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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Formation of zinc carbonate phases on dissolving calcite, aragonite, and vaterite in acidic aqueous solutions

Calcium carbonate (CaCO 3 ) minerals serve as a major sink to retain metal ions through mineral-water interfacial reactions in which the capacity and long-term stability of contaminant uptake are influenced by coupled dissolution and precipitation reactions of both primary and secondary carbonate minerals (i.e., mineral replacement). Notably, recent studies of calcite reactivity in acidic solutions containing high levels of metal ions demonstrated complex behavior under conditions of sustained disequilibrium. Here, we explored the reactivity of three CaCO 3 polymorphs (calcite, aragonite, and vaterite) with acidic Zn 2+ -containing aqueous solutions using a suite of imaging techniques including optical and scanning electron microscopies, synchrotron-based micro X-ray fluorescence, and transmission X-ray microscopy. Zn uptake by calcite occurred through a two-step process: the formation of a thin layer of the zinc precipitate on the substrate surface followed by the growth of fibrous and radiating hydrozincite particles from the layer. In contrast, Zn uptake by aragonite occurred by mineral replacement where the secondary Zn carbonate phase preserved the external morphology of the original crystal (i.e., a pseudomorph). The replacement of vaterite by hydrozincite occurred within the confined space beneath the porous shell of vaterite, signifying that the primary mechanism driving Zn carbonate precipitation was chemical exchange through the pores. When multiple CaCO 3 polymorphs coexisted, the replacement of aragonite and vaterite occurred preferentially over that of calcite. These results demonstrate the distinct morphological and mineralogical controls over the reactivities of calcium carbonate minerals with Zn 2+ under acidic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Significance of Plant Root Microorganisms in Reclaiming Water in CELSS

Since many microorganisms demonstrate the ability to quickly break down complex mixtures of waste and environmental contaminants, examining their potential use for water recycling in a closed environment is appealing. Water contributes approximately 90 percent of the life sustaining provisions in a human space habitat. Nearly half of the daily water requirements will be used for personal hygiene and dish washing. The primary contaminants of the used "gray" water will be the cleansing agents or soaps used to carry out these functions. Reclaiming water from the gray water waste streams is one goal of the NASA program, Controlled Ecological Life Support Systems (CELSS). The microorganisms of plane roots are well documented to be of a beneficial effect to promote plant growth. Most plants exhibit a range of bacteria and fungi which can be highly plant-specific. In our investigations with lettuce grown in hydroponic culture, we identified a microflora of normal rhizosphere. When the roots were exposed to an anionic surfactant, the species diversity changed, based on morphological characteristics, with the numbers of species being reduced from 7 to 2 after 48 hours of exposure. In addition, the species that became dominant in the presence of the anionic surfactant also demonstrated a dramatic increase in population density which corresponded to the degradation of the surfactant in the root zone. The potential for using these or other rhizosphere bacteria as a primary or secondary waste processor is promising, but a number of issues still warrant investigation; these include but are not limited to: (1) the full identification of the microbes, (2) the classes of surfactants the microbes will degrade, (3) the environmental conditions required for optimal processing efficiency and (4) the ability of transferring the microbes to a non-living solid matrix such as a bioreactor.

Bubenheim, David L.↗
DOE OSTI2025

Hydrometallurgical Recycling of Black Mass of Spent Lithium-Ion Batteries Using Methanesulfonic Acid: Leaching, Kinetic Studies, and Potential for Total Recovery of Valuable Components

Methanesulfonic acid (MSA) exhibits several advantageous properties rendering it a promising candidate for circular hydrometallurgical processes. These properties include a high acidity (pKa = - 1.9) comparable to that of classical mineral acids as well as biodegradability, high stability, and high solubility of metal-MSA complexes in aqueous solutions. In this study, MSA was employed as a lixiviant for the leaching of metals (lithium, nickel, cobalt, and manganese) from the black mass of spent lithium-ion batteries (LIBs). The effect of various parameters, including MSA concentration, H 2 O 2 concentration, temperature, and pulp density, was systematically investigated. Under the optimized conditions (1.5 M MSA, 0.2 M H 2 O 2 , 60 °C, and 50 g/L pulp density), quantitative leaching of lithium was achieved within 30 min, while for nickel and cobalt it was after 2 h, and 4 h for manganese leaching. The leaching kinetics of Li, Ni, Co, and Mn were studies using the shrinking particle models (SPM) and the Avrami model. The results indicated that the Avrami model provided the best fit to the kinetic data, with apparent activation energies of 46.81 kJ/mol for Li, 58.61 kJ/mol for Ni, 59.69 kJ/mol for Co, and 58.86 kJ/mol for Mn, within the temperature range of 25-70 °C (except for Li, which was analyzed in the range of 25-60 °C), consistent with chemical reaction control. Subsequently, residual contaminants in the leaching residue were eliminated through pyrolysis. The quantitative leaching of metals in MSA solution (a green lixiviant), combined with the pyrolytic treatment of leaching residues, represents a circular strategy for the total recovery of valuable components from the black mass of spent LIBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Innovative Strategies for Long-Term Monitoring of Complex Groundwater Plumes at DOE’s Legacy Sites (Workshop Report)

Most remaining Department of Energy (DOE) sites will require extended periods of institutional control, especially at complex groundwater sites where attenuation-based strategies have been implemented to facilitate closure. The current practice of monitoring—obtaining and analyzing contaminant concentration in groundwater samples at numerous wells—will account for a large portion of the projected life-cycle at these DOE sites unless a new approach is adopted. State-of-the-art technologies are being developed, including in situ sensors, geophysics, radiation mapping, numerical modeling and AI/ML. These technologies can optimize monitoring strategies in space and time, provide spatially extensive information at vulnerable regions and/or provide more continuous monitoring at lower cost. As part of DOE’s Office of Environmental Management (DOE-EM’s) efforts to advance long-term monitoring systems, an in-person/virtual hybrid workshop was hosted by Savannah River National Laboratory (SRNL) on January 24 and 25, 2023, in Augusta, Georgia. Because DOE-EM’s complex sites will eventually be transferred to DOE’s Office of Legacy Management (DOE-LM), representatives of DOE-LM were important participants in the workshop. The purpose of the workshop was to identify challenges and opportunities for deploying advanced technologies for long-term monitoring at DOE sites. The key questions during the workshop were: 1) the regulatory acceptance of replacing a process that traditionally has used laboratory sampling and analysis of groundwater samples, and 2) the application of this strategy to the southwestern arid sites that include many of the remaining DOE-EM and DOE-LM complex groundwater plumes. Characteristics common to most arid sites present both limitations and opportunities for advanced technologies. DOE-EM has funded a National Laboratory team from SRNL, Lawrence Berkeley National Laboratory (LBNL), and Pacific Northwest National Laboratory (PNNL) to establish the overarching framework of long-term monitoring by systematically combining advanced hardware and software technologies. This project is titled “Advanced Long-Term Environmental Monitoring Systems (ALTEMIS)” and is sponsored by the DOE-EM Technology Development Program. The multi-laboratory team is currently developing and testing innovative monitoring strategies, including the use of in situ groundwater sensors, geophysics, drone/satellite-based remote sensing, reactive transport modeling, and artificial intelligence/machine learning (AI/ML). The project’s demonstration testbed is at the Savannah River Site (SRS) F-Area Seepage Basins, where a well-characterized complex groundwater plume composed of uranium and other radionuclides is in the latter stages of remediation. The workshop included more than 70 participants, presentations, a field visit to F-Area, breakout working groups, and large group discussion. Participants developed recommendations on five topics: in situ sensors, spatially integrative tools, challenges to regulatory acceptance, AI/ML strategies, and transitioning sites to DOE-LM.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

High-Precision Zinc Isotopic Measurement of Certified Reference Materials Relevant to the Environmental, Earth, Planetary and Biomedical Sciences

The zinc (Zn) stable isotope system has emerged as a powerful tool for investigating natural and anthropogenic processes of interest to disciplines extending from the Earth and planetary sciences to biomedical research. In nature, Zn isotopes typically fractionate ( 66 Zn/ 64 Zn) within the range of –1 and +1 permil (‰), and however, analytical limitations restrict the application of the Zn isotope system. Specifically, there is a lack of well-characterised matrix-matched reference materials covering most Zn isotope applications that are essential for validating laboratory performance, particularly given the contamination prone nature of Zn. Furthermore, the increasing demand for analysis of size-limited materials and sample types displaying small, sub-permil level Zn isotope variations requires improvements in measurement procedures. To address these limitations, the δ 66 Zn values of two pure Zn solutions and eighteen reference materials including the previously uncharacterised RGM-2, BCR-279, DOLT-4, DOLT-5, NASS-7, SBC-1, SGR-1b, MESS-3 and HISS-1, and the understudied QLO-1, SDC-1, BCR-414, NASS-6 and COQ-1 materials are reported. Furthermore, a 70 Zn- 67 Zn double-spike design has been implemented that routinely achieves intermediate measurement precision better than ± 0.02‰. This represents at least a two-fold improvement when compared with other double-spike designs, providing a robust platform of δ 66 Zn values required for quality control procedures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Co-Firing Switchgrass and Waste Coal in A Power Plant: A Techno-Economic and Life Cycle Evaluation for The Ohio River Valley (SWITCH) (Final Technical Report for Ohio State/FE0032204)

Abandoned coal mine lands (AMLs) represent one of the most persistent environmental challenges in the United States. Prior to the enactment of the Surface Mining Control and Reclamation Act (SMCRA) in 1977, coal mining operations were not legally required to reclaim disturbed lands, leaving behind approximately 500,000 AML sites nationwide. These sites pose severe environmental and health risks, including acid mine drainage, soil and water contamination, and spontaneous combustion of waste coal piles. Millions of Americans live within one mile of these AMLs, underscoring the urgency of remediation. Traditional reclamation practices, such as planting cool-season grasses, often fail to fully restore ecological function or leverage the economic potential of these lands. This project addressed these challenges by developing integrated strategies for resource recovery, land reclamation, and sustainable energy production. This project evaluated an integrated strategy to convert this liability into an opportunity by recovering waste coal and co-firing it with switchgrass (Panicum virgatum L.) cultivated on reclaimed or marginal AML areas in existing coal-fired power plants. Switchgrass not only provides a renewable feedstock but also aids in land reclamation and carbon sequestration. 1) Remote Sensing and Machine Learning for Waste Coal Identification Using Sentinel-2 satellite imagery and supervised classification, we applied four machine learning models to detect historical waste coal piles. Random Forest achieved the highest accuracy (precision: 86%, recall: 77%). Time-series analysis revealed gradual vegetation recovery since 1986, indicating natural reclamation processes in historical sites, while active mining areas showed ongoing disturbance. This workflow enables scalable monitoring and prioritization of reclamation efforts. 2) UAS-Based Stockpile Volume Estimation To quantify recoverable waste coal, we evaluated Unmanned Aerial Systems (UAS) equipped with Light Detection and Ranging (LiDAR) and multispectral sensors. Structure-from-Motion (SfM) photogrammetry combined with interpolated Digital Terrain Models (DTMs) achieved strong agreement with LiDAR reference volumes (Root Mean Square Error (RMSE) ≈147 m 3 , Mean Absolute Percentage Error (MAPE) ≈2%). Sensitivity analysis confirmed that spatial resolution significantly influences accuracy, emphasizing the need for high-resolution data for precise volume estimation. This approach offers a scalable, cost-effective, and accurate alternative to conventional ground-based surveys. 3) Switchgrass Cultivation for Bioenergy and Water Quality Improvement We assessed the hydrological and water quality impacts of converting AMLs to switchgrass production areas using the Soil and Water Assessment Tool (SWAT). Results showed that converting 10% of the watershed area into the switchgrass production zone reduced streamflow by 3.1%, total suspended solids by 18.1%, total nitrogen by 7.6%, and total phosphorus by 6.2%, while achieving biomass yields of 8.6–9.2 metric tons per hectare. These findings highlight switchgrass as a dual-benefit strategy for land reclamation and bioenergy feedstock production. 4) Integrated Co-Firing and CCS for Carbon-Negative Power Generation We modeled co-firing scenarios using the Power Plant Flexible Model (PPFM) to evaluate plant efficiency, greenhouse gas (GHG) emissions, and levelized cost of electricity (LCOE). Without carbon capture and storage (CCS), increasing switchgrass co-firing ratios reduced LCOE from $\$$150/MWh at 0% biomass to $\$$110/MWh at full substitution. Under CCS, costs remained higher (~$\$$250/MWh at 0% biomass) but decreased to $\$$200/MWh at 100% biomass, while enabling net-zero or carbon-negative electricity due to switchgrass sequestration benefits. Although CCS introduced efficiency penalties, pairing it with biomass co-firing offset these impacts and maximized climate benefits. Overall, optimizing co-firing ratios between 60-100%, supported by reliable logistics and storage strategies, emerged as a practical pathway to balance affordability, sustainability, and net-zero or negative GHG emissions while promoting productive reuse of AMLs.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2012

Multi-Scale Mass Transfer Processes Controlling Natural Attenuation and Engineered Remediation: An IFRC Focused on Hanford’s 300 Area Uranium Plume

The Integrated Field Research Challenge (IFRC) at the Hanford Site 300 Area uranium (U) plume addresses multi-scale mass transfer processes in a complex subsurface biogeochemical setting where groundwater and riverwater interact. A series of forefront science questions on reactive mass transfer motivates research. These questions relate to the effect of spatial heterogeneities; the importance of scale; coupled interactions between biogeochemical, hydrologic, and mass transfer processes; and measurements and approaches needed to characterize and model a mass-transfer dominated biogeochemical system. The project was initiated in February 2007, with CY 2007, CY 2008, CY 2009, and CY 2010 progress summarized in preceding reports. A project peer review was held in March 2010, and the IFRC project acted upon all suggestions and recommendations made in consequence by reviewers and SBR/DOE. These responses have included the development of 'Modeling' and 'Well-Field Mitigation' plans that are now posted on the Hanford IFRC web-site, and modifications to the IFRC well-field completed in CY 2011. The site has 35 instrumented wells, and an extensive monitoring system. It includes a deep borehole for microbiologic and biogeochemical research that sampled the entire thickness of the unconfined 300 A aquifer. Significant, impactful progress has been made in CY 2011 including: (i) well modifications to eliminate well-bore flows, (ii) hydrologic testing of the modified well-field and upper aquifer, (iii) geophysical monitoring of winter precipitation infiltration through the U-contaminated vadose zone and spring river water intrusion to the IFRC, (iv) injection experimentation to probe the lower vadose zone and to evaluate the transport behavior of high U concentrations, (v) extended passive monitoring during the period of water table rise and fall, and (vi) collaborative down-hole experimentation with the PNNL SFA on the biogeochemistry of the 300 A Hanford-Ringold contact and the underlying redox transition zone. The modified well-field has functioned superbly without any evidence for well-bore flows. Beyond these experimental efforts, our site-wide reactive transport models (PFLOTRAN and eSTOMP) have been updated to include site geostatistical models of both hydrologic properties and adsorbed U distribution; and new hydrologic characterization measurements of the upper aquifer. These increasingly robust models are being used to simulate past and recent U desorption-adsorption experiments performed under different hydrologic conditions, and heuristic modeling to understand the complex functioning of the smear zone. We continued efforts to assimilate geophysical logging and 3D ERT characterization data into our site wide geophysical model, with significant and positive progress in 2011 that will enable publication in 2012. Our increasingly comprehensive field experimental results and robust reactive transport simulators, along with the field and laboratory characterization, are leading to a new conceptual model of U(VI) flow and transport in the IFRC footprint and the 300 Area in general, and insights on the microbiological community and associated biogeochemical processes influencing N, S, C, Mn, and Fe. Collectively these findings and higher scale models are providing a unique and unparalleled system-scale understanding of the biogeochemical function of the groundwater-river interaction zone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2011

Microbial Characterization of Solid-Wastes Treated with Heat Melt Compaction Technology

The research purpose of the project was to determine the fate of microorganisms in space-generated solid wastes after processing by a Heat Melt Compactor (HMC), which is a candidate solid waste treatment technology. Five HMC product disks were generated at Ames Research Center (ARC), Waste Management Systems element. The feed for two was simulated space-generated trash and feed for three was Volume F compartment wet waste returned on STS 130. Conventional microbiological methods were used to detect and enumerate microorganisms in HMC disks and in surface swab samples of HMC hardware before and after operation. Also, biological indicator test strips were added to the STS trash prior to compaction to test if HMC processing conditions, 150 C for approx 3 hr and dehydration, were sufficient to eliminate the test bacteria on the strips. During sample acquisition at KSC, the HMC disk surfaces were sanitized with 70% alcohol to prevent contamination of disk interiors. Results from microbiological assays indicated that numbers of microbes were greatly reduced but not eliminated by the 70% alcohol. Ten 1.25 cm diameter cores were aseptically cut from each disk to sample the disk interior. The core material was run through the microbial characterization analyses after dispersal in sterile diluent. Low counts of viable bacteria (5 to 50 per core) were found but total direct counts were 6 to 8 orders of magnitude greater. These results indicate that the HMC operating conditions might not be sufficient for complete waste sterilization, but the vast majority of microbes present in the wastes were dead or non-cultivable after HMC treatment. The results obtained from analyses of the commercial spore test strips that had been added fo the wastes prior to HMC operation further indicated that the HMC was sterilizing the wastes. Nearly all strips were recovered from the HMC disks and all of these were negative for spore growth when run through the manufacturer's protocol. The 10(exp 6) or so spores impregnated into the strips were no longer viable. Control test strips, i.e., not exposed to the HMC conditions, were all strongly positive. All isolates from the cultivable counts were identified, leading to one concern: several were identified as Staphylococcus aureus, a human pathogen. The project reported here provides microbial characterization support to the Waste Management Systems element of the Life Support and Habitation Systems program.

Strayer, Richard F.↗
DOE OSTI2012

Dismantling Structures and Equipment of the MR Reactor and its Loop Facilities at the National Research Center 'Kurchatov Institute' - 12051

In 2008 a design of decommissioning of research reactors MR and RFT has been developed in the National research Center 'Kurchatov institute'. The design has been approved by Russian State Authority in July 2009 year and has received the positive conclusion of ecological expertise. In 2009-2010 a preparation for decommissioning of reactors MR and RFT was spent. Within the frames of a preparation a characterization, sorting and removal of radioactive objects, including the irradiated fuel, from reactor storage facilities and pool have been executed. During carrying out of a preparation on removal of radioactive objects from reactor sluice pool water treating has been spent. For these purposes modular installation for clearing and processing of a liquid radioactive waste 'Aqua - Express' was used. As a result of works it was possible to lower volume activity of water on three orders in magnitude that has allowed improving essentially of radiating conditions in a reactor hall. Auxiliary systems of ventilation, energy and heat supplies, monitoring systems of radiating conditions of premises of the reactor and its loop-back installations are reconstructed. In 2011 the license for a decommissioning of the specified reactors has been received and there are begun dismantling works. Within the frames of works under the design the armature and pipelines are dismantled in a under floor space of a reactor hall where a moving and taking away pipelines of loop facilities and the first contour of the MR reactor were replaced. A dismantle of the main equipment of loop facility with the gas coolant has been spent. Technologies which were used on dismantle of the radioactive contaminated equipment are presented, the basic works on reconstruction of systems of maintenance of on the decommissioning works are described, the sequence of works on the decommissioning of reactors MR and RFT is shown. Dismantling works were carried out with application of means of a dust suppression that, in aggregate with standard means at such works of individual protection of the personnel and devices of radiating control, has allowed to lower risk of action of radiation on the personnel, the population and environment at the expense of reduction of volume activity of radioactive aerosols in air. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

DOE 2012 Occupational Radiation Exposure October 2013

The U.S. Department of Energy (DOE) Office of Analysis within the Office of Health, Safety and Security (HSS) publishes the annual DOE Occupational Radiation Exposure Report to provide an overview of the status of radiation protection practices at DOE (including the National Nuclear Security Administration [NNSA]). The DOE 2012 Occupational Radiation Exposure Report provides an evaluation of DOE-wide performance regarding compliance with Title 10, Code of Federal Regulations (C.F.R.), Part 835, Occupational Radiation Protection dose limits and as low as reasonably achievable (ALARA) process requirements. In addition, the report provides data to DOE organizations responsible for developing policies for protection of individuals from the adverse health effects of radiation. The report provides a summary and an analysis of occupational radiation exposure information from the monitoring of individuals involved in DOE activities. Over the past 5-year period, the occupational radiation exposure information is analyzed in terms of aggregate data, dose to individuals, and dose by site. As an indicator of the overall amount of radiation dose received during the conduct of operations at DOE, the report includes information on collective total effective dose (TED). The TED is comprised of the effective dose (ED) from external sources, which includes neutron and photon radiation, and the internal committed effective dose (CED), which results from the intake of radioactive material into the body. The collective ED from photon exposure decreased by 23% between 2011 and 2012, while the neutron dose increased by 5%. The internal dose components of the collective TED decreased by 7%. Over the past 5-year period, 99.99% of the individuals receiving measurable TED have received doses below the 2 roentgen equivalent in man (rems) (20 millisievert [mSv]) TED administrative control level (ACL), which is well below the DOE regulatory limit of 5 rems (50 mSv) TED annually. The occupational radiation exposure records show that in 2012, DOE facilities continued to comply with DOE dose limits and ACLs and worked to minimize exposure to individuals. The DOE collective TED decreased 17.1% from 2011 to 2012. The collective TED decreased at three of the five sites with the largest collective TED. u Idaho Site – Collective dose reductions were achieved as a result of continuing improvements at the Advanced Mixed Waste Treatment Project (AMWTP) through the planning of drum movements that reduced the number of times a container is handled; placement of waste containers that created highradiation areas in a centralized location; and increased worker awareness of high-dose rate areas. In addition, Idaho had the largest decrease in the total number of workers with measurable TED (1,143 fewer workers). u Hanford Site (Hanford) – An overall reduction of decontamination and decommissioning (D&D) activities at the Plutonium Finishing Plant (PFP) and Transuranic (TRU) retrieval activities resulted in collective dose reductions. u Savannah River Site (SRS) – Reductions were achieved through ALARA initiatives employed site wide. The Solid Waste Management Facility used extended specialty tools, cameras and lead shield walls to facilitate removal of drums. These tools and techniques reduce exposure time through improved efficiency, increase distance from the source of radiation by remote monitoring, shield the workers to lower the dose rate, and reduce the potential for contamination and release of material through repacking of waste. Overall, from 2011 to 2012, there was a 19% decrease in the number of workers with measurable dose. Furthermore, due to a slight decrease in both the DOE workforce (7%) and monitored workers (10%), the ratio of workers with measurable doses to monitored workers decreased to 13%. Another primary indicator of the level of radiation exposure covered in this report is the average measurable dose, which normalizes the collective dose over the population of workers who actually received a measurable dose. The average measurable TED increased by 3% from 2011 to 2012. Additional analyses show that the dose distribution in 2012 was similar to the distribution in 2011. In 2012, 13% of the monitored workers received a measurable TED and the average measurable TED, 0.069 rem, was less than 2% of the DOE limit. From 2011 to 2012, the collective TED and the number of individuals with measurable TED decreased 17.1% and 19%, respectively. These decreases were mainly due to an overall reduction of D&D activities at the PFP and TRU retrieval activities at Hanford; a 78% decrease in the number of targeted waste drums that were processed at the Idaho Site’s Accelerated Retrieval Project (ARP) from 5,566 drums in 2011 to a total of 1,211 drums processed in 2012; and ALARA initiatives employed site wide at SRS. In addition, the decreases were the result of decreased American Recovery and Reinvestment Act (ARRA) activities and continuing D&D, particularly at the DOE sites that comprise the majority of DOE collective dose. Over the past 5 years, the size of the monitored workforce has remained at a fairly stable level (within 12%), while the collective dose has varied up to 37%. No reported doses exceeded the DOE occupational limit of 5 rems TED in 2012 and no reported doses exceeded the DOE ACL of 2 rems TED.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2012

Diffusion Dominant Solute Transport Modelling in Fractured Media Under Deep Geological Environment - 12211

Deep geologic disposal of high activity and long-lived radioactive waste is gaining increasing support in many countries, where suitable low permeability geological formation in combination with engineered barriers are used to provide long term waste contaminant and minimise the impacts to the environment and risk to the biosphere. This modelling study examines the solute transport in fractured media under low flow velocities that are relevant to a deep geological environment. In particular, reactive solute transport through fractured media is studied using a 2-D model, that considers advection and diffusion, to explore the coupled effects of kinetic and equilibrium chemical processes. The effects of water velocity in the fracture, matrix porosity and diffusion on solute transport are investigated and discussed. Some illustrative modelled results are presented to demonstrate the use of the model to examine the effects of media degradation on solute transport, under the influences of hydrogeological (diffusion dominant) and microbially mediated chemical processes. The challenges facing the prediction of long term degradation such as cracks evolution, interaction and coalescence are highlighted. The potential of a novel microstructure informed modelling approach to account for these effects is discussed, particularly with respect to investigating multiple phenomena impact on material performance. The GRM code is used to examine the effects of media degradation for a geological waste disposal package, under the combined hydrogeological (diffusion dominant) and chemical effects in low groundwater flow conditions that are typical of deep geological disposal systems. An illustrative reactive transport modelling application demonstrates the use of the code to examine the interplay of kinetic controlled biogeochemical reactive processes with advective and diffusive transport, under the influence of media degradation. The initial model results are encouraging which show the disposal system to evolve in a physically realistic manner. In the example presented the reactive-transport coupling develops chemically reducing zones, which limit the transport of uranium. This illustrates the potential significance of media degradation and chemical effect on the transport of radionuclides which would need to be taken into account when examining the long-term behaviour and containment properties of the geological disposal system. Microstructure-informed modelling and its potential linkage with continuum flow modelling is a subject of ongoing studies. The approach of microstructure-informed modelling is discussed to provide insight and a mechanistic understanding of macroscopic parameters and their evolution. The proposed theoretical and methodological basis for microstructure-informed modelling of porous quasi-brittle media has the potential to develop into an explanatory and predictive tool for deriving mechanism-based, as opposed to phenomenological, evolution laws for macroscopic properties. These concepts in micro-scale modelling are likely to be applicable to the diffusion process, in addition to advective transport illustrated here for porous media. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale (Final Report)

This project titled “Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale” represents a collaborative effort between the University of Michigan (Jason Demers, PI) and Oak Ridge National Laboratory (Scott Brooks, co-I). Much has been learned about mercury (Hg) cycling in stream ecosystems, and East Fork Poplar Creek (EFPC) in particular, through decades of previous research. Nevertheless, some of the most fundamental questions regarding the sources of bioavailable Hg and its transformation to toxic methylmercury (MeHg) have remained unanswered. These fundamental questions include: (1) what are the sources and biogeochemical processes that lead to the input of dissolved Hg to stream water across critical subsurface interfaces within stream ecosystems, and EFPC in particular? and (2) what are the sources and biogeochemical processes that control the production and fate of bioaccumulative MeHg within stream ecosystems, and in EFPC in particular? To address these fundamental questions, our project aimed to couple laboratory experiments and field observations, both utilizing natural abundance Hg stable isotope techniques, to identify the processes responsible for generating mobile, bioavailable dissolved Hg from recalcitrant legacy sources within critical subsurface zones (e.g., streambed hyporheic zone, riparian floodplain subsurface). We used the isotopic signature of this bioavailable dissolved Hg to track its mobilization across these critical interfaces in order to link diffuse subsurface sources of dissolved Hg with increases in surface water dissolved Hg flux measured at the watershed scale. Additionally, our research aimed to determine the isotopic composition of MeHg within these same critical subsurface zones. We directly assessed the isotopic composition of MeHg within biota in order to gain insight into which subsurface sources of inorganic Hg and toxic MeHg are available for bioaccumulation within the EFPC ecosystem. Net fluxes of dissolved Hg along the flow path of EFPC were shown to vary spatially and temporally. In the Upper EFPC, within the Y12 boundary, stream water flux of dissolved Hg consistently decreased between the outfall and the downstream boundary of Y12 (57% ± 29%, 1SD). Within the Upper EFPC, an assessment of Hg isotopic composition suggested that losses were strongly reaction-driven, although isotopic diagnostics did not conform to any known processes. Downstream of Y12, in the upper reach of the Lower EFPC, dissolved Hg fluxes tended to increase during the dormant season (net gain of 11-120%), and decrease during the growing season (net loss of 23% +/- 18%, 1SD). In the downstream-most reach of Lower EFPC, dissolved Hg fluxes increased by 12-108% in 9 out of 10 monthly assessments. Overall, diffuse fluxes from the non-Y12 watershed accounted for 34% (+/- 17%, 1SD) of all dissolved Hg exported during base flow. Within Lower EFPC, an assessment of Hg isotopic composition was consistent with the contribution of diffuse Hg inputs from high-concentration hotspots within riparian floodplains and streambed hyporheic pore water. To investigate remobilization of recalcitrant Hg from legacy sediment sources, we developed procedures that coupled isotopic analysis with sequential extractions of streambed sediment. We found that the proportion of weakly-bound Hg within EFPC streambed sediment was relatively small, but could still account for a large proportion of the annual flux of dissolved Hg from EFPC. These sequential extractions also showed that this weakly-bound Hg fraction could be replenished from the much larger fraction of recalcitrant Hg in sediment. The isotopic composition of these weakly-bound and remobilized recalcitrant Hg fractions within the sediment was consistent with high-concentration dissolved Hg hotspots within hyporheic pore water. Thus, this research provided novel evidence that legacy mercury sources within streambed sediment could provide an ongoing contribution of dissolved Hg to surface waters. Finally, we developed new methods for the direct determination of the MeHg isotopic composition of organisms, which allowed a more direct evaluation of inorganic Hg and MeHg sources accumulating in the food web. We found that fish and aquatic invertebrates in both EFPC and a regional background site obtained inorganic Hg and MeHg from multiple isotopically distinct sources, including sediment, suspended particulates, and periphyton. Photodemethylation was found to be an important reaction influencing MeHg dynamics at both sites. However, the balance of microbial methylation and demethylation processes differed between the two streams, with fractionation resulting from methylation and demethylation processes being relatively in balance within the regional background site, whereas microbial methylation appeared to be dominant over microbial demethylation within the EFPC ecosystem. Broadly, the application of Hg isotopic analysis in this study led to numerous novel insights regarding the biogeochemical cycling of Hg in stream ecosystems. This research project promoted the development of two new approaches, including the coupling of sequential extractions with Hg isotopic analysis to assess remobilization of recalcitrant Hg within sediments, and a new method for the isotopic analysis of MeHg isolated from environmental samples. Both of these efforts represent advances in capacity for the field of mercury isotopic analysis and environmental assessment. Overall, this study demonstrates that the application of Hg stable isotope techniques continues to provide new insights into the biogeochemical cycling of Hg in complex aquatic environments, both within the EFPC and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Preliminary Evaluation of Cesium Distribution for Wet Sieving Process Planned for Soil Decontamination in Japan - 13104

For the purpose of decontaminating radioactive cesium from a huge amount of soil, which has been estimated to be 1.2x10{sup 8} m{sup 3} by excavating to a 5-cm depth from the surface of Fukushima Prefecture where a severe nuclear accident occurred at TEPCO's power generating site and has emitted a significant amount of radioactive materials, mainly radioactive cesium, a wet sieving process was selected as one of effective methods available in Japan. Some private companies have demonstrated this process for soil treatment in the Fukushima area by testing at their plants. The results were very promising, and a full-fledged application is expected to follow. In the present study, we spiked several aqueous samples containing soil collected from an industrial wet sieving plant located near our university for the recycling of construction wastes with non-radioactive cesium hydroxide. The present study provides scientific data concerning the effectiveness in volume reduction of the contaminated soil by a wet sieving process as well as the cesium distribution between the liquid phase and clay minerals for each sub-process of the full-scale one, but a simulating plant equipped with a process of coagulating sedimentation and operational safety fundamentals for the plant. Especially for the latter aspect, the study showed that clay minerals of submicron size strongly bind a high content of cesium, which was only slightly removed by coagulation with natural sedimentation (1 G) nor centrifugal sedimentation (3,700 G) and some of the cesium may be transferred to the effluent or recycled water. By applying ultracentrifugation (257,000 G), most of submicron clay minerals containing cesium was removed, and the cesium amount which might be transferred to the effluent or recycled water, could be reduced to less than 2.3 % of the original design by the addition of a cesium barrier consisting of ultracentrifugation or a hollow fiber membrane. (authors)

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DOE OSTI2016

Highly-defective nanocrystals of ZnS formed via dissimilatory bacterial sulfate reduction: A comparative study with their abiogenic analogues

The physicochemical properties of a (nano)mineral are strongly affected by its formation processes, and thus, may indicate the (nano)mineral’s formation environment and mechanism. This correlation, although relevant to a myriad of geological, environmental, and material-science processes, has not yet been fully appreciated and systematically explored. In this study, using the Zn–S system, we demonstrate that biological and abiotic processes at similar experimental conditions can produce distinctive particle size, morphology, and crystal structure in the formed ZnS. Specifically, bacterial sulfate reduction led to the formation of highly-defective nanocrystals of mixed sphalerite and wurtzite in a range of ~4–12 nm. By comparison, the abiotic procedures of titration- or diffusion-controlled precipitation resulted in the formation of polycrystalline aggregates that contained randomly-oriented, ultrafine crystals below ~2–3 nm. The poor crystallinity in the abiogenic samples, regardless of the sulfide addition rates, reveals an overall nucleation-dominated, crystal growth-restricted pathway for the formation of ZnS from low-temperature aqueous solutions. The difficulty in the ZnS crystallization likely stems from the intrinsic surface instability of the ZnS growth units (i.e., in the form of nanoclusters) resulting from the dipole–dipole interactions of the unit with surrounding water molecules. In the biogenic samples, the ZnS crystallinity was significantly improved, indicating that the presence of bacterial metabolites somehow promoted the crystallization process. With evidence for the enlarged {1 1 1} planes in the biogenic nanocrystals, we attribute this enhancement mainly to the selective interaction of the bacterial metabolites with polar faces of the ZnS growth units, which might have effectively screened the dipole moments in the growth units and enabled their crystallographic assembly. By revealing the intrinsic difficulty and specific pathways for the ZnS crystallization, we also present viable explanations for the exclusive occurrence of structural defects in {1 1 1} planes of the biogenic nanocrystals. The findings of our study provide insight into the origin and fate of metal sulfide nanoparticles in the environment, and have implications for biomineralization, bioremediation of metal-contaminated sites, and bacterial production of functional nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Laboratory Evaluation to Increase Effectiveness of Field-Scale Soil Flushing in the Hanford 100 Areas

This laboratory study was initiated to develop an improved technical understanding of the key controlling geochemical and physical processes of mobilizing residual Cr(VI) in Hanford sediments to provide increased effectiveness in soil flushing activities planned for Hanford 100 Areas. This was accomplished by (1) quantifying Cr mass, release rate, and surface phase changes as Cr is leached from different Hanford sediments; (2) maximizing Cr leaching during soil flushing by evaluating different leach solutions and leach strategies; and (3) minimizing leaching of remaining residual Cr after soil flushing ends. To quantify geochemical controls on Cr leaching from sediments, sequential liquid extractions were used to identify aqueous, adsorbed, and solid Cr surface phases (precipitates or Cr incorporated into other phases) before and after water-saturated and unsaturated leach experiments with pH 8 artificial groundwater and with other amendment solutions. Changes in the Cr release rate from sediments were also correlated to changes in Cr surface phases. During unsaturated infiltration, water advection occurs primarily through larger pores, with less movement through smaller grain layers leading to a slower release of Cr trapped in smaller pores next to smaller grains. To quantify these physical controls on Cr leaching from sediments, 10 ft high 1-D infiltration experiments were conducted at differing leach solution application rates, and Cr leaching during application and subsequent residual water flow was quantified. Qualitative 2-D experiments were also conducted to evaluate surfactant addition to increase flow in low-permeability zones. Cr-contaminated Hanford sediments from the 100-H, 100-K, 100-D, and 200 East Areas exhibited a wide variety of leach behavior from rapid release of a small amount of Cr to fast (i.e., minutes) and slow (i.e., hours or more) release of high Cr. Sediments with low labile Cr (< 0.2 µg/g) exhibited fast Cr release but less overall release, and most (>95%) leached from the sediments within a few pore volumes in water-saturated columns. With nearly no sorption of chromate, aqueous and sorbed Cr (as chromate) were released quickly from sediment within the first few pore volumes, resulting in high leach concentrations, fast initial Cr release rates, and changes in pre- and post-leach extractions. In contrast, sediments with high labile Cr (0.2 to 20 µg/g) exhibited a combination of fast and slow Cr release due to multiple Cr surface phases contributing to Cr release from the sediment at different rates with greater overall release. This resulted in elevated Cr effluent concentrations even after dozens of pore volumes were leached. In addition, the Cr release rate decreased with increasing time during leaching. A decrease in labile Cr (aqueous Cr, adsorbed Cr, pH 5 acetate dissolved precipitates) in post-leach extractions compared to pre-leach extractions showed initial aqueous and adsorbed Cr release, followed by dissolution of high-solubility precipitates such as CaCrO 4 (if present), then slow dissolution of calcite that may contain some chromate and possibly BaCrO 4 . The labile Cr in all sediments correlated well with the Cr release rate (r 2 = 0.81). Labile Cr also correlated well with the leached mass in water-saturated columns (r 2 = 0.98), and therefore can be used for prediction of potential removal with flushing applications.

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DOE OSTI2017

Using Prescribed Fire to Manage the Fernald On-Site Disposal Facility Vegetated Cap - 17401

The Fernald Preserve is a former uranium processing plant that underwent extensive remediation pursuant to the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). It is situated on a 425 ha (1,050 acre) tract of land, approximately 29 km (18 miles) northwest of Cincinnati, Ohio. Remedial activities and subsequent ecological restoration have converted the site from an industrial production facility to an undeveloped park, encompassing a series of wetlands, prairies, and forested communities. The remediation of buildings and soil contamination was completed in 2006, but aquifer remediation is ongoing. Since 2007, the site has been managed by the US Department of Energy (DOE) Office of Legacy Management. Portions of the site are open to the public, with approximately 11 km (7 miles) of walking trails that are open year-round and a visitors center. Site remediation included the construction of an On-Site Disposal Facility (OSDF) for the long-term disposal of contaminated soil and building materials. The OSDF consists of eight disposal cells that encompass approximately 30 hectares (75 acres) on the eastern portion of the Fernald site. Cells are lined and capped, and each has a separate leak detection and leachate collection system. The integrated cap is vegetated with native grasses and forbs. Management of the Fernald Preserve includes the monitoring and maintenance of ecologically restored communities and the vegetated OSDF cap, as required by the site's institutional controls plan. Prescribed burning is recognized as the preferred method for prairie management. Prescribed fire has been used at the Fernald site since 2009 for established prairies in restored areas, but not on the OSDF cap. Stakeholders had reservations regarding the safety of using prescribed fire on the OSDF cap. Because of that, vegetation on the cap was managed as a grassland community. It was mowed, raked, and baled to remove thatch, and promote the continued establishment of native grasses and forbs. Since agricultural use is restricted at the site, the resulting hay bales were kept on property and reused as organic matter and mulch. Over time, more hay bales were being generated in a season than were reused. Therefore in 2015, DOE decided to revisit stakeholder acceptance of prescribed fire on the OSDF cap. Ongoing relationships with local stakeholders allowed for extensive discussions regarding the current management and proposed use of prescribed fire on the OSDF cap. The public was provided information about the planning and implementation of prescribed burns at the site and invited to observe the execution of a successful site burn. This approach led to stakeholder acceptance of DOE's proposal, and vegetation on the caps of cells 4, 5, and 6 was burned in late March 2016. The burn was successful and resulted in several benefits from a land stewardship and cost perspective. This paper details the stakeholder engagement approach and the resulting benefits from the use of prescribed fire on the OSDF cap. (authors)

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DOE OSTI2014

Radionuclide Migration through Sediment and Concrete: 16 Years of Investigations

The Waste Management Project provides safe, compliant, and cost-effective waste management services for the Hanford Site and the U.S. Department of Energy (DOE) complex. Part of these services includes safe disposal of low-level waste and mixed low-level waste at the Hanford Low-Level Waste Burial Grounds in accordance with the requirements of DOE Order 435.1, Radioactive Waste Management. To partially satisfy these requirements, performance assessment analyses were completed and approved. DOE Order 435.1 also requires continuing data collection to increase confidence in the critical assumptions used in these analyses to characterize the operational features of the disposal facility that are relied on to satisfy the performance objectives identified in the order. Cement-based solidification and stabilization is considered for hazardous waste disposal because it is easily done and cost-efficient. One critical assumption is that concrete will be used as a waste form or container material at the Hanford Site to control and minimize the release of radionuclide constituents in waste into the surrounding environment. Concrete encasement would contain and isolate the waste packages from the hydrologic environment and act as an intrusion barrier. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. The radionuclides iodine-129, selenium-75, technetium-99, and uranium-238 have been identified as long-term dose contributors (Mann et al. 2001; Wood et al. 1995). Because of their anionic nature in aqueous solutions, these constituents of potential concern may be released from the encased concrete by mass flow and/or diffusion and migrate into the surrounding subsurface environment (Serne et al. 1989; 1992; 1993a, b; 1995). Therefore, it is necessary to assess the performance of the concrete encasement structure and the ability of the surrounding soil to retard radionuclide migration. Each of the test methods performed throughout the lifetime of the project has focused on different aspects of the concrete waste form weathering process. Diffusion of different analytes [technetium-99 (Tc-99), iodine-125 (I-125), stable iodine (I), uranium (U), and rhenium (Re)] has been quantified from experiments under both saturated and unsaturated conditions. The water-saturated conditions provide a conservative estimate of the concrete’s performance in situ, and the unsaturated conditions provide a more accurate estimate of the diffusion of contaminants from the concrete.

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DOE OSTI2020

The Nature and State of Groundwater Contamination at the Nevada National Security Site: What Have We Learned from Decades of Groundwater Analysis? - 20337

The regulatory framework for remediating radionuclide contamination from underground nuclear testing at the Nevada National Security Site (NNSS) is based on a combination of characterization and modeling studies, monitoring, and institutional controls [1]. Currently, tritium is the largest contributor (∼90%) to the estimated 44.6 million-curie radionuclide inventory resulting from underground testing [2]. Because of its short half-life (12.32 years), its relative contribution reduces below 10% of the total radiologic inventory over the next 120 years as a result of radioactive decay. Although tritium levels are observed well above the Safe Drinking Water Act (SDWA) maximum contaminant levels (MCLs) in groundwater, other radionuclides are well below their MCLs except within the nuclear test near-field (nuclear test cavity and chimney) environment. In fact, most device-derived radionuclides are below their MCL in groundwater even in samples collected from this near-field environment. The distribution of radionuclides following the nuclear detonation greatly influences the availability of potential contaminants for groundwater transport. Tritium is initially distributed in the gas phase, later as tritiated water in steam, and finally as liquid water, and is available to groundwater transport away from the near-field environment. Other radionuclides that are mobile in groundwater are {sup 14}C, {sup 36}Cl, {sup 99}Tc, and {sup 129}I though their radiologic inventory is small when compared to tritium. Many radionuclides (e.g. U, Pu, Am) are incorporated to a significant extent into the melt glass at the bottom of the cavity and are accessible to groundwater primarily through the slow process of glass dissolution. These radionuclides are also adsorbed to the surfaces of the crushed rock within the cavity and chimney which limits their migration in groundwater. Although colloid facilitated transport of radionuclides at the NNSS has been observed [3], radionuclide concentrations decrease with time and migration distances due to desorption and colloid filtration processes. Current studies indicate that radionuclides associated with colloids are unlikely to migrate downgradient from NNSS underground nuclear tests at concentrations above the SDWA MCL [4][5]. The results of over 50 years of sampling, along with an understanding of these post detonation processes, indicate that tritium is the only contaminant of concern downgradient of testing and that even tritium will not exceed its MCL in groundwater after ∼120 years. Although other longer-lived radionuclides may continue to be released slowly from the near-field environment they will likely never reach levels exceeding their MCLs in groundwater downgradient of the NNSS. Groundwater monitoring will continue to verify these observations. (authors)

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