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Un-numbered Operational Areas, PRL 229, Railroad Tie Disposal Area Pond Confirmatory Sampling Work Plan

This Confirmatory Sampling Work Plan presents the approach to be used to determine if the pond in the Un-numbered Operational Areas (Potential Release Location 229) has contamination associated with the adjacent railroad tie disposal area. The Work Plan describes sampling and analytical requirements and the approach that will be used for the screening level ecological assessment.

railroad tie↗

Per- and Polyfluoroalkyl Substances Confirmatory Sampling Report, South Repeater Building (SWMU 121), Kennedy Space Center, Florida

This Per- and Polyfluoroalkyl Substances (PFAS) Confirmatory Sampling (CS) Report was prepared by AECOM Technical Services, Inc. (AECOM) for the National Aeronautics and Space Administration (NASA) under Contract 80KSC019D0010, Task Order 80KSC021F0096. The purpose of this report is to document CS activities at the South Repeater Building, Solid Waste Management Unit (SWMU) 121, formerly known as the Area 3 Repeater Building (A3RB). A Phase I SWMU Assessment and Confirmatory Sampling Report (NASA 2019) and a Phase II and III SWMU Assessment and Confirmatory Sampling Report (NASA 2022b) were previously submitted detailing Center-Wide assessment activities performed at the John F. Kennedy Space Center (KSC) in Florida that identified 33 locations of concern and 19 areas of potential concern at KSC associated with the storage, use, or release of materials containing PFAS. A review of the analytical results from investigation derived waste samples collected in 2020 from the South Repeater Building area indicated concentrations of perfluorooctanesulfonic acid (PFOS) were above Florida Department of Environmental Protection (FDEP) provisional Groundwater Cleanup Target Levels of 70 nanograms per liter (ng/L) at a concentration of 1,750 ng/L. Following this review, the KSC Fire Chief was contacted; the Chief recalled fighting a brush fire in 1998 in the area, during which an unknown volume of aqueous film-forming foam was used to extinguish the fire. The Phase II and Phase III SWMU Assessment Report recommended this area proceed to CS. Historical results in this area are provided in Appendix A . PFAS CS activities were contracted at the South Repeater Building. Initial CS activities were conducted in accordance with the PFAS Assessment and Mitigation Work Plan (AECOM 2022), which was submitted to the NASA Remediation Project Management team and accepted by the team on November 1 and 8, 2021. The objectives of the PFAS CS were to: - - Confirm and begin to assess the extent of PFAS affected media in the South Repeater Building area. - - Identify locations for groundwater, soil, surface water, and soil core sampling. - - Qualitatively characterize the migration potential of released PFAS to environmental media (soil, groundwater, and surface water). The following activities were completed to meet the PFAS CS objectives: - - Installation of monitoring wells via direct push technology (DPT) and rotosonic techniques - - Groundwater, soil, and surface water sampling - - Collection of soil cores to evaluate site lithology - - Development of initial PFAS plume characterization

PFAS↗

KSC Child Development Center (Potential Release Location 149) Confirmatory Sampling Report and Interim Measures Work Plan

This Confirmatory Sampling (CS) Report and Interim Measures (IM) Work Plan was prepared for the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Florida, by HydroGeoLogic, Inc. (HGL) under Contract Number 80KSC019D0012, Task Order 80KSC019F0118. This document presents the results of the CS activities performed in March 2022, and May 202, at the KSC Child Development Center (KCDC), Potential Release Location (PRL) 149, KSC, Florida. This report additionally presents the results of an assessment conducted in July 2023 to determine whether construction activities in 2023 to replace certain playground equipment and the rubberized play surface allowed soil contaminated by arsenic (As) to migrate from beneath the play surface.

arsenic↗

Firex Water Tank, SWMU 069, Confirmatory Sampling Report: Revision 2

The National Aeronautics and Space Administration (NASA) Resource Conservation and Recovery Act (RCRA) permit requires identification and evaluation of known Solid Waste Management Units (SWMU) located at the Kennedy Space Center (KSC). Firex Water Tank (FWT), or the “site,” is designated as SWMU 069 under the NASA RCRA permit. This report summarizes the results of the Confirmatory Sampling (CS) field activities carried out during Fall 2021, at FWT, SWMU 069, KSC, Florida. Three locations of concern (LOCs) were identified by screening historical sample results to current State of Florida soil cleanup target levels (SCTL). A total of 18 soil samples were collected to investigate the historical exceedance locations. Samples at LOC 1 and 2 were analyzed for arsenic and the results for all were below the SCTL. Samples at LOC 3 were analyzed for polynuclear aromatic hydrocarbons and it was determined that certain locations have results that remain above the SCTL. The current land use controls will remain in place at FWT to mitigate potential risks.

Firex↗

Stand Alone Electrical Equipment PRL 227a (Formerly PRL 227 LOC3) Confirmatory Sampling Report Addendum

HydroGeoLogic, Inc. (HGL) prepared this Confirmatory Sampling Report Addendum (CSRA) for the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Florida. PRL 227a Location of Concern (LOC) 3 is located on 10th Street, west of the former Vertical Processing Facility (M7-1469), SWMU 077. The Load Break Switches (LBS) were installed in 1986 and are suspected to have formerly contained dielectric fluid that contained polychlorinated biphenyls (PCBs). The LBS were replaced in 1993 with new LBSs that do not contain PCBs. The LBS are located on a concrete pad surrounded by grass that is mowed and maintained. A total of 330 soil samples were collected between June 2020 and December 2022 from 88 locations at depths ranging from 0-0.5 to 19-20 ft bls. In general, soil samples collected from depths less than 5 ft were collected via hand auger and samples collected beyond 5 ft bls were collected using a direct-push technology drill rig. Soil samples collected from greater than 5 ft bls to 20 ft bls were collected to confirm PCBs were not present at depth in the aquifer matrix. Delineation samples were collected using an approximately 20 ft horizontal spacing. PCB impacted soil has been completely delineated to the State of Florida residential soil cleanup target level (SCTL) at PRL 227a horizontally and vertically. PCB concentrations have been identified above the residential and industrial SCTL as well as concentrations greater than or equal to 50 ppm requiring coordination with EPA and disposal at a facility authorized under TSCA. Based upon the CSRA sampling, an interim measure is recommended to remove PCB impacted soil above the residential SCTL. The total volume of PCB impacted soil to be removed is 591.6 cubic yards. This includes approximately 9.3 cubic yards of soil with PCB concentrations greater than or equal to 50 ppm. An interim measure work plan is included as an attachment to this report.

electrical equipment↗

Phase II and III Solid Waste Management Unit Assessment and Confirmatory Sampling Report for Per- and Polyfluorinated Alkyl Substances, Potential Release Location 237, Kennedy Space Center, Florida

Per- and polyfluoroalkyl substances (PFAS) Phase II and III Solid Waste Management Unit (SWMU) Assessment (SA) and Confirmatory Sampling (CS) were conducted at the John F. Kennedy Space Center (KSC), Potential Release Location (PRL) 237, located in Merritt Island, Brevard County, Florida for the National Aeronautics and Space Administration (NASA) under Contract 80KSC019D0010/80KSC019F0289. A Phase I SA and CS Report was previously submitted that identified 33 locations of concern (LOCs) at KSC associated with the storage, use, or release of materials containing PFAS. The objectives of the Phase II and III SA and CS were to: - Complete site and source characterization of identified LOCs; - Identify areas of potential concern (AOPCs) where past or present activities may have resulted in a release of PFAS to the environment; - Qualitatively characterize migration potential of released PFAS to environmental media (primarily soil, groundwater, surface water, and sediment); and - Identify potential receptors for exposure to PFAS-impacted environmental media. Surface water samples were collected from LOCs/AOPCs and locations on the KSC periphery during PFAS CS Phases I, II and III. Including duplicate samples, 143 environmental samples were analyzed for 14 PFAS compounds and 104 environmental samples were analyzed for 18 PFAS compounds. Ten of the analytes on the 14 compound list were detected at least once in surface water at KSC, with a wide range in magnitude of detections. The State of Florida has surface water screening levels (SWSLs) for perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in surface water, both for human and ecological receptors. The human health screening levels are lower than the ecological ones and are used in this report. PFOA was not detected in surface water at concentrations exceeding the SWSL at any LOC or Area of Potential Concern (AOPC). PFOS was detected in surface water at concentrations exceeding the SWSL at 28 LOCs/AOPCs, plus 42 locations on the KSC periphery. The data suggest a wide distribution of PFAS, particularly PFOS, in surface water but the sources of surface water contamination are not yet adequately understood. Sediment samples were collected during Phases II and III but not Phase I. Including duplicate samples, 104 environmental samples were analyzed for 14 PFAS compounds and 10 environmental samples were analyzed for 18 PFAS compounds. Twelve compounds were detected in sediment at KSC, with a wide range in magnitude of detections. There are currently no screening levels or cleanup target levels (CTLs) for sediment. The need to delineate and further characterize PFAS in sediment will be evaluated for those sites that move forward into Site Assessment. Groundwater samples were collected via DPT from LOCs/AOPCs and locations on the KSC periphery during PFAS CS Phases I, II and III. Including duplicate samples, 812 environmental DPT groundwater samples were analyzed for 14 PFAS compounds and 247 environmental samples were analyzed for 18 PFAS compounds. Twelve of the 14 compounds were detected in groundwater at KSC, with a wide range in magnitude of detections. The State of Florida has provisional groundwater cleanup target levels (GCTLs) for PFOA, PFOS and the additive concentration of PFOA+PFOS. PFOA was detected in groundwater at concentrations exceeding its provisional GCTL at 16 LOCs/AOPCs, with no exceedances on the KSC periphery. PFOS was detected in groundwater at concentrations exceeding its provisional GCTL at 30 LOCs/AOPCs, plus two locations on the KSC periphery. PFOA+PFOS was detected in groundwater at concentrations exceeding the provisional GCTL at 31 LOCs/AOPCs, plus two locations on the KSC periphery. Soil samples were collected during Phases II and III but not Phase I. Including duplicate samples, 292 environmental samples were analyzed for 14 PFAS compounds and 80 environmental samples were analyzed for 18 PFAS compounds. Fourteen compounds were detected in soil at KSC, with a wide range in magnitude of detections. The State of Florida has provisional soil cleanup target levels (SCTLs) for PFOA and PFOS. There were no PFOA results above its provisional SCTL. There was one LOC with a result above the provisional SCTL for residential settings. Recommendations are presented for each LOC and AOPC.

PFAS↗

Firex Water Tank, SWMU 069, Confirmatory Sampling Report

The National Aeronautics and Space Administration (NASA) Resource Conservation and Recovery Act (RCRA) permit requires identification and evaluation of known Solid Waste Management Units (SWMU) located at the Kennedy Space Center (KSC). Firex Water Tank (FWT), or the “site,” is designated as SWMU 069 under the NASA RCRA permit. This report summarizes the results of the Confirmatory Sampling (CS) field activities carried out during Fall 2021, at FWT, SWMU 069, KSC, Florida. Three locations of concern (LOCs) were identified by screening historical sample results to current State of Florida soil cleanup target levels (SCTL). A total of 18 soil samples were collected to investigate the historical exceedance locations. Samples at LOC 1 and 2 were analyzed for arsenic and the results for all were below the SCTL. Samples at LOC 3 were analyzed for polynuclear aromatic hydrocarbons and it was determined that certain locations have results that remain above the SCTL. The current land use controls will remain in place at FWT to mitigate potential risks.

Firex↗

Area 3 Support Buildings (A3SB) H5-0992, H5-0996 PRL 218 Confirmatory Sampling Report

The Area 3 Support Buildings site (A3SB) consists of two separate areas located on the north side of Beach Road in the northern portion of Kennedy Space Center, Florida (KSC), outside the secured perimeter of KSC. The A3SB areas are approximately 0.6 miles apart, and were developed as Shiffler's Grocery Store and Service Station (west site) and as a residence (east site) prior to acquisition by the National Aeronautics and Space Administration (NASA) in 1963. Both areas were used by the Bendix Company in support of NASA as chemical laboratories from 1963 through 1969. Both of the buildings were demolished by 1987. The west portion of the site was used by the US Fish & Wildlife Service (F&W) in support of the Merritt Island National Wildlife Refuge (MINWR) for parking at the entrance to the Hammock Trails from 1969 to the present. The east portion of the site was used for intermittent suspect materials staging in the early 1990s and is still used as an apiary location, but is otherwise no longer active. In support of the NASA HSWA permit requirements, this site was identified as Potential Release Location (PRL) 218 and a Solid Waste Management Unit (SWMU) Assessment (SA) was conducted in 2013. Confirmatory Sampling (CS) was recommended and approved by the KSC Remediation Team (KSCRT). Three locations of concern (LOCs) were identified and sampled at the site. The LOCs include two former chemical labs and a former suspect staging area. The CS was conducted in March of 2015 at three locations by means of Direct Push Technology (DPT) groundwater sampling and at one location for soil sampling. The samples were collected and analyzed in accordance with the approved CS Work Plan. There were no exceedances of criteria detected in any of the samples from the three LOCs. The results of this investigation indicate that past and/or present operations have not negatively impacted environmental media at the A3SB. Based upon no confirmed groundwater detections above GCTLs and no soil impacts above applicable screening criteria no further investigation is warranted at the A3SB. A No Further Action (NFA) status for all locations was approved by the KSCRT at the June 2015 meeting.

Confirmatory sampling↗

KSC Child Development Center (PRL 149) Confirmatory Sampling Report and Interim Measures Work Plan

The National Aeronautics and Space Administration (NASA) Resource Conservation and Recovery Act (RCRA) permit requires identification and evaluation of known Solid Waste Management Units (SWMU) located at the Kennedy Space Center (KSC). The KSC Child Development Center (KCDC), the “site,” is designated as potential release location (PRL) 149 under the NASA RCRA permit. This report summarizes the results of the Confirmatory Sampling (CS) activities carried out on March 19, 2022, and May 16, 2023, at KCDC, PRL 149, KSC, Florida. This report additionally presents the results of an assessment conducted between July 7 and July 27, 2023, to determine whether construction activities in 2023 to replace certain playground equipment and the rubberized play surface released arsenic (As) contaminated soil.

CDC↗

Un-Numbered Operational Areas PRL 229 Railroad Tie Disposal Area Pond Confirmation Sampling Report

This Confirmatory Sampling (CS) Report (CSR) was prepared for the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), Florida in accordance with the CS Work Plan (CSWP) (HGL, 2022a). The CSR summarizes investigation activities performed on the Railroad Tie Disposal Area (RTDA) of the Un-Numbered Operational Areas (UNOA), Potential Release Location (PRL) 229 located at KSC. HydroGeoLogic, Inc. (HGL) prepared this report under Contract Number 80KSC019D0012. The purpose of the CSR is to provide information to evaluate the level of potential contamination in surface water and sediment samples collected from the RTDA PRL 229 Pond and determine if contaminants pose unacceptable risks to ecological receptors. The CSR provides analytical data of 10 sets of surface water and sediment samples collected in 2021. Surface water samples were analyzed for volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs), polynuclear aromatic hydrocarbon (PAHs), metals, hardness, and salinity, while sediment samples were analyzed for metals, total organic carbon (TOC), SVOCs, PAHs, and total petroleum hydrocarbons (TPH). The CSR includes a Screening Level Ecological Risk Assessment (SLERA) conducted under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program to determine if unacceptable risks to ecological receptors exist at PRL 229 Pond. Metals and PAHs were detected in surface water samples, including detections of antimony, arsenic, barium, calcium, copper, lead, magnesium, thallium, zinc, anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Based on measured salinity (1.03 to 1.21 parts per thousand), the pond was identified as freshwater. Sediment analytical results also contained detections of metals and PAHs, including antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, zinc, anthracene benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3-c,d)pyrene and pyrene. Potential risks to ecological receptors were evaluated in accordance with the SLERA Work Plan and the Decision Process Document for the Resource Conservation and Recovery Act (RCRA) Corrective Action Program at KSC (DPD) (Geosyntec, 2019), and using the 2021 sediment and surface water analytical results. Potential ecological receptors evaluated in the SLERA include the aquatic community, benthic invertebrates, aquatic birds, and aquatic mammals. The SLERA included Steps 2a through 2c of the Ecological Risk Assessment (ERA) process in accordance with the DPD. Using multiple lines of evidence, the SLERA concluded that many of the detected analytes are present at concentrations similar to those in background or reference locations at KSC, and/or at concentrations that would not pose a significant risk to ecological communities. There are no screening values available for the avian community, and PAHs are bioaccumulative compounds. For this reason, food web modeling was completed as a supplement to Step 2c to provide a quantitative evaluation of this exposure pathway. Food web modeling indicates that PAHs are unlikely to pose a risk to birds exposed to site sediment and surface water. Based on the results of the SLERA, the contaminants in sediment and surface water pose no to minimal risk to the ecological communities that could live or forage at the site. Based on the results of the SLERA, no further study is recommended for the RTDA Pond at PRL 229.

Confirmation Sampling↗

A novel framework for increasing research transparency: Exploring the connection between diversity and innovation

A split sample/dual method research protocol is demonstrated to increase transparency while reducing the probability of false discovery. We apply the protocol to examine whether diversity in ownership teams increases or decreases the likelihood of a firm reporting a novel innovation using data from the 2018 United States Census Bureau’s Annual Business Survey. Transparency is increased in three ways: 1) all specification testing and identifying potentially productive models is done in an exploratory subsample that 2) preserves the validity of hypothesis test statistics fromde novoestimation in the holdout confirmatory sample with 3) all findings publicly documented in an earlier registered report and in this journal publication. Bayesian estimation procedures that leverage information from the exploratory stage included in the confirmatory stage estimation replace traditional frequentist null hypothesis significance testing. In addition to increasing statistical power by using information from the full sample, Bayesian methods directly estimate a probability distribution for the magnitude of an effect, allowing much richer inference. Estimated magnitudes of diversity along academic discipline, race, ethnicity, and foreign-born status dimensions are positively associated with innovation. A maximally diverse ownership team on these dimensions would be roughly six times more likely to report new-to-market innovation than a homophilic team.

Science & Technology - Other Topics↗

Soil Interim Measures Implementation Report Q6 Radar Station – Solid Waste Management Unit 112 Locations of Concern 3 and 10 Kennedy Space Center, Florida

This report presents a summary of the soil interim measures (IM) implementation activities that occurred from January 23 through June 6, 2023, at the Q6 Radar Station (Q6RS) Solid Waste Management Unit (SWMU) 112, located at the John F. Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act Corrective Action Program, which also meets the requirements of Chapter 62-780, Florida Administrative Code. Assessment activities have previously been performed at 10 Q6RS Locations of Concern (LOCs), identified during a SWMU assessment in 2013 (NASA 2013). Since the SWMU assessment, further confirmatory sampling and assessment was conducted for each LOC, and based on the data collected during these assessments, it was determined that Resource Conservation and Recovery Act Facility Investigation to further evaluate soil and groundwater was to be conducted at two LOCs: LOC 1 – Former Underground Storage Tanks (groundwater) and LOC 3 – Radar Antenna Refurbishment Area (soil). The LOC 1 groundwater assessment is ongoing, and the results will be presented under a separate cover. It was also determined that soil IM would be completed at two of the LOCs, LOC 3 and LOC 10 – Compressor Building Condensate Discharge. A Soil IM Work Plan was prepared and submitted in October 2021 (NASA 2021). The plan proposed excavation and disposal of barium and copper impacted soil in the LOC 3 and 10 areas. This report presents a summary and results of the soil IM implementation activities conducted at LOCs 3 and 10. The site contaminates of concern for this soil IM are barium and copper. The activities presented in this report includes soil IM implementation and groundwater sampling. From January 23 through March 24, 2023, AECOM Technical Services, Inc. (AECOM) field personnel conducted IM implementation activities in the LOC 3 and 10 areas. As presented in the IM Work Plan, shallow soils, impacted with metals, were excavated to a depth of 2 feet below land surface in the central area of the site around the radar antenna and associated equipment. AECOM personnel excavated 77.43 tons of soil using hand tools and, when able, heavy equipment. The soils were placed into lined roll-off containers, which were covered and transported under manifest to the Cedar Trail Landfill in Bartow, Florida. The site was restored to original condition using certified clean backfill material (sand), with filter fabric, and gravel. Areas outside of the excavation were restored with grass seed. On June 6, 2023, AECOM field personnel conducted groundwater sampling activities within the soil IM excavation area. AECOM personnel collected one groundwater sample from monitoring well Q6RS-MW0003. The sample was submitted to a fixed-based laboratory for analysis by United States Environmental Protection Agency Method 6020B for metals (barium and copper). Barium and copper were detected at 18 micrograms per liter (µg/L) and 14 µg/L, respectively, and were below the State of Florida Groundwater Cleanup Target Levels (GCTLs) for barium at 2,000 µg/L and copper at 1,000 µg/L.

Chadwick Sloan Lee↗

High-Energy X-ray Diffraction Microscopy for Nuclear Forensics FY2022 Project Report

Morphological information on nuclear material has been identified using visible light and scanning electron microscopy. These identify qualitative differences in particle morphology. Three-dimensional imaging of materials through alternating scanning electron microscopy imaging and focused ion beam milling has also been used. Unfortunately, these techniques are time- and labor-intensive, with significant sample preparation required and lengthy analysis times. Further, the resulting 3D images are qualitative, require manual identification, and do not capture statistically-representative populations. High energy X-ray 3D imaging using a direct-beam or diffracted-beam (High-Energy Diffraction Microscopy) have been developed at the Advanced Photon Source and can produce quantitative information on grains (phase, location, etc.) and pores (size distribution, sphericity) in a material. These techniques require only minutes to characterize a sample volume and are non-destructive, thus suitable for a wide range of existing samples and for confirmatory analyses to be carried out using conventional microscopy techniques. In this first year of the project, all uranium oxide samples were synthesized and characterized using conventional analyses by the analytical chemistry laboratory. Conventional analysis methods included powder x-ray diffraction, scanning electron microscopy, impurity analysis via inductively coupled plasma mass spectrometry, and infrared spectroscopy. Impurity analysis shows a drop in boron content from UO 3 to the lowest U 3 O 8 calcination temperature, but otherwise no appreciable difference in any sample. Analysis of diffraction data shows a flip of peaks from UO 3 dominated for the 600 °C calcined sample to U 3 O 8 dominated at 700 °C and 800 °C. Analysis of scanning electron microscopy images shows that with increased calcination temperature the size distribution of particles seems to increase and broaden. Both of these last findings are in line with previously published data, though this work used significantly fewer particles to simply show similar trends instead of getting truly quantitative particle analysis. Infrared analysis similarly shows ingrowth of U 3 O 8 as calcination temperature is increased, along with depression of peaks associated with UO 3 and water. Samples were prepared for analysis at the Advanced Photon Source at beamline 1-ID. It is anticipated that analysis will occur in November of 2022. AI/ML techniques to de-noise data coming out of 1-ID during the analyses was also developed during this time using previously gathered data. Preliminary results using a self-supervision technique called Noise2Selfshow good de-noising of data. Once the uranium oxide samples are analyzed, real data will be used to test the de-noising and other AI/ML techniques that may be developed in the second year of the project.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-Energy X-ray Diffraction Microscopy for Nuclear Forensics (FY23 Project Report)

Morphological information on nuclear material has been identified using visible light and scanning electron microscopy. These identify qualitative differences in particle morphology. Three-dimensional imaging of materials through alternating scanning electron microscopy imaging and focused ion beam milling has also been used. Unfortunately, these techniques are time- and labor-intensive, with significant sample preparation required and lengthy analysis times. Further, the resulting 3D images are qualitative, require manual identification, and do not capture statistically-representative populations. High energy X-ray 3D imaging using a direct-beam or diffracted-beam (High-Energy Diffraction Microscopy) have been developed at the Advanced Photon Source and can produce quantitative information on grains (phase, location, etc.) and pores (size distribution, sphericity) in a material. These techniques require only minutes to characterize a sample volume and are non-destructive, thus suitable for a wide range of existing samples and for confirmatory analyses to be carried out using conventional microscopy techniques.

36 MATERIALS SCIENCE↗

Infrared spectroscopic method for uranium isotopic analysis

A high performance infrared (HPIR) system was developed and demonstrated for the infrared absorption analysis of {sup 235}U and {sup 238}U isotopes in uranium hexafluoride gas samples. Sweeping the quantum cascade laser light source over the spectral range and sampling via a high-rate analog-to-digital converter provided 0.0005 cm-1 spectral resolution, which allowed for high-precision measurements of the isotopic peak shift. A data analysis method was developed using principal component analysis to predict the isotope weight % content of {sup 235}U. The HPIR precision, accuracy, and error were evaluated for a wide range of isotopic ratio samples (0.287 – 93.7 weight % {sup 235}U), and the results were compared to the International Target Values (ITVS) set forth by the International Atomic Energy Agency (IAEA) for non-destructive and destructive analytical techniques. The method meets or surpasses the IAEA ITVs for non-destructive analysis of samples with isotopic content of depleted to highly enriched. The results also demonstrated the capability of the HPIR system to correctly predict the {sup 235}U weight % content of a mislabeled sample whose isotopic distribution was validated by mass spectroscopic measurements. The HPIR measurement is nondestructive and, thus, allows for confirmatory analyses of the exact sample at a designated IAEA lab if higher-resolution or a certified analysis is needed. (author)

07 ISOTOPE AND RADIATION SOURCES↗

Spectral Induced Polarization-Biogeochemical Relationships for Remediation Amendment Monitoring

Geophysical tools such as electrical resistivity (ER) can indirectly monitor subsurface changes in response to remedial injections. These methods exhibit relatively low spatial resolution compared to sediment core characterization but are advantageous due to the ability to collect measurements non-intrusively over time across large volumes of the subsurface. Moreover, along with confirmatory groundwater or core sampling, geophysical methods can be used during active biogeochemical remedies to monitor short-term contaminant transformations and mobility, as well as part of an overall strategy for long-term monitoring of subsurface contaminated sites. The use of alternating current spectral induced polarization (SIP) provides significantly more information than conventional geophysical methods like direct current ER. SIP allows for monitoring changes in both solution and surface conductivity by separation of real and imaginary conductivity, respectively, as well as surface capacitance. In principle, SIP can measure indicators of remedy progression such as precipitation reactions that sequester contaminants, potentially providing a better indication of amendment delivery and reactivity as compared to conventional ER methods. However, multiple processes and material properties have overlapping (interacting) electrical responses across a range of frequencies. Hence, the purpose of this scoping study was to evaluate if SIP can be used to monitor (a) amendment delivery and (b) precipitation and reactivity of amendments under consideration at Hanford. SIP measurements were collected in fully saturated columns packed with sand and Hanford formation sediments containing (a) amendments that were highly conductive with significant capacitance (zero valent iron – ZVI, sulfur modified iron – SMI) and (b) amendments that exhibited low electrical conductivity with a small capacitance (calcite, apatite, bismuth). The sand was a quartz material with homogenous particle size that exhibited a relatively low surface conductivity. It was used as a control for comparison with the sediments from the Hanford Site, which have a greater surface conductivity because of their complex mineralogy and heterogeneous particle size distribution and may have complex interactions with amendments. The amendment mass fraction was varied to represent the different stages and subsurface locations associated with the delivery of a remedy. The primary objective was to identify the solution and solid surface changes associated with the delivery amendments and their secondary reactions within the subsurface. The figure below summarizes results for the amendments tested through this project. The SIP phase shift or imaginary conductivity change for the high conductivity amendments was more than 10 times that of the low conductivity amendments, highlighting the relative ease of detection of ZVI and SMI independent of the background signal from sand or Hanford sediments. The ZVI phase shift and imaginary conductivity changes occur primarily at high frequency (> 100 Hz) whereas SMI changes were at low frequency (0.01 to 10 Hz). SIP signals of SMI also increased over time and the maximum shifted to lower frequencies. The low conductivity amendments (calcite, abiotic and biotic apatite, bismuth subnitrate) exhibited relatively small phase and imaginary conductivity changes when added to sediments. The changes were above minimum detection limits (0.5 mrad for phase shift, 0.03 µS/cm for imaginary conductivity) for the highest concentration except for the commercial bismuth material. The lowest amendment concentration that can be detected is likely sediment specific, as minerals in sediments (clays, magnetite, Fe-oxides) have some capacitance and, therefore, exhibit a variable phase shift.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗