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At least 631 records · Page 35

Advanced Sorbent Structure Recovery of REEs, Precious Metals and Other Valuable Metals from Geothermal Waters and Its Associated Technoeconomics

This work evaluates, develops and demonstrates flexible, scalable mineral extraction technology for geothermal brines based upon solid phase sorbent materials with a specific focus upon rare earth elements (REEs). The selected organic and inorganic sorbent materials demonstrated high performance for collection of trace REEs, precious and valuable metals beyond commercially available sorbents. This report details the organic and inorganic sorbent uptake, performance, and collection efficiency results for La, Eu, Ho, Ag, Cu and Zn, as well as the characterization of these select sorbent materials. The report also contains estimated costs from an in-depth techno-economic analysis of a scaled up separation process. The estimated financial payback period for installing this equipment varies between 3.3 to 5.7 years depending on the brine flow rate of the geothermal resource.

15 GEOTHERMAL ENERGY↗

Marine Corps Base Camp Lejeune Barrier Morphology- Elevation of Bear Island Sept 2011

Critical military training and testing on lands along the nation’s coastal and estuarine shorelines are increasingly placed at risk because of encroachment pressures in surrounding areas, impairments due to other anthropogenic disturbances, and changes in climate and sea level. The U.S. Department of Defense (DoD) intends to enhance and sustain its training and testing assets and also optimize its stewardship of natural resources through the development and application of an ecosystem-based management approach on DoD installations. To accomplish this goal, particularly for installations in estuarine/coastal environments, the Strategic Environmental Research and Development Program (SERDP) launched the Defense Coastal/Estuarine Research Program (DCERP) as a 10-year effort at Marine Corps Base Camp Lejeune (MCBCL) in North Carolina. The results of the second 5 years of the program (DCERP2) are presented in the DCERP2 Final Report.There were four overarching objectives of DCERP2. The first objective was to understand the effects of climate change impacts, including warming temperatures, variability in the hydrological cycle, storm events, and sea level rise on the coastal ecosystems at MCBCL from observations and measurements made over the 10-year program. The second objective was to understand the carbon cycle of the coastal and terrestrial ecosystems at MCBCL through a highly integrated sampling program. The third objective was to develop models, tools, and indicators to evaluate current and projected future ecosystem state changes and translate scientific findings into actionable information for installation managers. The last objective was to recommend adaptive management strategies to sustain ecosystem natural resources within the context of an active military installation.This grid file was created from data collected using a Riegl 3-D laser scanner. Millions of x, y, and z points from Onslow Beach were processed using the MARS software package to define a bare-earth model. The beach was broken into a series of zones, each zone was processed separately, and this grid covers all of the zones. Data were collected during the same week and around the low tide (two hours before and after low tide).

54 ENVIRONMENTAL SCIENCES↗

Marine Corps Base Camp Lejeune Bear Island Laser Scanning data

Critical military training and testing on lands along the nation’s coastal and estuarine shorelines are increasingly placed at risk because of development pressures in surrounding areas, impairments due to other anthropogenic disturbances, and increasing requirements for compliance with environmental regulations. The U.S. Department of Defense (DoD) intends to enhance and sustain its training and testing assets and to optimize its stewardship of natural resources through the development and application of an ecosystem-based management approach on DoD installations. To accomplish this goal, particularly for installations in estuarine/coastal environments, the Strategic Environmental Research and Development Program (SERDP) launched the Defense Coastal/Estuarine Research Program (DCERP) as a minimum 10-year effort at Marine Corps Base Camp Lejeune (MCBCL) in North Carolina. The results of the first six years of the program (DCERP1) are presented here.The overarching objectives of DCERP are to: (1) understand the effects of military training activities, infrastructure development, and other coastal military installations; (2) develop models, tools, and indicators to evaluate ecosystem health; and (3) recommend adaptive management strategies to sustain ecosystem natural resources within the context of an active military installation.This grid file was created from data collected using a Riegl 3-D laser scanner. Millions of x, y, and z points from Onslow Beach were processed using the Terrasolid software package to define a bare-earth model. The beach was broken into a series of zones, each zone was processed separately, and this grid covers all of the zones. Data were collected during the same week and around the low tide (two hours before and after low tide).

54 ENVIRONMENTAL SCIENCES↗

Marine Corps Base Camp Lejeune Barrier Morphology - Elevation of Onslow Beach

Critical military training and testing on lands along the nation’s coastal and estuarine shorelines are increasingly placed at risk because of encroachment pressures in surrounding areas, impairments due to other anthropogenic disturbances, and changes in climate and sea level. The U.S. Department of Defense (DoD) intends to enhance and sustain its training and testing assets and also optimize its stewardship of natural resources through the development and application of an ecosystem-based management approach on DoD installations. To accomplish this goal, particularly for installations in estuarine/coastal environments, the Strategic Environmental Research and Development Program (SERDP) launched the Defense Coastal/Estuarine Research Program (DCERP) as a 10-year effort at Marine Corps Base Camp Lejeune (MCBCL) in North Carolina. The results of the second 5 years of the program (DCERP2) are presented in the DCERP2 Final Report.There were four overarching objectives of DCERP2. The first objective was to understand the effects of climate change impacts, including warming temperatures, variability in the hydrological cycle, storm events, and sea level rise on the coastal ecosystems at MCBCL from observations and measurements made over the 10-year program. The second objective was to understand the carbon cycle of the coastal and terrestrial ecosystems at MCBCL through a highly integrated sampling program. The third objective was to develop models, tools, and indicators to evaluate current and projected future ecosystem state changes and translate scientific findings into actionable information for installation managers. The last objective was to recommend adaptive management strategies to sustain ecosystem natural resources within the context of an active military installation.This grid file was created from data collected using a Riegl 3-D laser scanner. Millions of x, y, and z points from Onslow Beach were processed using the MARS software package to define a bare-earth model. The beach was broken into a series of zones, each zone was processed separately, and this grid covers all of the zones. Data were collected during the same week and around the low tide (two hours before and after low tide).

54 ENVIRONMENTAL SCIENCES↗

A Sustainable Approach to Decision-Making in CCUS Systems

This study proposes a methodology for operational decision-making leading to the sustainability CO 2 -EOR systems. The methodology is a simple, yet comprehensive, integration of environmental and economic carbon capture, utilization and storage (CCUS) performance. Understanding the interplay between the environmental and economic conditions allows the EOR operator to manage the CO 2 -EOR flood so it remains within the limits of carbon balance neutrality and favorable economics under given prices and costs. The environmental performance and the main operational inputs (fluid production, CO 2 injection, and purchase requirements) were taken from a dynamic carbon Life Cycle Assessment (LCA) study previously performed for a CO 2 -EOR site in Cranfield, Mississippi. The LCA study accounts for greenhouse gases (GHG) emissions within a gate-to-grave CCUS system boundary, considering four different CO 2 injection strategies and four gas separation processes. The economic performance assessment was made through a marginalist analysis (Marginalist Production Theory), which determines important technical and economic relations through basic differential calculus derived from production, cost, and income functions. This method allows to define the operational economic optimum (optimum profit). The assessment considers four CO 2 price scenarios and uses World Bank estimated oil prices. In a first step of the proposed methodology, environmental limits of the operation are estimated. These limits are then compared with operative maximum productivity as well as with the economic optimum. According to the methodology, the EOR operation is sustainable as long as the environmental optimum is greater, or lasts longer, than the economic optimum along the project’s life. Results show that for this operation and assumed parameters, CO 2 -EOR could be classified as a sustainable activity depending on the operator’s strategic decision-making. In the case study, all injection strategies reach the environmental optimum after maximum productivity is reached. As a result, only two strategies (continuous gas injection and water alternating gas) find their economic optimum within the environmental limits, fulfilling the defined necessary and sufficient condition for CCUS sustainability.

02 PETROLEUM↗

Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products

Glass-ceramic waste form development began in FY 2010 examining two combined waste stream options: (1) alkaline earth (CS) + lanthanide (Ln), and (2) + transition metal (TM) fission-product waste streams generated by the uranium extraction (UREX+) separations process. Glass-ceramics were successfully developed for both options however; Option 2 was selected over Option 1, at the conclusion of 2010, because Option 2 immobilized all three waste streams with only a minimal decrease in waste loading. During the first year, a series of three glass (Option 2) were fabricated that varied waste loading-WL (42, 45, and 50 mass%) at fixed molar ratios of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali both at 1.75. These glass-ceramics were slow cooled and characterized in terms of phase assemblage and preliminary irradiation stability. This fiscal year, further characterization was performed on the FY 2010 Option 2 glass-ceramics in terms of: static leach testing, phase analysis by transmission electron microscopy (TEM), and irradiation stability (electron and ion). Also, a new series of glass-ceramics were developed for Option 2 that varied the additives: Al{sub 2}O{sub 3} (0-6 mass%), molar ratio of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali (1.75 to 2.25) and waste loading (50, 55, and 60 mass%). Lastly, phase pure powellite and oxyapatite were synthesized for irradiation studies. Results of this fiscal year studies showed compositional flexibility, chemical stability, and radiation stability in the current glass-ceramic system. First, the phase assemblages and microstructure of all of the FY 2010 and 2011 glass-ceramics are very similar once subjected to the slow cool heat treatment. The phases identified in these glass-ceramics were oxyapatite, powellite, cerianite, and ln-borosilicate. This shows that variations in waste loading or additives can be accommodated without drastically changing the phase assemblage of the waste form, thus making the processing and performance characteristics of the waste form more predictable/flexible. However, in the future, the glass phase still needs to be accurately characterized to determine the effects of waste loading and additives on the glass structure. Initial investigations show a borosilicate glass phase rich in silica. Second, the normalized concentrations of elements leached from the waste form during static leach testing were all below 0.6 g/L after 28d at 90 C, by the Product Consistency Test (PCT), method B. These normalized concentrations are on par with durable waste glasses such as the Low-Activity Reference Material (LRM) glass. The release rates for the crystalline phases (oxyapatite and powellite) appear to be lower (more durable) than the glass phase based on the relatively low release rates of Mo, Ca, and Ln found in the crystalline phases compared to Na and B that are mainly observed in the glass phase. However, further static leach testing on individual crystalline phases is needed to confirm this statement. Third, Ion irradiation and In situ TEM observations suggest that these crystalline phases (such as oxyapatite, ln-borosilicate, and powellite) in silicate based glass ceramic waste forms exhibit stability to 1000 years at anticipated doses (2 x 10{sup 10}-2 x 10{sup 11} Gy). This is adequate for the short lived isotopes in the waste, which lead to a maximum cumulative dose of {approx}7 x 10{sup 9} Gy, reached after {approx}100 yrs, beyond which the dose contributions are negligible. The cumulate dose calculations are based on a glass-ceramic at WL = 50 mass%, where the fuel has a burn-up of 51GWd/MTIHM, immobilized after 5 yr decay from reactor discharge.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Alternative Electrochemical Salt Waste Forms, Summary of FY/CY2011 Results

This report summarizes the 2011 fiscal+calendar year efforts for developing waste forms for a spent salt generated in reprocessing nuclear fuel with an electrochemical separations process. The two waste forms are tellurite (TeO 2 -based) glasses and sol-gel-derived high-halide mineral analogs to stable minerals found in nature.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Independent Verification Survey of the SPRU Lower Level Hillside Area at the Knolls Atomic Power Laboratory, Niskayuna, New York (Final Report)

During August 10, 2011 through August 19, 2011, and October 23, 2011 through November 4, 2011, ORAU/ORISE conducted verification survey activities at the Separations Process Research Unit (SPRU) site that included in-process inspections, surface scans, and soil sampling of the Lower Level Hillside Area. According to the Type-B Investigation Report, Sr-90 was the primary contributor to the majority of the activity (60 times greater than the Cs-137 activity). The evaluation of the scan data and sample results obtained during verification activities determined that the primary radionuclide of concern, Sr-90, was well below the agreed upon soil cleanup objective (SCO) of 30 pCi/g for the site. However, the concentration of Cs-137 in the four judgmental samples collected in final status survey (FSS) Units A and B was greater than the SCO. Both ORAU and aRc surveys identified higher Cs-137 concentrations in FSS Units A and B; the greatest concentrations were identified in FSS Unit A.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Award ER25844: Minimizing System Noise Effects for Extreme-Scale Scientific Simulation Through Function Delegation

In software running on distributed computing clusters, time spent on communication between nodes in the cluster can be a significant portion of the overall computation time; background operating system tasks and other computational noise on the nodes of the system can have a significant impact on the amount of time this communication takes, especially on large systems. The research completed in this period has improved understanding of when such noise will have a significant impact. Specifically, it was demonstrated that not just noise on the nodes, but also noise on the network between nodes can have a significant impact on computation time. It was also demonstrated that noise patterns matter more than noise intensity: very regular noise can cause less disruption than lighter (on average) but less regular noise. It was also demonstrated that the effect of noise is more prominent as the speed of the network between nodes is increased. Furthermore, a tracing tool, Netgauge, was improved via our work, and a system simulator, LogGOPSim, was developed; they can be used by application developers to improve performance of their program and by system designers to mitigate the effects of noise by adjusting the noise characteristics of the operating system. Both have been made freely available as open source programs. In the course of developing these tools, we demonstrated weaknesses in existing methodologies for modeling communication, and we introduced a more detailed model, LogGOPS, for simulating systems. Not only were the deleterious effects of noise explored but we have also offered solutions. Our studies of simulations of system noise have led to specific recommendations on tuning systems to mitigate noise. We have also improved existing approaches to mitigating noise. Non-blocking collective communication avoids the effects of noise by letting communication continue simultaneously with computation (thus being non-blocking), so that the delays in communication introduced by noise have a smaller impact on overall computation time. Potentially, noise can be reduced much further by offloading communication tasks to a separate processing element than the operating system is using. We have improved our library LibNBC, which provides an implementation of non-blocking collectives, via this work. During this research, our proposal to include non-blocking collectives (which used LibNBC as a reference implementation) in the upcoming MPI-3 standard was accepted. As MPI is a ubiquitous and important standard for communication in parallel computing, this demonstrates a certain acceptance of the practicality and desirability of non-blocking collectives. Now that non-blocking collectives are a part of the standard we can expect to see optimized platform-specific implementations of non-blocking collectives. Also as part of this work we have also developed a language GOAL (Global Operation Assembly Language) that can be used as a starting point for defining languages to express optimized communication algorithms.

97 MATHEMATICS AND COMPUTING↗

Extractant Design by Covalency

This project aims to provide an electronic structure-to-function understanding of extractants for actinide selective separation processes. The research entails a multi-disciplinary approach that integrates chemical syntheses, structural determination, K-edge X-ray Absorption Spectroscopy (XAS), and Density Functional Theory (DFT) calculations. In FY15, the project reached the final stage of testing the extraction performance of a new ligand design and preparing an americium-extractant complex for analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DIORAMA Communications

Diorama is written as a collection of modules that can run in separate threads or in separate processes. This defines a clear interface between the modules and also allows concurrent processing of different parts of the pipeline. The pipeline is determined by a description in a scenario file[Norman and Tornga, 2012, Tornga and Norman, 2014]. The scenario manager parses the XML scenario and sets up the sequence of modules which will generate an event, propagate the signal to a set of sensors, and then run processing modules on the results provided by those sensor simulations. During a run a variety of “observer” and “processor” modules can be invoked to do interim analysis of results. Observers do not modify the simulation results, while processors may affect the final result. At the end of a run results are collated and final reports are put out. A detailed description of the scenario file and how it puts together a simulation are given in [Tornga and Norman, 2014]. The processing pipeline and how to program it with the Diorama API is described in Tornga et al. [2015] and Tornga and Wakeford [2015]. In this report I describe the communications infrastructure that is used.

97 MATHEMATICS AND COMPUTING↗

Alpha Radiolysis of Nuclear Solvent Extraction Ligands Used for An(III) and Ln(III) Separations

This document is the final report for the Nuclear Energy Universities Program (NEUP) grant 10-910 (DE-AC07-05ID14517) “Alpha Radiolysis of Nuclear Solvent Extraction Ligands used for An(III) and Ln(III) Separations”. The goal of this work was to obtain a quantitative understanding of the impacts of both low Linear Energy Transfer (LET, gamma-rays) and high LET (alpha particles) radiation chemistry occurring in future large-scale separations processes. This quantitative understanding of the major radiation effects on diluents and ligands is essential for optimal process implementation, and could result in significant cost savings in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Depolymerization and Upgrading of Lignin for Vanillin Production: Cooperative Research and Development Final Report, CRADA Number CRD-14-545

Examine catalytic conversion of lignin using multifunctional catalysts that are able to depolymerize and oxidize lignin to a vanillin-rich stream. Examine separation processes for isolation of vanillin from product mixtures. Conduct preliminary experiments to determine if deconstructed lignin streams can be metabolized by Pseudomonas putida.

09 BIOMASS FUELS↗

Non-Ideality in Solvent Extraction Systems: PNNL FY 2014 Status Report

The overall objective of this project is to develop predictive modeling capabilities for advanced fuel cycle separation processes by gaining a fundamental quantitative understanding of non-ideality effects and speciation in relevant aqueous and organic solutions. Aqueous solutions containing actinides and lanthanides encountered during nuclear fuel reprocessing have high ionic strength and do not behave as ideal solutions. Activity coefficients must be calculated to take into account the deviation from ideality and predict their behavior. In FY 2012-2013, a convenient method for determining activity effects in aqueous electrolyte solutions was developed. Our initial experiments demonstrated that water activity and osmotic coefficients of the electrolyte solutions can be accurately measured by the combination of two techniques, a Water Activity Meter and Vapor Pressure Osmometry (VPO). The water activity measurements have been conducted for binary lanthanide solutions in wide concentration range for all lanthanides (La-Lu with the exception of Pm). The osmotic coefficients and Pitzer parameters for each binary system were obtained by the least squares fitting of the water activity data. However, application of Pitzer model for the quantitative evaluation of the activity effects in the multicomponent mixtures is difficult due to the large number of the required interaction parameters. In FY 2014, the applicability of the Bromley model for the determination of the Ln(NO 3 ) 3 activity coefficients was evaluated. The new Bromley parameters for the binary Ln(NO 3 ) 3 electrolytes were obtained based on the available literature and our experimental data. This allowed for the accurate prediction of the Ln(NO 3 ) 3 activity coefficients for the binary Ln(NO 3 ) 3 electrolytes. This model was then successfully implemented for the determination of the Ln(NO 3 ) 3 activity coefficients in the ternary Nd(NO 3 ) 3 /HNO 3 /H2O, Eu(NO 3 ) 3 /HNO 3 /H 2 O, and Eu(NO 3 ) 3 /NaNO 3 /H 2 O systems. The main achievement of this work is the verified pathway for the estimation of the activity coefficients in the multicomponent aqueous electrolyte systems. The accurate Bromley electrolytes contributions obtained in this work for the entire series of lanthanide(III) nitrates (except Pm) can be applied for predicting activity coefficients and non-ideality effects for multi-component systems containing these species. This work also provides the proof-of-principle of extending the model to more complex multicomponent systems. Moreover, this approach can also be applied to actinide-containing electrolyte systems, for determination of the activity coefficients in concentrated radioactive solutions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Radical Cations and Acid Protection during Radiolysis

Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO 3 . It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Radiation Chemistry of the Hydrophilic DGAs

Short chain diglycolamides (DGAs) are water soluble, and have been used as aqueous stripping and hold back agents in both European and American fuel cycle solvent extraction proposals. An understanding of the influence of radiation on these ligands is critical to the development and implementation of robust separation processes. Therefore, the rates of degradation under radiolysis were measured for four hydrophilic DGAs and compared to the organic-soluble DGAs. Water soluble DGAs were degraded at a faster rate than lipophilic DGAs, but were more stable with increasing molecular weight. The degradation products of the tetraethyldiglycolamide (TEDGA) were also identified and found to be analogous to those produced for lipophilic DGAs in irradiated alkanes. It was concluded that similar products are obtained since reactions in both diluents are by oxidation followed rupture of the weak ether linkage. The fast rate constants of the reactions of two hydrophilic DGAs with the oxidizing •OH radical product of water radiolysis are also shown. Since water-soluble DGAs have been proposed for use as stripping or holdback agents in both European and American fuel cycle scenarios this work was performed in collaboration with colleagues at Forschungszentrum Jülich (FZJ).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Functionalized Porous Organic Polymers as Uranium Nano-Traps for Efficient Recovery of Uranium from Seawater

The long-term use of nuclear power for energy applications relies on the secure and economical supply of nuclear fuel. Among various natural sources of uranium for use in nuclear reactors, seawater is highly appealing given that the oceans contain about 4.5 billion tons of dissolved uranium, almost 1000 times that estimated for mineral reserves. Nonetheless, the concentration of uranium in seawater is extremely low (3-3.3 mg L -1 or 3-3.3 ppb); this, coupled with the presence of a relatively high concentration of other metal ions, makes uranium recovery from seawater a challenge that requires the development of efficient and effective separation processes. Various adsorbent technologies based upon synthetic organic polymers, biopolymers, inorganic materials, mesoporous silica materials, porous carbon-based adsorbents, and ionic liquids have been widely developed for the extraction of uranium from seawater. However, these benchmark sorbent materials suffer from a number of drawbacks such as low adsorption capacity (typically 0.1~3.2 mg-U g -1 adsorbent), poor selectivity, and slow kinetics. Given the extreme complexity and vast volume of seawater, as well as the very low concentration of uranium present, to attain this ambitious task demands the design of adsorbents with high affinity and fast kinetics. The main objective of this project is to develop functional porous organic polymers (POPs) as a new type of adsorbent for mining uranium from seawater. This class of porous materials has quickly moved to the forefront of materials research due to their high internal surface areas, exceptional water/chemical stability, facile chemical tunability, and extraordinary capability to selectively adsorb large quantities of guest species The potential to deploy POPs in uranium extraction is related to the ease with which their internal surfaces can be decorated with high densities of strong binding sites. Beyond introducing postsynthetic modification, the specific functionalities also can be used as building units to be incorporated into porous frameworks. Our approach to fulfill this task involves the custom-design of POP-based uranium “nano-traps” via a “crystal engineering” guided design followed by stepwise post-synthetic modification. Furthermore, to increase the density of chelating groups and to enhance their affinity towards uranyl ions, judiciously designed chelating systems were constructed into porous organic polymers. Moreover, to improve the accessibility of the chelating groups and thereby the utilization efficiency, we assembled the chelating groups into highly crystalline materials where they are aligned in periodic arrays on the open channels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗