoparticle aggregation and monomer growth. However, NOM consists of macromolecular structures that may interact with nano-HgS in non-specific ways (e.g. electrosteric surface interactions. The methylation potential of nano-HgS in sediments may depend on size and crystallinity of nanoparticles and interactions with NOM. For specific aim #2, sediment core samples were collected in three separate locations along the East Fork Poplar Creek in Oak Ridge, TN in June 2011. Analysis of the sediment samples indicated that more than 90% of the Hg in the porewater is associated with colloidal material. These results highlight the importance of small particles for dominating Hg speciation in sediment porewater. Overall, this project highlights the importance of nanoscale phases for mercury speciation. Nanoparticulate HgS will be of particular importance in the anaerobic habitats of methylating microorganisms. In previous models for Hg bioavailability, nanoparticles of Hg are presumed to be unavailable for methylating bacteria. However, recent work shows that nanoparticles contribute to bioavailable Hg that greatly exceeds the contribution from larger HgS microparticles (Zhang et al., 2012). The work performed for this exploratory project lays the groundwork for further study on nanoscale mercury sulfide geochemistry and contributes to an improved understanding of Hg bioavailability and methylation potential.

54 ENVIRONMENTAL SCIENCES↗

Critical Skills at SRS Radcon Inspectors

This video series provides a first-hand look at critical skills positions at the Savannah River Site and required qualifications. Meet the people behind the jobs and learn what they do to support important SRS missions.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Implementation of Enhanced Attenuation at the DOE Mound Site OU-1 Landfill: Accelerating Progress and Reducing Costs - 16270

A field demonstration of enhanced attenuation (EA) was initiated in 2014 to expedite the remediation of industrial solvents in the groundwater impacted by the former landfill Operable Unit 1 (OU-1) at the US Department of Energy (DOE) Mound, Ohio, Site. EA uses active engineering solutions to alter the target site so that the contaminant plume will passively stabilize and shrink. For OU-1, the EA was implemented by targeted injection of an electron donor (vegetable oil) to create 'structured geochemical zones'. Volatile organic compounds (VOCs) in the altered subsurface system encounter alternating anaerobic and aerobic environments along the plume flow path. The effect of these structured geochemical zones is effective and rapid degradation of parent compounds such as trichloroethene (TCE) and tetrachloroethene (PCE), and daughter compounds such as cis-1,2-dichloroethene and vinyl chloride. EA at Mound OU-1 provides a transition to natural attenuation and is an alternative to the baseline pump-and-treat (P and T) system. Industrial solvents (primarily TCE) and other VOCs that originated from the former solid-waste landfill contaminated the groundwater in the Buried Valley Aquifer beneath the Mound site. A groundwater P and T system was initiated in 1996 to control the plume, and a soil vapor extraction system was installed and operated from 1997 to 2003 to remove the bulk of the VOC sources from the vadose zone. Physical removal of the landfill waste and contaminated soil was performed between 2006 and 2010. Approximately 76,100 cubic meters (99,500 cubic yards) of material were removed from the OU-1 landfill area. Operation of the groundwater P and T system continued throughout this period. The principles and technical basis of the ongoing EA field demonstration were developed by the Interstate Technology and Regulatory Council. The goal of the EA implementation is to provide a bridge between active groundwater treatments and monitored natural attenuation. EA relies on understanding and manipulating the contaminant mass balance. Technologies are applied to sustainably reduce the contaminant loading from the source and/or increase the rate of natural attenuation processes within the plume. In 2014, a core team that included DOE, the US Environmental Protection Agency (EPA), the Ohio EPA, and technical support organizations evaluated remedial options for OU-1. During the 2014 evaluation, the team projected a cleanup time frame for the baseline P and T system of 26 additional years and a cleanup time frame for the EA remedy of 13 years. On the basis of that evaluation, EPA approved the implementation of the EA remedy that required the shutdown of the P and T system. The combination of technologies implemented for OU-1 EA included (a) neat vegetable oil in the vadose zone in the former landfill and (b) emulsified vegetable oil within the footprint of the groundwater plume. In the first part of the deployment, neat oil spreads laterally and forms a thin layer on the water table beneath residual soil sources to intercept and reduce future VOC loading and to reduce oxygen inputs to the local groundwater. In the second part of the deployment, emulsified oil forms active bioremediation anaerobic treatment zones within the plume footprint to degrade existing groundwater contaminants (via reductive dechlorination, co-metabolism, or both) and stimulates long-term attenuation capacity in the down-gradient aerobic plume (via co-metabolism). The results from the first year of the field demonstration indicate that the dissolved TCE and PCE plumes have decreased in size and mass. Statistical tests indicate that the VOC concentrations in the majority of the source-area wells are decreasing. The VOC concentrations throughout the plume are projected to be below the target maximum contaminant level of 2 to 5 μg/L within 5 to 10 years-sooner than the design projection of 13 years. The biogeochemistry and microbial community within the structured geochemical zones are consistent with the design and appear to be stable. At Mound OU-1, EA has accelerated progress toward the remedial action objectives and reduced costs. Ongoing monitoring will determine whether the EA remedy has transitioned the site into monitored natural attenuation status and whether the EA will continue to be effective, timely, and sustainable. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Environmental Systems Biology Approach to Bioremediation

Pollution is everywhere. Microbes are also everywhere, and many have the ability to degrade environmental contaminants. Understanding how these microbial communities work to degrade environmental contaminants will enable us to use these microbes to clean up the pollution. Understanding, monitoring, and controlling the environment with biological processes, i.e., an environmental systems biology approach to bioremediation, answer the need which is everywhere. By using an environmental systems approach to bioremediation, we make sure we know of any “fatal flaws” in the approach, get a much better handle on life-cycle cost analysis, and can grade an engineered solution into a natural attenuation solution. The whole is greater than the sum of its parts. By using an environmental systems biology approach to bioremediation and cross-linkage of systems at all levels providing multiple lines of evidence involving environmental observations, laboratory testing, microcosm simulations, hypothesis refinement, field testing and validation, and multiple iterations of this circle, we will be able to make new theories and paradigms for bioremediation of contaminated environments.

Hazen, Terry C.↗

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↗

2015 Advanced Site Investigation and Monitoring Report Riverton, Wyoming, Processing Site September 2016

The U.S. Department of Energy conducted initial groundwater characterization of the Riverton, Wyoming, Processing Site in the 1990s. The characterization culminated in a Site Observational Work Plan in 1998 that recommended a natural flushing compliance strategy. Results of verification monitoring indicated that natural flushing was generally progressing as expected until June 2010, when significant increases in contaminant concentrations were measured in several monitoring wells downgradient of the site after the area flooded. In response to the unexpected results following the flood, an enhanced characterization of the surficial aquifer was conducted in 2012, which included installation of 103 boreholes along nine transects with a Geoprobe, collection of 103 water samples and 65 soil samples, laboratory tests on the soil samples, and additional groundwater modeling. This advanced site investigation report summarizes additional investigation in 2015 through the use of backhoe trenching, sonic drilling, multilevel monitoring wells, direct-push drilling, and temporary well points to collect soil and groundwater samples. Additional surface water measurements were made included the installation of a stilling well and the measurement of stream elevation along the Wind River to approximate upgradient groundwater heads. Groundwater sampling included the addition of geochemical constituents and isotopes that have not been sampled in the past to better understand post-flood conditions and the possibility of additional or ongoing contaminant sources. This sampling was performed to (1) better define the contaminant plumes, (2) verify the occurrence of persistent secondary contaminant sources, (3) better understand the reason for the contaminant spikes after a 2010 flood, and (4) assess contaminant plume stagnation near the Little Wind River. This report provides data analyses and interpretations for the 2015 site investigation that addresses these issues and provides recommendations for future efforts. Observations from trenches and sonic drilling indicate the general lithology of the shallow, unconsolidated sediments consists of a silt zone at the surface that ranges from 2.5 to 4.8 feet below ground surface, underlain by sand and gravel, underlain by the top of the weathered bedrock (Wind River Formation). Soil data from trenches and sonic drilling indicate (1) elevated concentrations of several constituents in the silt zone, likely due to the formation of evaporites, (2) uranium is the only measured element that appears to be concentrated in the silt over the groundwater contaminant plume, (3) in the former tailings impoundment area, there may be a thin unsaturated zone with elevated uranium in the native material just below the fill, (4) in the former tailings impoundment area, slightly higher uranium concentrations occur in the underlying saturated sand and gravel, and (5) several bedrock samples have a unique geochemical signature, generally related to a higher silt content. Assessment of groundwater flow included measuring river elevations along the Wind River and installing the temporary well points adjacent to the Little Wind River that provided additional data points to refine contours for water table elevations. These data confirm past interpretations of groundwater flow to the southeast across the site toward the Little Wind River. Hydraulic head elevations between paired surficial and semiconfined aquifer wells indicate variable vertical gradients across the site with the potential for upward and downward flow. Additional direct-push drilling and groundwater sampling confirmed the contaminant plume configuration, but it also revealed a low-sulfate-concentration zone at the edge of the former tailings impoundment. Temporary well points provided better definition of plume concentrations at the bank of the Little Wind River, and data from these wells indicate plume discharge to the river. Additional sampling in an area southwest of the plume that had elevated uranium groundwater concentrations in the past did not have any uranium concentrations above the U.S. Environmental Protection Agency maximum concentration limit for uranium. Results from multilevel monitoring wells indicate some geochemical differences with depth, but overall concentrations are similar to those in nearby conventional monitoring wells in the long-term monitoring program. Geochemistry data from these multilevel monitoring wells confirm the general increase in contaminant concentrations toward the river and toward the plume centerline for chloride, sulfate, and uranium but highlight geochemical controls on calcium. Iron data indicate slightly reducing conditions, especially near water table and bedrock surfaces, with more oxidizing conditions in the middle of the sand and gravel. Uranium activity ratios (234U/238U) confirm the uranium plume in the surficial aquifer as being mill related, and the area to the southwest outside the plume as natural, non-mill related. In the semiconfined aquifer, evidence of aquifer connection and impacts from the mill is inconclusive. Values of δD and δ 18 O suggest water is derived from different sources and tritium data confirm that the semiconfined aquifer water is generally older than the surficial aquifer water. However, these data do indicate some groundwater communication from the surficial aquifer into the semiconfined aquifer, which resulted in δD and δ 18 O and tritium values in the semiconfined aquifer that are more similar to those in the surficial aquifer. Values of δ 34 S sulfate in the semiconfined aquifer combined with sulfate concentrations indicate the potential for some mill- related sulfate in the semiconfined aquifer, albeit limited to an area near and beneath the former tailings impoundment. Uranium and molybdenum concentrations in the semiconfined aquifer are below groundwater standards in all wells. However, the elevated molybdenum concentrations at one semiconfined aquifer well underneath the former tailings impoundment suggests a mill- derived source for the uranium and molybdenum in that well. It is possible that aquifer cross- communication occurred when the tailings impoundment was active and created a higher head. Current cross-communication appears unlikely given the large differences in tritium values and an upward hydraulic head at this location. Nine domestic wells are located within the institutional control boundary (eight in the confined aquifer and one in the semiconfined aquifer). Uranium and molybdenum concentrations in all samples collected from these wells were one or two orders of magnitude below the groundwater standards. Surface water flow in the Little Wind River in September 2015 was low compared to historical averages for that time of year. As a result, the uranium concentration measured in the Little Wind River was at a historical maximum at the sampling location upstream of the site. However, the impact of uranium discharge from the groundwater plume into the Little Wind River was not measureable. Elevated sulfate concentrations were observed in an outfall ditch related to an active sulfuric acid plant. Uranium concentrations in the oxbow lake remain at concentrations above the groundwater standard. Plume contaminant concentrations had returned to levels found prior to the 2010 flood by the end of 2015. However, these concentrations still exceed model predictions for natural flushing, and the current data indicate that natural flushing to achieve remediation goals within the 100-year time period is not likely, especially with the high potential for additional floods in the update to the conceptual site model (CSM), soil data indicate additional contaminant sources, specifically uranium, in evaporites within the silt layer over the uranium plume and in naturally reduced zones (NRZs). Additional zones of slightly elevated uranium concentration are in the native sediments just above the water table but below the fill layer in the former tailings impoundment area. This area also has slightly elevated uranium in the sand and gravel below the water table. Mass balance calculations indicate that small amounts of dissolution in any of these zones with increased uranium in the solid phase can produce groundwater uranium concentrations above the groundwater standard and could account for the post-flood uranium spike. The additional uranium near the former tailings impoundment provides a mechanism for a continuing source for the uranium plume that was not considered in earlier natural flushing models. In addition, uranium released from the silt layer or the NRZs seasonally and during flooding may add uranium to the groundwater plume near the Little Wind River. These mechanisms provide a possible explanation for plume persistence, along with spikes in concentrations during floods, that creates the current plume configuration. Additional updates to the CSM include (1) chloride flushes more rapidly than uranium beneath the former mill site, (2) chloride in the silt layer provides a scenario in which chloride cannot be used as a conservative tracer (especially in areas prone to flooding), (3) uranium concentrations with depth can be variable (especially below NRZs), and (4) calcite and gypsum solubility limits appear to provide important geochemical controls on groundwater geochemistry. The conclusion of this study provides several recommendations for additional work to refine the CSM and continue assessment of the natural flushing compliance strategy. Recommendations for additional work include targeted soil and groundwater sampling to assess geochemical conditions, distribution of contaminants, and groundwater/surface water interaction; additional column tests to provide data for geochemical modeling; and development of an updated groundwater flow model, which will be used in conjunction with a geochemical model to assess the viability of the natural flushing compliance strategy.

2015 Monitoring Riverton, WY↗

Load planning in the dark: RH-TRU waste container load planning at Sandia National Laboratories/New Mexico - 15116

Sandia National Laboratories (Sandia) performed several sets of experiments during the 1970's and 1980's with fresh and irradiated mixed oxide (MOX) and uranium oxide (UO{sub 2}) materials designed to simulate various fuel responses under varying reactor conditions. These research materials were from light water and breeder mixed oxide reactors. The experimental vessels and extraneous piece parts resulting from the experiments were identified as eligible for disposal at the Waste Isolation Pilot Plant (WIPP) as remote-handled (RH) transuranic (TRU) waste. Once Sandia received the approval to dispose at WIPP, discussions began with the Carlsbad Field Office (CBFO) and Nuclear Waste Partnerships, LLC (NWP) to provide Central Characterization Program (CCP) support for certified acceptable knowledge, visual examination, and dose-to-curie for the repackaging effort. In addition to the WIPP support, Sandia was required to prepare a load plan describing the configuration of the parent containers and how they could be repackaged to meet WIPP and other regulatory requirements. However, all of these containers were packaged as material twenty (20) or thirty (30) years ago and the records of the packaging process and configuration were not documented as waste. Therefore, it seemed that the load plans were prepared with limited information regarding parent container configuration, hence in the dark. The design of the Auxiliary Hot Cell Facility (AHCF) in technical area (TA) V, where the repackaging was to take place, along with the shipping requirements for the RH 72-B cask, limited the options for repackaging. This configuration required that 0.114 m{sup 3} (30-gallon) containers be packaged in the hot cell, removed and placed into 0.208 m{sup 3} (55-gallon) containers to mitigate contamination issues. The material had been tracked as accountable nuclear material and Sandia had verified Material Control and Accountability (MC and A) data on each parent container. Based on the MC and A data, scaling factors could be determined and sampling and analysis was not required. However, it meant that parent containers could not be split into two daughter containers, though two or more parent containers could be combined into one daughter. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mercury in Water

Mercury (Hg) is a global pollutant threatening our water resources and human health. Every one of us contains some levels of Hg or methylmercury (MeHg) in our body due to consumption of contaminated food such as fish and rice. Our understanding of the behavior of Hg in natural aquatic environments is limited as the major factors controlling microbial uptake and conversion of inorganic Hg to neurotoxic MeHg remain obscure. MeHg concentrations in water can bioaccumulate up to eight orders of magnitude in the food chain. Metallic or elemental Hg can evaporate and transport around the globe, and also readily undergoes chemical, photochemical and biological transformations (i.e., oxidation, reduction, methylation and demethylation) in water and sediments. Natural dissolved organic matter (DOM) plays a critical role in mediating these transformations because of its exceptionally strong binding affinity for Hg and its dual functional roles in reducing and oxidizing Hg. While the discovery of Hg-methylation genes significantly advanced our understanding of MeHg biosynthesis, the simultaneous degradation of MeHg at low concentrations (i.e., picomolar to nanomolar) by a range of methanotrophic and anaerobic bacteria has recently been recognized possibly as an important process for controlling net MeHg production, a key factor that determines Hg concentrations and bioaccumulation in biota. Although treatment technologies for Hg removal from water are available, they are mostly applicable to industrial waste streams and at localized contamination sites with high Hg concentrations (i.e., micromolar to millimolar). Reductions in Hg human exposure may be achievable by decreasing anthropogenic releases, such as coal combustion, over the long-term since Hg methylation responds to Hg inputs, particularly freshly deposited Hg in natural aquatic systems.

Gu, Baohua↗