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Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H2 Production

A series of heteroleptic 17e- cobalt complexes, [CpCoII(PtBu2NPh2)](BF4), [CpC6F5CoII(PtBu2NPh2)](BF4), [CpC5F4NCoII(PtBu2NPh2)](BF4), [where P2tBuN2Ph = 1,5-diphenyl-3,7-di(tert-butyl)-1,5-diaza-3,7-diphosphacyclooctane, CpC6F5 = C5H4(C6F5), and CpC5F4N = C5H4(C5F4N)] were synthesized, and structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the CoIII/II couple of [CpC5F4NCoII(PtBu2NPh2)]+ appears 250 mV positive of the CoIII/II couple of [CpCoII(PtBu2NPh2)] as a result of the strongly electron-withdrawing perfluorpyridyl substituent on the Cp ring. Reduction of these paramagnetic CoII complexes by KC8 led to the diamagnetic 18e- complexes CpICo(PtBu2NPh2), CpC6F5CoI(PtBu2NPh2), CpC5F4NCoI(PtBu2NPh2), which were also characterized by crystallography. Protonation of these neutral CoI complexes led to the cobalt hydrides [CpCoIII(PtBu2NPh2)H](BF4), [CpC6F5CoIII(PtBu2NPh2)H](BF4), and [CpC5F4NCoIII(PtBu2NPh2)H](BF4). The cobalt hydride with the most electron-withdrawing Cp ligand, [CpC5F4NCoIII(PtBu2NPh2)H]+ is an electrocatalyst for production of H2 using 4-MeOC6H4NH3BF4 (pKaMeCN = 11.86) with a turnover frequency of 350 s-1 and an overpotential of 0.75 V. Experimental measurement of thermochemical data provided further insights into the thermodynamics of H2 elimination. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

hydrogen, catalysis, electrocatalysis, proton rela↗

Iron Complexes Bearing Diphosphine Ligands with Positioned Pendant Amines as Electrocatalysts for the Oxidation of H2

The synthesis and spectroscopic characterization of CpC5F4NFe(PtBu2NBn2)Cl, [3-Cl] (where C5F4N is the tetrafluorpyridyl substituent and PtBu2NBn2 = 1,5-di(tert-butyl)-3,7-di(benzyl)-1,5-diaza-3,7-diphosphacyclooctane) are reported. Complex 3-Cl and previously reported [CpC5F4NFe(PtBu2NtBu2)Cl], 4-Cl, are precursors to intermediates in the catalytic oxidation of H2, including CpC5F4NFe(PtBu2NBn2)H (3-H), CpC5F4NFe(PtBu2NtBu2)H (4-H), [CpC5F4NFe(PtBu2NBn2)]BArF4 ([3](BArF4), [CpC5F4NFe(PtBu2NtBu2)]BArF4 ([4](BArF4), [CpC5F4NFe(PtBu2NBn2)(H2)]BArF4 ([3-H2]BArF4), and [CpC5F4NFe(PtBu2NtBu2H)H]BArF4 ([4-FeH(NH)]BArF4). All of these complexes were characterized by spectroscopic and electrochemical studies; 3-Cl, 3-H and 4-Cl were also characterized by single crystal diffraction studies. 3-H and 4-H are electrocatalysts for H2 (1.0 atm) oxidation in the presence of a excess of the amine base N-methylpyrrolidine, with turnover frequencies at 22 °C of 2.5 s-1 and 0.5 s-1, and overpotentials at Ecat/2 of 235 mV and 95 mV, respectively. Studies of individual chemical and/or electrochemical reactions of the various intermediates provide important insights into the factors governing the overall catalytic activity for H2 oxidation, and provide important insights into the role of the pendant base of the [FeFe] hydrogenase active site. This work was supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

catalysis, iron, hydrogen↗

The interaction of reactants, intermediates and products with Cu ions in Cu-SSZ-13 NH3 SCR catalysts: An energetic and ab initio X-ray absorption modeling study

Copper-exchanged SSZ-13 (Cu-SSZ-13) provides excellent catalytic activity and hydrothermal stability in the selective catalytic reduction (SCR) of NOx by using NH3 as a reductant. In this contribution, we compare the most likely positions for Cu with a single charge compensating Al atom (ZCu), including the effect of the adsorption of reactants, intermediates and products of a NH3 SCR reaction by using first-principles calculations based on density functional theory. We find that the 6-membered ring (6MR) site is the most energetically favorable while the 8-membered ring (8MR) sites are less favorable with energy differences about 0.5 eV with respect to the 6MR site. Upon molecular adsorption, the energy differences between Cu in the 8MR and 6MR sites decreases and almost disappears, which means that the thermodynamic stability of ZCu with molecularly adsorbed species is nearly identical for Cu in different sites. Considering more complicated scenarios of NO (or CO) adsorption, we find that the co-adsorption of 2 NO (or 2 CO) molecules weakens their interaction with Cu, as well as their co-adsorption with OH and H2O. The X-ray absorption near edge structure (XANES) of Cu in Cu-SSZ-13 under different conditions was also modeled from first principles. We find that the pre-edge feature in the K-edge XANES of Cu in clean Cu-SSZ-13 with Cu in a 8MR site is induced by a 1s to 4s transition while there is no pre-edge peak when Cu is in a 6MR site. Molecular adsorption onto Cu in a 6MR or a 8MR site results in the same K-edge XANES. When NO is adsorbed onto Cu in SSZ-13, we find that the origin of the small pre-edge peak in the K-edge XANES lies in a 1s to 3d electron transition. On the other hand, when CO or N2 is adsorbed onto an isolated Cu atom in SSZ-13, a transition from the 1s state to the hybridized state of 3d and 4p results in a pre-edge peak in the K-edge of the XANES spectrum. It is also found that the edge position and intensity of the maximum peak of Cu K-edge XANES depend on the Cu locations and the adsorbed molecules. By studying the Cu K-edge XANES of ZCu with adsorption of species of different oxidizing power, we conclude that a higher oxidation state of Cu will result in a higher energy edge position in the Cu K-edge XANES. These results are expected to greatly aid our understanding of Cu-SSZ-13 SCR catalysts. This work was supported by institutional funds provided to JSM from the Voiland School of Chemical Engineering and Bioengineering. Financial support was also provided by the National Science Foundation GOALI program under contract Nos. CBET-1258717, CBET-1258715 and CBET-1258690. We thank Prof. Fabio Ribeiro, Mr. Atish Parekh, Prof. W. F. Schneider, Mr. Christopher Paolucci, Mr. Trunjoyo Anggara and Prof. Jeff Miller for stimulating discussions on the modeling of the XANES spectrum and Ms. Alyssa Hensley for her comments on the manuscript. J.Sz. acknowledges the financial support of this work by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. A portion of the computer time for the computational work was performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL. PNNL is a multi-program national laboratory operated for the US DOE by Battelle.

Zhang, Renqin↗

AVTA Federal Fleet PEV Readiness Data Logging and Characterization Study for the United States Forest Service: Caribou-Targhee National Forest

Battelle Energy Alliance, LLC, managing and operating contractor for the U.S. Department of Energy’s Idaho National Laboratory, is the lead laboratory for U.S. Department of Energy Advanced Vehicle Testing. Battelle Energy Alliance, LLC contracted with Intertek Testing Services, North America (ITSNA) to collect and evaluate data on federal fleet operations as part of the Advanced Vehicle Testing Activity’s Federal Fleet Vehicle Data Logging and Characterization study. The Advanced Vehicle Testing Activity study seeks to collect and evaluate data to validate the utilization of advanced electric drive vehicle transportation. This report focuses on the Caribou-Targhee National Forest (CTNF) fleet to identify daily operational characteristics of select vehicles and report findings on vehicle and mission characterizations to support the successful introduction of plug-in electric vehicles (PEVs) into the agencies’ fleets. Individual observations of these selected vehicles provide the basis for recommendations related to electric vehicle adoption and whether a battery electric vehicle (BEV) or plug-in hybrid electric vehicle (PHEV) (collectively plug-in electric vehicles, or PEVs) can fulfill the mission requirements. ITSNA acknowledges the support of Idaho National Laboratory and CTNF for participation in the study. ITSNA is pleased to provide this report and is encouraged by enthusiasm and support from the Forest Service and CTNF personnel.

33 ADVANCED PROPULSION SYSTEMS↗

Summary of Calcine Disposal Development Using Hot Isostatic Pressing

Battelle Energy Alliance, LLC, has demonstrated the effectiveness of the hot isostatic press (HIP) process for treatment of hazardous high-level waste known as calcine that is stored at the Idaho Nuclear Technology and Engineering Center (INTEC) at Idaho National Laboratory. HIP trials performed with simulated calcines at Idaho National Laboratory’s Materials and Fuels Complex and an Australian Nuclear Science and Technology Organization facility from 2007 to 2010 produced a dense, monolithic waste form with increased chemical durability and effective (storage) volume reductions of ~10 to ~70% compared to granular calcine forms. In December 2009, the U.S. Department of Energy signed an amended Record of Decision selecting HIP technology as the treatment method for the 4,400 m3 of granular zirconia and alumina calcine stored at INTEC. Testing showed that HIP treatment reduces the risks associated with radioactive and hazardous constituent release, post-production handling, and long-term (repository) storage of calcines and would result in estimated storage cost savings in the billions of dollars. Battelle Energy Alliance has the ability to complete pilot-scale HIP processing of INTEC calcine, which is the next necessary step in implementing HIP processing as a calcine treatment method.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Testing Novel CR-39 Detector Deployment System for Identification of Subsurface Fractures, Soda Springs, ID

The Environmental Protection Agency (EPA) has teamed with Battelle Energy Alliance, LLC (BEA) at Idaho National Laboratory (INL) to facilitate further testing of geologic-fracture-identification methodology at a field site near the Monsanto Superfund Site located in Soda Springs, Idaho. INL has the necessary testing and technological expertise to perform this work. Battelle Memorial Institute (BMI) has engaged INL to perform this work through a Work for Others (WFO) Agreement. This study continues a multi-year collaborative effort between INL and EPA to test the efficacy of using field deployed Cr-39 radon in soil portals. This research enables identification of active fractures capable of transporting contaminants at sites where fractures are suspected pathways into the subsurface. Current state of the art methods for mapping fracture networks are exceedingly expensive and notoriously inaccurate. The proposed WFO will evaluate the applicability of using cheap, readily available, passive radon detectors to identify conductive geologic structures (i.e. fractures, and fracture networks) in the subsurface that control the transport of contaminants at fracture-dominated sites. The proposed WFO utilizes proven off-the-shelf technology in the form of CR-39 radon detectors, which have been widely deployed to detect radon levels in homes and businesses. In an existing collaborative EPA/INL study outside of this workscope, CR-39 detectors are being utilized to determine the location of active transport fractures in a fractured granitic upland adjacent to a landfill site at the Fort Devens, MA that EPA-designated as National Priorities List (NPL) site. The innovative concept of using an easily deployed port that allows the CR-39 to measure the Rn-222 in the soil or alluvium above the fractured rock, while restricting atmospheric Rn-222 and soil sourced Ra from contaminating the detector is unique to INL and EPA approach previously developed. By deploying a series of these inexpensive detector-casing combinations statistical samples of the Rn-222 flux can be measured, elucidating the most communicative fractures (i.e. fractures that are actively transporting water and gasses). The Rn-222 measurements can then be used as an input to create a more accurate conceptual model to be used for transport modeling and related cleanup activities. If the team’s approach is demonstrated to be applicable to a wide variety of rock types and soil conditions it might potentially offer significant cost saving without a reduction in data quality at Monsanto Superfund and other sites underlain by fracture-dominated bedrock.

58 GEOSCIENCES↗

Nanolipoprotein Particles (NLPs) as Versatile Vaccine Platforms for Co-delivery of Multiple Adjuvants with Subunit Antigens from Burkholderia spp. and F. tularensis - Annual Technical Report

The goal of this proposal is to demonstrate that co-localization of protein subunit antigens and adjuvants on nanolipoprotein particles (NLPs) can increase the protective efficacy of recombinant subunit antigens from Burkholderia spp. and Francisella tularensis against an aerosol challenge. NLPs are are biocompatible, high-density lipoprotein mimetics that are amenable to the incorporation of multiple, chemically-disparate adjuvant and antigen molecules. We hypothesize that the ability to co-localize optimized adjuvant formulations with subunit antigens within a single particle will enhance the stimulation and activation of key immune effector cells, increasing the protective efficacy of subunit antigen-based vaccines. While Burkholderia spp. and F. tularensis subunit antigens are the focus of this proposal, we anticipate that this approach is applicable to a wide range of DOD-relevant biothreat agents. The F344 rat aerosol challenge model for F. tularensis has been successfully established at Battelle under this contract, and Year 3 efficacy studies performed at Battelle demonstrated that an NLP vaccine formulation was able to enhance survival of female F344 rats relative to naïve animals. In addition, Year 3 focused on the incorporation of multiple Burkholderia antigens (both polysaccharides and proteins) onto adjuvanted NLPs, with immunological analysis poised to begin in the next quarter.

59 BASIC BIOLOGICAL SCIENCES↗

INL Fleet Vehicle Characterization Study for the U.S. Department of Navy

Battelle Energy Alliance, LLC, managing and operating contractor for the U.S. Department of Energy’s Idaho National Laboratory, is the lead laboratory for U.S. Department of Energy Advanced Vehicle Testing. Battelle Energy Alliance, LLC collected and evaluated data on federal fleet operations as part of the Advanced Vehicle Testing Activity’s Federal Fleet Vehicle Data Logging and Characterization Study. The Advanced Vehicle Testing Activity’s study seeks to collect and evaluate data to validate use of advanced plug-in electric vehicle (PEV) transportation. This report focuses on US Department of Navy's fleet to identify daily operational characteristics of select vehicles and report findings on vehicle and mission characterizations to support the successful introduction of PEVs into the agency’s fleets. Individual observations of these selected vehicles provide the basis for recommendations related to electric vehicle adoption and whether a battery electric vehicle or plug-in hybrid electric vehicle (collectively referred to as PEVs) can fulfill the mission requirements.

33 ADVANCED PROPULSION SYSTEMS↗

Implementation Approach for Electric Vehicles at Marine Corps Base Camp Lejeune. Task 4

Battelle Energy Alliance, LLC, managing and operating contractor for the U.S. Department of Energy’s Idaho National Laboratory, is the lead laboratory for U.S. Department of Energy Advanced Vehicle Testing. Battelle Energy Alliance, LLC contracted with Intertek Testing Services, North America (Intertek) to conduct several U.S. Department of Defense base studies to identify potential U.S. Department of Defense transportation systems that are strong candidates for introduction or expansion of plug-in electric vehicles (PEVs). This study is focused on the Marine Corps Base Camp Lejeune (MCBCL) located in North Carolina. Task 1 consisted of a survey of the non-tactical fleet of vehicles at MCBCL to begin the review of vehicle mission assignments and types of vehicles in service. In Task 2, daily operational characteristics of vehicles were identified to select vehicles for further monitoring and attachment of data loggers. Task 3 recorded vehicle movements in order to characterize the vehicles’ missions. The results of the data analysis and observations were provided. Individual observations of the selected vehicles provided the basis for recommendations related to PEV adoption, i.e., whether a battery electric vehicle (BEV) or plug-in hybrid electric vehicle (PHEV) (collectively PEVs) can fulfill the mission requirements. It also provided the basis for recommendations related to placement of PEV charging infrastructure. This report focuses on an implementation plan for the near-term adoption of PEVs into the MCBCL fleet. Intertek acknowledges the support of Idaho National Laboratory, Marine Corps headquarters, and Marine Corps Base Camp Lejeune fleet management and personnel for participation in this study. Intertek is pleased to provide this report and is encouraged by enthusiasm and support from MCBCL personnel.

33 ADVANCED PROPULSION SYSTEMS↗

Micro Climate Assessment of Grid-Connected Electric Drive Vehicles and Charging Infrastructure. Final Report

Battelle Energy Alliance, LLC, managing and operating contractor for the U.S. Department of Energy’s Idaho National Laboratory, is the lead laboratory for the U.S. Department of Energy’s advanced vehicle testing. Battelle Energy Alliance, LLC contracted with Intertek Testing Services, North America to conduct several U.S. Department of Defense-based micro-climate studies to identify potential U.S. Department of Defense transportation systems that are strong candidates for introduction or expansion of plug-in electric vehicles (PEVs). The study included Joint Base Lewis McChord, located in Washington State; Naval Air Station Whidbey Island, located in Washington State; and United States Marine Corp Base Camp Lejeune, located in North Carolina. The project was divided into four tasks for each of the three bases studied. Task 1 consisted of surveying the non-tactical fleet of vehicles to begin review of vehicle mission assignments and types of vehicles in service. In Task 2, the daily operational characteristics of the vehicles were identified to select vehicles for further monitoring and attachment of data loggers. Task 3 recorded vehicle movements in order to characterize the vehicles’ missions. Results of the data analysis and observations were provided. Individual observations of these selected vehicles provided the basis for recommendations related to PEV adoption (i.e., whether a battery electric vehicle or plug-in hybrid electric vehicle [collectively referred to as PEVs] can fulfill the mission requirements). It also provided the basis for recommendations related to placement of PEV charging infrastructure. In Task 4, an implementation approach was provided for near-term adoption of PEVs into the respective fleets. Each facility was provided detailed reports on each of these tasks. This paper summarizes and provides observations on the project and completes Intertek’s required actions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Utilization Assessment of Target Electrification Vehicles at Marine Corps Base Camp Lejeune. Task 3

Battelle Energy Alliance, LLC, managing and operating contractor for the U.S. Department of Energy’s Idaho National Laboratory, is the lead laboratory for U.S. Department of Energy Advanced Vehicle Testing. Battelle Energy Alliance, LLC contracted with Intertek Testing Services, North America (Intertek) to conduct several U.S. Department of Defense base studies to identify potential U.S. Department of Defense transportation systems that are strong candidates for introduction or expansion of plug-in electric vehicles (PEVs). Task 1 consisted of a survey of the non-tactical fleet of vehicles at MCBCL to begin the review of vehicle mission assignments and types of vehicles in service. Task 2 involved identifying daily operational characteristics of select vehicles and initiating data logging of vehicle movements in order to characterize the vehicle’s mission. Individual observations of these selected vehicles provide the basis for recommendations related to PEV adoption and whether a battery electric vehicle or plug-in hybrid electric vehicle (collectively referred to as PEVs) can fulfill the mission requirements and provide observations related to placement of PEV charging infrastructure. This report provides the results of the data analysis and observations related to replacement of current vehicles with PEVs. This fulfills part of the Task 3 requirements. Task 3 also includes an assessment of the charging infrastructure required to support this replacement, which is the subject of a separate report. Intertek acknowledges the support of Idaho National Laboratory, Marine Corps headquarters, and Marine Corps Base Camp Lejeune Fleet management and personnel for participation in this study. Intertek is pleased to provide this report and is encouraged by enthusiasm and support from MCBCL personnel.

33 ADVANCED PROPULSION SYSTEMS↗

Assessment of Charging Infrastructure for Plug-in Electric Vehicles at Marine Corps Base Camp Lejeune. Task 3

Battelle Energy Alliance, LLC, managing and operating contractor for the U.S. Department of Energy’s Idaho National Laboratory, is the lead laboratory for the U.S. Department of Energy’s advanced vehicle testing. Battelle Energy Alliance, LLC contracted with Intertek Testing Services, North America (Intertek) to conduct several U.S. Department of Defense-based studies to identify potential U.S. Department of Defense transportation systems that are strong candidates for introduction or expansion of plug-in electric vehicles (PEVs). Task 1 consisted of a survey of the non-tactical fleet of vehicles at Marine Corps Base Camp Lejeune to begin the review of vehicle mission assignments and types of vehicles in service. Task 2 selected vehicles for further monitoring and involved identifying daily operational characteristics of these select vehicles. Data logging of vehicle movements was initiated in order to characterize the vehicle’s mission. The Task 3 vehicle utilization report provided results of the data analysis and observations related to the replacement of current vehicles with PEVs. Finally, this report provides an assessment of charging infrastructure required to support the suggested PEV replacements. Intertek acknowledges the support of Idaho National Laboratory, Marine Corps headquarters, and Marine Corps Base Camp Lejeune Fleet management and personnel for participation in this study. Intertek is pleased to provide this report and is encouraged by enthusiasm and support from Marine Corps Base Camp Lejeune personnel.

33 ADVANCED PROPULSION SYSTEMS↗

Wildlife Management Plan for the Oak Ridge Reservation

This document outlines a plan for management of the wildlife resources on the US Department of Energy’s (DOE’s) Oak Ridge Reservation. Management includes wildlife population control through restoration of wildlife species; preservation, management, and enhancement of wildlife habitats; coordination of wildlife studies and characterization of areas, hunting, trapping, removal, and habitat manipulation; wildlife damage control; and law enforcement. Wildlife resources are divided into several categories, each with a specific set of objectives and procedures to attain the goals. These objectives are management of (1) wildlife habitats to ensure that all resident wildlife species exist on the Reservation in viable numbers; (2) focal species to promote healthy populations on designated land units; (3) game species for research, education, recreation, and public safety; (4) the Three Bend Scenic and Wildlife Management Refuge Area; (5) nuisance wildlife, including nonnative species, to achieve adequate population control for the maintenance of health and safety on the Reservation; (6) sensitive species (i.e., state or federally listed as Endangered, Threatened, Of Special Concern, or In Need of Management) through preservation and protection of both the species and habitats critical to the survival of those species; and (7) wildlife disease. Achievement of the objectives is a joint effort between Oak Ridge National Laboratory and the Tennessee Wildlife Resources Agency (TWRA) through agreements between DOE and the University of Tennessee (UT)-Battelle LLC, between TWRA and DOE, and between Tennessee Department of Environment and Conservation (TDEC) and DOE. Implementation of objectives is to be informed by leading-edge research and a strong collaborative approach between UT-Battelle and TWRA.

54 ENVIRONMENTAL SCIENCES↗

PNNL 2017 Richland Campus Master Plan

Based in Richland, Washington, Pacific Northwest National Laboratory (PNNL) is one of 10 United States (U.S.) Department of Energy (DOE) Office of Science (SC) national laboratories. PNNL is DOE’s premier chemistry, earth sciences and data analytics Laboratory, delivering vital mission impacts in energy resiliency and national security. PNNL has 19 core capabilities, each a powerful combination of world-class staff, state-of-the-art equipment, and mission ready facilities. These capabilities represent a collective set of skills and a body of world-leading scientific and engineering work that provides exceptional value and mission delivery to DOE, the National Nuclear Security Administration (NNSA), the U.S. Department of Homeland Security (DHS), and the missions of other federal agencies and industry through strategic partnership projects. Operated by Battelle Memorial Institute (Battelle), PNNL has more than: 2.3 million gross square feet and 4,400 staff members. PNNL is implementing a rolling 10-year campus strategy (initiated in FY 2013) designed to deliver the foundation for the multidisciplinary science and engineering expertise, equipment, instrumentation, facilities, and infrastructure required to continue providing exceptional value and mission delivery. PNNL’s annual ten-year plan is published with SC’s Ten-Year Plans for the Science National Laboratories. The most recent publication is available at: https://science.energy.gov/lp/laboratory-planning-process/. This edition of the PNNL Richland Campus Master Plan (CMP) is an update to the 2012 CMP.

99 GENERAL AND MISCELLANEOUS↗

Critical and Californium Source-Driven Noise Analysis Subcritical Measurements with an Unreflected Cylindrical Tank of Mixed Uranium-Plutonium Nitrate Solution

The reported experiments were performed by Oak Ridge National Laboratory (ORNL) at the Battelle Northwest Laboratory’s (now Pacific Northwest National Laboratory) critical experiments facility at Hanford, Washington in 1981 and used 16 days of critical facility time, not including 10 days for setup and removal of ORNL equipment. These measurements were to assess the capability of the Cf source-driven noise analysis (CSDNA) method to measure the subcriticality (keff) of mixed U-Pu nitrate solutions. In addition to the CSNDA measurements, measurements were also performed near delayed criticality where CSDNA measurements cannot be performed. This report documents the experiments that were not reported at that time by presenting the ORNL experimental results and any online analysis performed during and shortly after the measurements. The mixed nitrate solution had a U concentration at 188 grams per liter (g/L), a Pu concentration of 280 g/L, free acid normality of 2.80, H ion molarity of 5.9 and a specific gravity of 1.754 g/cm 3 , a 240 Pu isotopic content of 7.981 wt. %, and a 235 U isotopic content of 0.724 wt. %. The stainless-steel tank for the solution had an inside diameter of 35.38 cm, an outside diameter of 35.53 cm, a height of 56.72 cm, and bottom thickness of 0.9525 cm. A Zircaloy pipe with a 3.1496 cm outside diameter, a 2.7788 cm inside diameter, and bottom thickness of 0.635 cm was available for insertion of the Cf source in the center of the fissile solution. The Cf source was also located at the outside surface of the tank (solution height varied from 10 to 53 cm) and in the center of the solution (solution height varied from 10 to 60.7 cm). The CSDNA measurements were not analyzed online to determine the subcritical neutron multiplication factors. At all subcritical states, the break frequency noise analysis data was fitted to obtain the prompt neutron decay constant. The neutron multiplication factors were determined for the two configurations of the measurements near delayed criticality. The subcritical neutron multiplication factors from the CNSDA measurements can be obtained with further analysis. However, the near delayed critical configuration, the prompt neutron decay constants, the count rates, and the measured cross and auto power spectral densities can be calculated directly for benchmarking. Much of data presented in this report are from ORNL notes—not in the ORNL logbooks. For the final benchmark analysis, the data from the Battelle Northwest Laboratory (which operated the critical facility in 1981) critical facility logbook should be consulted and be incorporated where appropriate. The purpose of this report is to document the experimental information for the measurements performed so that at a later date researchers could perform the required uncertainty and calculational analyses and documentation to use these data for an International Criticality Safety Benchmark Program (ICSBEP) or Nuclear Energy Agency benchmark. The data from these measurements are available from the ORNL Records Management Services Department, and the logbook is available from ICSBEP at Idaho National Laboratory. Preparation of the present report is part of a larger cooperative effort between Idaho National Laboratory (INL) and Oak Ridge National Laboratory (ORNL) to document more than 15 undocumented critical and subcritical experiments enumerated in ORNL/TM-2019/18 and performed by ORNL at ORCEF and other USDOE critical experiments facilities using more than 500 operational days of critical facility time.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Synthesizing, Compounding, and Characterizing a Heat Labile Polyurethane Foam

Savannah River National Laboratory (SRNL) is part of the National Laboratory system within US Department of Energy (DOE) • Located within the DOE’s Savanah River Site near Aiken, SC • Operated by Battelle Savannah River Alliance (BSRA) LLC, a consortium of Battelle Laboratories, SRNL, University of South Carolina, Clemson University, South Carolina State University, University of Georgia, and Georgia Tech University.

Kranjc, Mark D.↗

Pacific Northwest National Laboratory Facility Radionuclide Emission Points and Sampling Systems

Battelle–Pacific Northwest Division operates numerous research and development laboratories in Washington State. The U.S. Department of Energy (DOE) contracts to Battelle at Richland facilities on both the DOE Hanford Site and the Pacific Northwest National Laboratory (PNNL)-Richland campus. These facilities have the potential for radionuclide air emissions. The PNNL contract with DOE also includes operations at the PNNL-Sequim campus in Sequim, where there is also the potential for radionuclide air emissions. This document is a periodic update that describes current PNNL facility emission units and sampling systems.

54 ENVIRONMENTAL SCIENCES↗