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Challenges to Collection of High Quality Samples of Saltstone - 17468

The Savannah River Site (SRS) Saltstone Disposal Facility (SDF) is used to dispose of low-level radioactive liquid waste in the form of grout. The SDF is comprised of a series of concrete saltstone disposal units (SDUs) that receive the grout. The grout solidifies into a cementitious waste form known as saltstone. Properties of saltstone that influence contaminant release have been measured on simulant material but not on samples of emplaced saltstone because samples of emplaced radioactive saltstone are difficult to obtain, transport, and store in a manner that protects the properties of interest. Savannah River Remediation (SRR) initiated a project to obtain samples of emplaced saltstone such that the two critical properties, hydraulic conductivity and reduction capacity, are negligibly impacted by the sample collection effort. The sample collection project was established to manage sample collection efforts beginning with sample collection mock-up activities through field execution. The project focused on three phases: mock-up in a clean environment, development of equipment needed to maintain an inert environment during sample transport and laboratory storage, and coordination of Facility operations and support resources and schedules to support sample collection. A mock-up facility was constructed at SRS to mimic the SDU. Core drill equipment was tested, procedures developed, and operator training conducted using the mockup facility. Concurrent with mock-up activities, inert transportation and storage equipment was designed, manufactured, tested, and specific operating instruction included in the sample collection procedure. Inerting equipment minimized oxidation from the atmosphere as the samples were removed from the disposal unit, transported, and stored in the laboratory awaiting analysis. Coordination with the Saltstone Facility began during construction of the mock-up platform to collect current as-built information for platform construction. Baseline data was collected from the disposal unit vapor space to assess the potential for personnel exposure from chemical hazards associated with trapped vapors. Based on this data, mitigating actions were incorporated into the project scope. Finally, project and facility schedules were integrated to assure that facility non-processing windows, support personnel, equipment fabrication, and field preparation activities were in alignment and supportive of the overall sample collection objectives. During May 2014, 485 linear cm of approximately 5 cm diameter radioactive core material was successfully collected from three access ports in SDU Cell 2A, inerted, transported to the laboratory, and stored in an inert environment for analysis. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

RAPID RADIOCHEMICAL ANALYSES IN SUPPORT OF FUKUSHIMA NUCLEAR ACCIDENT

There is an increasing need to develop faster analytical methods for emergency response, including emergency soil and air filter samples. The Savannah River National Laboratory (SRNL) performed analyses on samples received from Japan in April, 2011 as part of a U.S. Department of Energy effort to provide assistance to the government of Japan, following the nuclear event at Fukushima Daiichi, resulting from the earthquake and tsunami on March 11, 2011. Of particular concern was whether it was safe to plant rice in certain areas (prefectures) near Fukushima. The primary objectives of the sample collection, sample analysis, and data assessment teams were to evaluate personnel exposure hazards, identify the nuclear power plant radiological source term and plume deposition, and assist the government of Japan in assessing any environmental and agricultural impacts associated with the nuclear event. SRNL analyzed approximately 250 samples and reported approximately 500 analytical method determinations. Samples included soil from farmland surrounding the Fukushima reactors and air monitoring samples of national interest, including those collected at the U.S. Embassy and American military bases. Samples were analyzed for a wide range of radionuclides, including strontium-89, strontium-90, gamma-emitting radionuclides, and plutonium, uranium, americium and curium isotopes. Technical aspects of the rapid soil and air filter analyses will be described. The extent of radiostrontium contamination was a significant concern. For {sup 89,90}Sr analyses on soil samples, a rapid fusion technique using 1.5 gram soil aliquots to enable a Minimum Detectable Activity (MDA) of <1 pCi {sup 89,90} Sr /g of soil was employed. This sequential technique has been published recently by this laboratory for actinides and radiostrontium in soil and vegetation. It consists of a rapid sodium hydroxide fusion, pre-concentration steps using iron hydroxide and calcium fluoride precipitations, followed by Sr-Resin separation and gas flow proportional counting. To achieve a lower detection limit for analysis of some of the Japanese soil samples, a 10 gram aliquot of soil was taken, acid-leached and processed with similar preconcentration chemistry. The MDA using this approach was ~0.03 pCi/g (1.1 mBq/g)/, which is less than the 0.05-0.10 pCi/g {sup 90}Sr levels found in soil as a result of global fallout. The chemical yields observed for the Japanese soil samples was typically 75-80% and the laboratory control sample (LCS) and matrix spike (MS) results looked very good for this work Individual QC results were well within the ± 25% acceptable range and the average of these results does not show significant bias. Additional data for a radiostrontium in soil method for 50 gram samples will also be presented, which appears to be a significant step forward based on looking at the current literature, with higher chemical yields for even larger sample aliquots and lower MDA. Hou et al surveyed a wide range of separation methods for Pu in waters and environmental solid samples. While there are many actinide methods in the scientific literature, few would be considered rapid due to the tedious and time-consuming steps involved. For actinide analyses in soil, a new rapid method for the determination of actinide isotopes in soil samples using both alpha spectrometry and inductively-coupled plasma mass spectrometry was employed. The new rapid soil method utilizes an acid leaching method, iron/titanium hydroxide precipitation, a lanthanum fluoride soil matrix removal step, and a rapid column separation process with TEVA Resin. The large soil matrix is removed easily and rapidly using these two simple precipitations with high chemical recoveries and effective removal of interferences. Vacuum box technology and rapid flow rates were used to reduce analytical time. Challenges associated with the mineral content in the volcanic soil will be discussed. Air filter samples were reported within twenty-four (24) hours of receipt using rapid techniques published previously. The rapid reporting of high quality analytical data arranged through the U.S. Department of Energy Consequence Management Home Team was critical to allow the government of Japan to readily evaluate radiological impacts from the nuclear reactor incident to both personnel and the environment. SRNL employed unique rapid methods capability for radionuclides to support Japan that can also be applied to environmental, bioassay and waste management samples. New rapid radiochemical techniques for radionuclides in soil and other environmental matrices as well as some of the unique challenges associated with this work will be presented that can be used for application to environmental monitoring, environmental remediation, decommissioning and decontamination activities.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Rapid Radiochemical Analyses in Support of Fukushima Nuclear Accident - 13196

There is an increasing need to develop faster analytical methods for emergency response, including emergency soil and air filter samples [1, 2]. The Savannah River National Laboratory (SRNL) performed analyses on samples received from Japan in April, 2011 as part of a U.S. Department of Energy effort to provide assistance to the government of Japan, following the nuclear event at Fukushima Daiichi, resulting from the earthquake and tsunami on March 11, 2011. Of particular concern was whether it was safe to plant rice in certain areas (prefectures) near Fukushima. The primary objectives of the sample collection, sample analysis, and data assessment teams were to evaluate personnel exposure hazards, identify the nuclear power plant radiological source term and plume deposition, and assist the government of Japan in assessing any environmental and agricultural impacts associated with the nuclear event. SRNL analyzed approximately 250 samples and reported approximately 500 analytical method determinations. Samples included soil from farmland surrounding the Fukushima reactors and air monitoring samples of national interest, including those collected at the U.S. Embassy and American military bases. Samples were analyzed for a wide range of radionuclides, including strontium-89, strontium-90, gamma-emitting radionuclides, and plutonium, uranium, americium and curium isotopes. Technical aspects of the rapid soil and air filter analyses will be described. The extent of radiostrontium contamination was a significant concern. For {sup 89,90}Sr analyses on soil samples, a rapid fusion technique using 1.5 gram soil aliquots to enable a Minimum Detectable Activity (MDA) of <1 pCi {sup 89,90}Sr /g of soil was employed. This sequential technique has been published recently by this laboratory for actinides and radiostrontium in soil and vegetation [3, 4]. It consists of a rapid sodium hydroxide fusion, pre-concentration steps using iron hydroxide and calcium fluoride precipitations, followed by Sr-Resin separation and gas flow proportional counting. To achieve a lower detection limit for analysis of some of the Japanese soil samples, a 10 gram aliquot of soil was taken, acid-leached and processed with similar preconcentration chemistry. The MDA using this approach was ∼0.03 pCi/g (1.1 mBq/g)/, which is less than the 0.05-0.10 pCi/g {sup 90}Sr levels found in soil as a result of global fallout. The chemical yields observed for the Japanese soil samples was typically 75-80% and the laboratory control sample (LCS) and matrix spike (MS) results looked very good for this work Individual QC results were well within the ± 25% acceptable range and the average of these results does not show significant bias. Additional data for a radiostrontium in soil method for 50 gram samples will also be presented, which appears to be a significant step forward based on looking at the current literature, with higher chemical yields for even larger sample aliquots and lower MDA [5, 6, 7] Hou et al surveyed a wide range of separation methods for Pu in waters and environmental solid samples [8]. While there are many actinide methods in the scientific literature, few would be considered rapid due to the tedious and time-consuming steps involved. For actinide analyses in soil, a new rapid method for the determination of actinide isotopes in soil samples using both alpha spectrometry and inductively-coupled plasma mass spectrometry was employed. The new rapid soil method utilizes an acid leaching method, iron/titanium hydroxide precipitation, a lanthanum fluoride soil matrix removal step, and a rapid column separation process with TEVA Resin. The large soil matrix is removed easily and rapidly using these two simple precipitations with high chemical recoveries and effective removal of interferences. [9, 10] Vacuum box technology and rapid flow rates were used to reduce analytical time. Challenges associated with the mineral content in the volcanic soil will be discussed. Air filter samples were reported within twenty-four (24) hours of receipt using rapid techniques published previously. [11] The rapid reporting of high quality analytical data arranged through the U.S. Department of Energy Consequence Management Home Team was critical to allow the government of Japan to readily evaluate radiological impacts from the nuclear reactor incident to both personnel and the environment. SRNL employed unique rapid methods capability for radionuclides to support Japan that can also be applied to environmental, bioassay and waste management samples. New rapid radiochemical techniques for radionuclides in soil and other environmental matrices as well as some of the unique challenges associated with this work will be presented that can be used for application to environmental monitoring, environmental remediation, decommissioning and decontamination activities. (authors)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The use of commercial and industrial waste in energy recovery systems - A UK preliminary study

Highlights: > Commercial and industrial waste samples collected. > Samples analysed for calorific value, moisture, ash and elemental composition. > Values similar to those of municipal solid waste and refuse derived fuel. > Sampled waste could be used in current energy recovery systems with minimal retrofitting. > Sampled waste could account 6.5% towards the UK's 2020 renewable electricity target if all qualifying waste is used. - Abstract: With 2020 energy targets set out by the EU fast approaching, the UK is trying to source a higher proportion of its energy from renewable resources. Coupled with this, a growing population and increasing trends in consumer demand have resulted in national waste loads increasing. A possible solution to both issues is energy-from-waste (EfW) technologies. Many studies have focused on municipal solid waste (MSW) as a potential feedstock, but appear to overlook the potential benefits of commercial and industrial waste (C and IW). In this study, samples of C and IW were collected from three North West waste management companies and Lancaster University campus. The samples were tested for their gross and net calorific value, moisture content, ash content, volatile matter, and also elemental composition to determine their suitability in EfW systems. Intra-sample analysis showed there to be little variation between samples with the exception two samples, from waste management site 3, which showed extensive variation with regards to net calorific value, ash content, and elemental analysis. Comparisons with known fuel types revealed similarities between the sampled C and IW, MSW, and refuse derived fuel (RDF) thereby justifying its potential for use in EfW systems. Mean net calorific value (NCV) was calculated as 9.47 MJ/kg and concentrations of sulphur, nitrogen, and chlorine were found to be below 2%. Potential electrical output was calculated using the NCV of the sampled C and IW coupled with four differing energy generation technologies. Using a conventional incinerator with steam cycle, total electrical output was calculated as 24.9 GWh, based on a plant operating at 100,000 tpa. This value rose to 27.0 GWh when using an integrated gasification combined cycle. A final aspect of this study was to deduce the potential total national electrical output if all suitable C and IW were to be used in EfW systems. Using incineration coupled with a steam turbine, this was determined to be 6 TWh, 1.9% of the national demand thereby contributing 6.5% towards the UK's 2020 renewable electricity target.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Optimal reference genes for RNA tissue analysis in small animal models of hemorrhagic fever viruses

Abstract Reverse-transcription quantitative polymerase chain reaction assays are frequently used to evaluate gene expression in animal model studies. Data analyses depend on normalization using a suitable reference gene (RG) to minimize effects of variation due to sample collection, sample processing, or experimental set-up. Here, we investigated the suitability of nine potential RGs in laboratory animals commonly used to study viral hemorrhagic fever infection. Using tissues (liver, spleen, gonad [ovary or testis], kidney, heart, lung, eye, brain, and blood) collected from naïve animals and those infected with Crimean–Congo hemorrhagic fever (mice), Nipah (hamsters), or Lassa (guinea pigs) viruses, optimal species-specific RGs were identified based on five web-based algorithms to assess RG stability. Notably, the Ppia RG demonstrated stability across all rodent tissues tested. Optimal RG pairs that include Ppia were determined for each rodent species ( Ppia and Gusb for mice; Ppia and Hrpt for hamsters; and Ppia and Gapdh for guinea pigs). These RG pair assays were multiplexed with viral targets to improve assay turnaround time and economize sample usage. Finally, a pan-rodent Ppia assay capable of detecting Ppia across multiple rodent species was developed and successfully used in ecological investigations of field-caught rodents, further supporting its pan-species utility.

Davies, Katherine A.↗

Biogeochemistry of upland to wetland soils, sediments, and surface waters across Mid-Atlantic and Great Lakes coastal interfaces

Transferable and mechanistic understanding of cross-scale interactions is necessary to predict how coastal systems respond to global change. Cohesive datasets across geographically distributed sites can be used to examine how transferable a mechanistic understanding of coastal ecosystem control points is. To address the above research objectives, data were collected by the EXploration of Coastal Hydrobiogeochemistry Across a Network of Gradients and Experiments (EXCHANGE) Consortium – a regionally distributed network of researchers that collaborated on experimental design, methodology, collection, analysis, and publication. The EXCHANGE Consortium collected samples from 52 coastal terrestrial-aquatic interfaces (TAIs) during Fall of 2021. At each TAI, samples collected include soils from across a transverse elevation gradient (i.e., coastal upland forest, transitional forest, and wetland soils), surface waters, and nearshore sediments across research sites in the Great Lakes and Mid-Atlantic regions (Chesapeake and Delaware Bays) of the continental USA. The first campaign measures surface water quality parameters, bulk geochemical parameters on water, soil, and sediment samples, and physicochemical parameters of sediment and soil.

54 ENVIRONMENTAL SCIENCES↗

Optimization of In-Field Alpha Spectrometry for Uranium Enrichment Determination in Uranium Hexafluoride

In response to needs identified by the International Atomic Energy Agency (IAEA) research is underway to develop In-Field Alpha Spectrometry (IFAS) as a method to allow IAEA safeguards inspectors to collect samples of uranium hexafluoride (UF6) at processing facilities to assess and verify uranium enrichment. For sample collection, the IFAS method uses Single-Use Destructive Assay (SUDA) samplers, which contain thin zeolite coatings that trap UF6 gas and convert it to the safer, more stable form uranyl fluoride (UO2F2). For alpha spectrometry, the IFAS instrument employs a large area silicon semiconductor transducer to detect and record alpha particle energy-deposition events. Over the past year optimization work has significantly increased the diameter of useful SUDA samples (from 12.7 mm to 48 mm), improved the manufacturability and reproducibility of SUDA samples, increased the area of the IFAS alpha spectrometer sensor from 1.2 cm to 3.1 cm, and improved source positioning within the IFAS. This paper will report on this optimization work, its impacts on IFAS performance, and future plans for IFAS miniaturization, improvements, and testing.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

Optimization Of In-field Alpha Spectrometry For Uranium Enrichment Determination In Uranium Hexafluoride

In response to needs identified by the International Atomic Energy Agency (IAEA) research is underway to develop In-Field Alpha Spectrometry (IFAS) as a method to allow IAEA safeguards inspectors to collect samples of uranium hexafluoride (UF6) at processing facilities to assess and verify uranium enrichment. For sample collection, the IFAS method uses Single-Use Destructive Assay (SUDA) samplers, which contain thin zeolite coatings that trap UF6 gas and convert it to the safer, more stable form uranyl fluoride (as a dihydrate, UO2F2&middot;2H2O). For alpha spectrometry, the IFAS instrument employs a large area silicon semiconductor transducer to detect and record alpha particle energy-deposition events. Over the past year optimization work has significantly increased the diameter of useful SUDA samples (from 12.7 mm to 48 mm), improved the manufacturability and reproducibility of SUDA samples, increased the area of the IFAS alpha spectrometer sensor from 1.2 cm to 3.1 cm, and improved source positioning within the IFAS. This paper will report on this optimization work, its impacts on IFAS performance, and future plans for IFAS miniaturization, improvements, and testing.

Chichester, David↗

In-Field Alpha Spectrometer Development FY2022 Mid-Year Report

In response to needs identified by the International Atomic Energy Agency (IAEA), Idaho National Laboratory (INL) has developed an In-Field Alpha Spectrometer (IFAS) to allow IAEA safeguards inspectors to collect samples of uranium hexafluoride (UF 6 ) at processing facilities, to perform field assessments to verify uranium enrichment. For sample collection, the IFAS method uses Single-Use Destructive Assay (SUDA) samplers, developed at Pacific Northwest National Laboratory (PNNL), which contain thin zeolite coatings that trap UF6 gas and convert it to the safer, more stable form uranyl fluoride (as a dihydrate, UO 2 F 2 ·2H 2 O). For alpha spectrometry, the IFAS instrument employs a large area silicon semiconductor transducer to detect and record alpha particle energy-deposition events. Over the course of this project INL, PNNL, Oak Ridge National Laboratory worked to optimize the SUDA sample design for alpha spectrometry, to optimize processes for manufacturing, loading, and shipping SUDA samples, and to allow the measurement of loaded SUDA samples. In fiscal year (FY) 2022 INL has bene investigating the reproducibility and measurement precision of IFAS measurements and the associated determination of uranium enrichment.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

A Corrected Score Function Framework for Modelling Circadian Gene Expression

Many biological processes display oscillatory behaviour based on an approximately 24 h internal timing system specific to each individual. One process of particular interest is gene expression, for which several circadian transcriptomic studies have identified associations between gene expression during a 24 h period and an individual's health. A challenge with analysing data from these studies is that each individual's internal timing system is offset relative to the 24 h day-night cycle, where day–night cycle time is recorded for each collected sample. Laboratory procedures can accurately determine each individual's offset and determine the internal time of sample collection. However, these laboratory procedures are labour-intensive and expensive. Here, in this paper, we propose a corrected score function framework to obtain a regression model of gene expression given internal time when the offset of each individual is too burdensome to determine. A feature of this framework is that it does not require the probability distribution generating offsets to be symmetric with a mean of zero. Simulation studies validate the use of this corrected score function framework for cosinor regression, which is prevalent in circadian transcriptomic studies. Illustrations with data from three circadian transcriptomic studies further demonstrate that the proposed framework consistently mitigates bias relative to using a score function that does not account for this offset.

59 BASIC BIOLOGICAL SCIENCES↗

Coal Fired Power Plant Configuration and Operation Impact on Plant Effluent Contaminants and Conditions

The primary objective of this project is to characterize coal contaminants in coal-fired power plant wastewater as a function of coal type, unit configurations, and unit operation profile with uncertainty analysis. This project was in response to the U.S. Department of Energy (DOE) Solicitation DE-FOA-0001842. The project duration was between September 01, 2018, and December 31, 2021 (no-cost extension filed, due to the Covid-19 pandemic restrictions, and approved). Field and lab test program was conducted with the main goal to characterize coal contaminants in coal-fired power plant wastewater as a function of coal type, unit configurations, and unit operation profile with uncertainty analysis. In this project, the team of Lehigh University (prime recipient) and Western Kentucky University identified two suitable Thermoelectric Power Plants (TTPs) firing bituminous and sub-bituminous coals respectively, designed test plans, and performed sample collection. Sampling included coal from each TTPs power generation units, Wet Flue Gas Desulfurization (WFGD) slurry material and waste-water samples taken from the outlet of the water treatment tank prior to discharge and other pertinent locations. Coal samples are dried, crushed, and pulverized according to the American Society for Testing and Materials (ASTM) methods. The prepared coal samples are analyzed for normal proximate and ultimate analysis tests in addition to the toxic metals and anions according to ASTM methods. The FGD slurry materials are analyzed for toxic metals and anions according to Electric Power Research Institute (EPRI) or Environmental Protection Agency (EPA) methods, as appropriate. The wastewater samples from the water treatment tank outlet are analyzed for toxic metals and anions according to EPA methods. The effluent species analyzed include mercury, arsenic, selenium, nitrate/nitrite, bromide, and chlorine. This project provided results of effluent conditions as a function of coal type, unit configuration, and unit operation profile, and identified the levels of uncertainty in the effluent results.

01 COAL, LIGNITE, AND PEAT↗

Nonparametric Multiparticle Set Methods for Interpreting Environmental Samples

Collection and analysis of environmental samples is commonly used by a range of stakeholders in nuclear safeguards and security contexts. While the ubiquity of samples and their transport in the environment allow regular collection, developing and demonstrating methods for analyzing these samples is difficult. In this work, an environmental sample consists of a set of one or more individual particles. Recent advances in reactor simulation have allowed us to generate data that are more representative of real-world environmental samples, enabling statistically defensible method development and testing. The most notable of these advances is a drastic increase in the number of material depletion regions, which allows our simulations to capture the variation in isotopic composition seen at length scales consistent with environmental samples. Traditional approaches for handling multiparticle samples treat each particle in the sample individually, estimating the quantity of interest (e.g., core-average burnup) resulting from measurement and analysis of signatures (e.g., nuclide assays) from each individual particle. Individual estimates are then averaged to generate a single estimate of the quantity of interest over the entire sample. In this presentation, we introduce two novel approaches for interpreting environmental samples that comprise of multiple particles: (1) the Quantile-Quantile Comparator, which uses a multivariate generalization of quantile-quantile plots for comparing unknown statistical distributions, and (2) the Set Transformer, an attention-based neural network module designed to model interactions among elements (particles) in the input set (sample). Statistically representative sampling cannot be guaranteed as samples are passively collected and are beholden to what particles are available in the environment. These new analysis methods for set-input problems are expected to be more robust than traditional approaches to issues of sampling bias where particles are not uniformly distributed throughout regions of interest, as well as generally outperform traditional approaches by jointly considering all elements in the set. We will present results comparing the performance of traditional single particle approaches and the novel Quantile-Quantile Comparator and Set Transformer for interpretation of simulated environmental samples.

Phathanapirom, Birdy↗

2021 Consequence Management Hotline Drill After Action Report

In March 2021, a functional area drill was held at the Remote Sensing Laboratory–Nellis that focused on using CBRNResponder and the Digital Field Monitoring (DFM) tablets for sample hotline operations and the new paper Sample Control Forms (SCFs) for sample collection. Participants included staff trained and billeted as sample control specialists and Consequence Management Response Team (CMRT) field monitoring personnel. Teams were able to successfully gather and transfer samples to the sample control hotline staff through the manual process, though there were several noted areas for improvement. In July and October 2021, two additional functional area drills were held at Sandia National Laboratories that focused on field sample collection and custody transfer at the sample control hotline for the Consequence Management (CM) Radiological Assistance Program (RAP) program. The overarching goal of the drills was to evaluate the current CM process for sample collection, sample drop off, and sample control using the CBRNResponder mobile and web-based applications. The July 2021 drill had an additional focus to have a subset of samples analyzed by the local analytical laboratory, Radiation Protection Sample Diagnostics (RPSD) laboratory, to evaluate the Laboratory Access portal on CBRNResponder. All three drills were able to accomplish their objectives however, there were several issues noted (Observations: 25 Urgent, 29 Important, and 22 Improvement Opportunities). The observations were prioritized according to their impact on the mission as well as categorized to align with the programmatic functional area required to address the issue. This report provides additional detail on each observation for skillset/program leads and software developers to consider for future improvement or mandatory efforts.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

Design of an Unattended Environmental Aerosol Sampling and Analysis System for Gaseous Centrifuge Enrichment Plants

The resources of the IAEA continue to be challenged by the rapid, worldwide expansion of nuclear energy production. Gaseous centrifuge enrichment plants (GCEPs) represent an especially formidable dilemma to the application of safeguard measures, as the size and enrichment capacity of GCEPs continue to escalate. During the early part of the 1990's, the IAEA began to lay the foundation to strengthen and make cost-effective its future safeguard regime. Measures under Part II of 'Programme 93+2' specifically sanctioned access to nuclear fuel production facilities and environmental sampling by IAEA inspectors. Today, the Additional Protocol grants inspection and environmental sample collection authority to IAEA inspectors at GCEPs during announced and low frequency unannounced (LFUA) inspections. During inspections, IAEA inspectors collect environmental swipe samples that are then shipped offsite to an analytical laboratory for enrichment assay. This approach has proven to be an effective deterrence to GCEP misuse, but this method has never achieved the timeliness of detection goals set forth by IAEA. Furthermore it is questionable whether the IAEA will have the resources to even maintain pace with the expansive production capacity of the modern GCEP, let alone improve the timeliness in reaching current safeguards conclusions. New safeguards propositions, outside of familiar mainstream safeguard measures, may therefore be required that counteract the changing landscape of nuclear energy fuel production. A new concept is proposed that offers rapid, cost effective GCEP misuse detection, without increasing LFUA inspection access or introducing intrusive access demands on GCEP operations. Our approach is based on continuous onsite aerosol collection and laser enrichment analysis. This approach mitigates many of the constraints imposed by the LFUA protocol, reduces the demand for onsite sample collection and offsite analysis, and overcomes current limitations associated with the in-facility misuse detection devices. Onsite environmental sample collection offers the ability to collect fleeting uranium hexafluoride emissions before they are lost to the ventilation system or before they disperse throughout the facility, to become deposited onto surfaces that are contaminated with background and historical production material. Onsite aerosol sample collection, combined with enrichment analysis, provides the unique ability to quickly detect stepwise enrichment level changes within the facility, leading to a significant strengthening of facility misuse deterence. We report in this paper our study of several GCEP environmental sample release scenarios and simulation results of a newly designed aerosol collection and particle capture system that is fully integrated with the Laser Ablation, Absorbance Ratio Spectrometry (LAARS) uranium particle enrichment analysis instrument that was developed at the Pacific Northwest National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Strategy for Long-Term Stewardship and Monitoring of Amchitka Island - 12190

The Long-Term Surveillance and Maintenance Plan (LTSMP) for Amchitka details how the U.S. Department of Energy (DOE) intends to fulfill its mission to maintain protection of human health and the environment at and around the sites on Amchitka Island. The LTSMP calls for monitoring to be performed every 5 years, at least in the initial phase of the project. The purpose of the monitoring is to develop a baseline of activity concentrations for selected radionuclides in biota, water, and soil, both on Amchitka and at the reference location on Adak Island, approximately 322 km (200 miles) northeast of Amchitka. Data compiled by the Consortium for Risk Evaluation with Stakeholder Participation (CRESP, 2006) are being included as part of the baseline data set. The specific biological, water, and sediment samples collected during the 2011 sampling event were developed through close coordination with the primary stakeholders, including the Alaska Department of Environmental Conservation, the Aleutian Pribilof Island Association, and the U.S. Fish and Wildlife Service (USFWS). Amchitka is managed by the USFWS as part of the Alaska Maritime National Wildlife Refuge. Two plans were developed to address specific needs of the biological- and the terrestrial-monitoring programs. Results from these monitoring programs will help determine whether the environment is being impacted by radionuclide migration and uptake, and if subsistence and commercial-catch seafood is safe for human consumption. The RESRAD-BIOTA code is being used to evaluate ecological health relative to the radionuclide levels determined from this sampling event. The samples were sent to three laboratories for analysis. With the exception of the seawater samples, most of the samples were sent to the Center for Accelerator Mass Spectrometry at the Lawrence Livermore National Laboratory. A smaller subset of rock-weed samples, Star reindeer lichen samples, and soil samples collected from beneath the lichen were sent to UAF for cesium-137 analysis. Marine sediment samples were also collected and sent to UAF for testing. The seawater samples were sent to the University of Miami Tritium Laboratory for enriched tritium analysis. Results from the seawater samples for tritium were received in September 2011. Results from the 2011 sampling are expected to be available on the LM web site in 2012. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Handbook: Collecting Groundwater Samples from Monitoring Wells in Frenchman Flat, CAU 98

Frenchman Flat basin on the Nevada National Security Site (NNSS) contains Corrective Action Unit (CAU) 98, which is comprised of ten underground nuclear test locations. Environmental management of these test locations is part of the Underground Test Area (UGTA) Activity conducted by the U.S. Department of Energy (DOE) under the Federal Facility Agreement and Consent Order (FFACO) (1996, as amended) with the U.S. Department of Defense (DOD) and the State of Nevada. A Corrective Action Decision Document (CADD)/Corrective Action Plan (CAP) has been approved for CAU 98 (DOE, 2011). The CADD/CAP reports on the Corrective Action Investigation that was conducted for the CAU, which included characterization and modeling. It also presents the recommended corrective actions to address the objective of protecting human health and the environment. The recommended corrective action alternative is “Closure in Place with Modeling, Monitoring, and Institutional Controls.” The role of monitoring is to verify that Contaminants of Concern (COCs) have not exceeded the Safe Drinking Water Act (SDWA) limits (Code of Federal Regulations, 2014) at the regulatory boundary, to ensure that institutional controls are adequate, and to monitor for changed conditions that could affect the closure conditions. The long-term closure monitoring program will be planned and implemented as part of the Closure Report stage after activities specified in the CADD/CAP are complete. Groundwater at the NNSS has been monitored for decades through a variety of programs. Current activities were recently consolidated in an NNSS Integrated Sampling Plan (DOE, 2014). Although monitoring directed by the plan is not intended to meet the FFACO long-term monitoring requirements for a CAU (which will be defined in the Closure Report), the objective to ensure public health protection is similar. It is expected that data collected in accordance with the plan will support the transition to long-term monitoring at each CAU. The sampling plan is designed to ensure that monitoring activities occur in compliance with the UGTA Quality Assurance Plan (DOE, 2012). The sampling plan should be referenced for Quality Assurance (QA) elements and procedures governing sampling activities. The NNSS Integrated Sampling Plan specifies the groundwater monitoring that will occur in CAU 98 until the long-term monitoring program is approved in the Closure Report. The plan specifies the wells that must be monitored and categorizes them by their sampling objective with the associated analytical requirements and frequency. Possible sample collection methods and required standard operating procedures are also presented. The intent of this handbook is to augment the NNSS Integrated Sampling Plan by providing well-specific details for the sampling professional implementing the Sampling Plan in CAU 98, Frenchman Flat. This handbook includes each CAU 98 well designated for sampling in the NNSS Integrated Sampling Plan. The following information is provided in the individual well sections: 1. The purpose of sampling. 2. A physical description of the well. 3. The chemical characteristics of the formation water. 4. Recommended protocols for purging and sampling. The well-specific information has been gathered from numerous historical and current sources cited in each section, but two particularly valuable resources merit special mention. These are the USGS NNSS website (http://nevada.usgs.gov/doe_nv/ntsarea5.cfm) and the UGTA Field Operations website (https://ugta.nv.doe.gov/sites/Field%20Operations/default.aspx). 2 Land surface elevation and measuring point for water level measurements in Frenchman Flat were a focus during CAU investigations (see Appendix B, Attachment 1 in Navarro-Intera, 2014). Both websites listed above provide information on the accepted datum for each well. A summary is found on the home page for the well on the USGS website. Additional information is available through a link in the “Available Data” section to an “MP diagram” with a photo annotated with the datum information. On the UGTA Field Operations well page, the same information is in the “Wellhead Diagram” link. Well RNM-2s does not have an annotated photo at this time. All of the CAU 98 monitoring wells are located within Area 5 of Frenchman Flat, with the exception of ER-11-2 in Area 11 (Figure 1). The wells are clustered in two areas: the northern area (Figure 2) and the central area (Figure 3). Each well is discussed below in geographic order from north to south as follows: ER-11-2, ER-5-3 shallow piezometer, ER-5-3-2, ER-5-5, RNM-1, RNM-2s, and UE-5n.

(1996↗

Impact of collection container material and holding times on sample integrity for mercury and methylmercury in water

Mercury (Hg) and methylmercury (MeHg) concentrations in streamwater can vary on short timescales (hourly or less) during storm flow and on a diel cycle; the frequency and timing of sampling required to accurately characterize these dynamics may be difficult to accomplish manually. Automated sampling can assist in sample collection; however use has been limited for Hg and MeHg analysis due to stability concerns of trace concentrations during extended storage times. We examined the viability of using automated samplers with disposable low-density polyethylene (LDPE) sample bags to collect industrially contaminated streamwater for unfiltered and filtered Hg and MeHg analysis. Specifically we investigated the effect of holding times ranging from hours to days on streamwater collected during baseflow and storm flow. Unfiltered and filtered Hg and MeHg concentrations decreased with increases in time prior to sample processing; holding times of 24 hours or less resulted in concentration changes (mean 11 7% different) similar to variability in duplicates collected manually during analogous field conditions (mean 7 10% different). Comparisons of samples collected with manual and automated techniques throughout a year for a wide range of stream conditions were also found to be similar to differences observed between duplicate grab samples. These results demonstrate automated sampling into LDPE bags with holding times of 24 hours or less can be effectively used to collect streamwater for Hg and MeHg analysis, and encourage the testing of these materials and methods for implementation in other aqueous systems where high-frequency sampling is warranted.

holding time↗

Size-resolved ice nucleating particle (INP) concentrations from the MOSAiC campaign

Sample collection: Ground-based immersion mode ice nucleation measurements were conducted on samples collected at the U.S. DOE ARM AMF2 onboard the R/V Polarstern P-deck during MOSAiC from 23 Oct 2019 to 01 Oct 2020. Samples were collected using a Davis Rotating-drum Unit for Monitoring (DRUM; DRUMAir, LLC) cascading impactor in 4 stages (i.e., size bins). Instrument information on the model used, the DA400, can be found at the DRUMAir website (http://www.drumair.com/). Stages A, B, C, and D had particle size cuts at 2.96, 1.21, 0.34, and 0.15 &micro;m in particle diameter, respectively. Strips of sample substrate (PFA, perfluoroalkoxy; McMaster) were adhered to each disc in each stage and coated with petrolatum to enable particles to stick on impact. The discs move slowly over time, such that aerosol loading is streaked onto the PFA. Every 24 hours, a blank is created on the PFA to separate daily samples. During MOSAiC, the pump typically pulled 20 &ndash; 35 lpm (average of 32 lpm) at the inlet with all the discs in place in each stage. Daily samples were collected for each of the four stages, equaling 28,800 &ndash; 50,400 total L of air (average of 46,080 L total L of air) per sample. Discs rotated for approximately 24 days before the sampling per strip was complete and changed to a new disc. Discs were stored frozen after collection. Sample preparation for analysis: Following collection and transport from MOSAiC to the Kreidenweis/DeMott laboratory, care of PI Creamean, in Fort Collins, CO, strips were removed from the discs and cut up to separate daily samples. Each daily portion of the strip was stored in separate sterile 15-mL centrifuge tubes and stored in a standard commercial freezer until analysis (approximately 4 &ndash; 12 months after collection). Sample analysis: Drop freezing assays (DFAs) were conducted on one daily sample set every 3 &ndash; 4 days of the study for all four stages using the Colorado State University (CSU) cold plate (CP). Sample set days were chosen to cover the entire year of MOSAiC and avoiding days where the AOS purge system was activated. Immediately after removal from the freezer, 2 mL of 0.1-&micro;m filtered deionized water was added with a single-use sterile syringe directly to the tubes, then mixed using a vortex mixer for at least 30 minutes at 500 rpm to resuspend particles from the PFA into the deionized water. Following sample preparation, another single-use syringe was used to create 100 aliquots on a 3-inch diameter copper plate, then covered with a transparent plastic dome. The drops were approximately the same volume (2.5 &micro;L each), though careful inspection. The plate was cooled at approximately 3 &ndash; 10 K min-1 from room temperature until all drops froze on the plate. Temperature was measured by an Omega thermocouple probes and meter. Drop freezing was visually detected but recorded through monitoring software to provide the time frozen, channel of the meter used, temperature, and cooling rate for each drop. Not all 100 drops were always detected; the total number of rows in each data file equals the number of drops recorded, which typically was > 80 %. Each sample was tested three times (i.e., a new set of 100 drops was created for each test). Data provided are files containing these parameters. From the freezing temperatures recorded, the fraction frozen was and INP concentrations were calculated per L of air using the equation from Vali (1971): [INPs] = &minus;(ln(f)/Valiquot)*(Vsuspension/Vair) where f is the proportion of droplets not frozen, Valiquot is the volume of each aliquot (i.e., 2.5e-6 L), Vsuspension is the volume of the suspension (i.e., 0.002 L), and Vair is the volume of air per sample (i.e., 36000 L). Data usage guidance: There are three files included with this dataset: (1) dumcp_inp_concentrations.csv which includes cumulative INP concentrations binned every 0.5 &deg;C from 0 to &ndash;30 &deg;C for all samples and size ranges (i.e., DRUM stages) processed via DFA using the CSU CP; (2) dumcp_inp_standard_deviation.csv which includes the standard deviations for all samples and temperatures in dumcp_inp_concentrations.csv; and (3) dumcp_blank_concentrations_standard_deviation.csv which includes the INP concentrations and standard deviations for the deionized water and PFA blanks binned every 0.5 &deg;C from 0 to &ndash;30 &deg;C. The first column in each file represents the freezing temperature in &deg;C binned every 0.5 &deg;C from 0 to &ndash;30 &deg;C (first cell in this column = header = &ldquo;temp&rdquo;). The second column in each file represents the standard deviation of each temperature bin in &deg;C (first cell in this column = header = &ldquo;temperr&rdquo;). For file (1) dumcp_inp_concentrations.csv, the remaining columns indicate the INP concentrations per L of air for each temperature bin. For each sample column, the header in the first row indicates the stage (i.e., size bin as &ldquo;A_&rdquo;, &ldquo;B_&rdquo;, &ldquo;C_&rdquo;, or &ldquo;D_&rdquo;) and date (&ldquo;_yyyymmdd) of collection. For file (2) dumcp_inp_standard_deviation.csv, the remaining columns indicate the INP concentration standard deviation per L of air for each temperature bin. For each sample column, the header in the first row indicates the stage (i.e., size bin as &ldquo;A_&rdquo;, &ldquo;B_&rdquo;, &ldquo;C_&rdquo;, or &ldquo;D_&rdquo;) and date (&ldquo;_yyyymmdd) of collection. For file (3) dumcp_blank_concentrations_standard_deviation.csv, the remaining columns indicate the INP concentrations and standard deviations for the deionized water blank (&ldquo;di_0.1&rdquo; and &ldquo;di_0.1sd&rdquo; for the concentrations and standard deviations, respectively) and PFA blank (&ldquo;pfa&rdquo; and &ldquo;pfasd&rdquo; for the concentrations and standard deviations, respectively). Please see Creamean et al. (2019a; 2018a; 2018b; 2019b) for additional details on DRUM sample collection and offline processing. For questions or help with data interpretation, contact Dr. Jessie Creamean (jessie.creamean@colostate.edu). References: Creamean, J. M., Mignani, C., Bukowiecki, N., and Conen, F.: Using spectra characteristics to identify ice nucleating particle populations during winter storms in the Alps, Atmos. Chem. Phys., 19, 8123&ndash;8140, 2019a. Creamean, J. M., Kirpes, R. M., Pratt, K. A., Spada, N. S., Maahn, M., de Boer, G., Schnell, R. C., and China, S.: Marine and terrestrial influences on ice nucleating particles during continuous springtime measurements in an Arctic oilfield location, Atmospheric Chemistry and Physics, 18, 18023-18042, 10.5194/acp-18-18023-2018, 2018a. Creamean, J. M., Primm, K. M., Tolbert, M. A., Hall, E. G., Wendell, J., Jordan, A., Sheridan, P. J., Smith, J., and Schnell, R. C.: HOVERCAT: A novel aerial system for evaluation of aerosol-cloud interactions, Atmospheric Measurement Techniques, 11, 3969-3985, 10.5194/amt-11-3969-2018, 2018b. Creamean, J. M., Cross, J. N., Pickart, R., McRaven, L., Lin, P., Pacini, A., Hanlon, R., Schmale, D. G., Ceniceros, J., Aydell, T., Colombi, N., Bolger, E., and DeMott, P. J.: Ice nucleating particles carried from below a phytoplankton bloom to the Arctic atmosphere, Geophys. Res. Lett., 46, 8572-8581, https://doi.org/10.1029/2019GL083039, 2019b. Vali, G.: Quantitative Evaluation of Experimental Results an the Heterogeneous Freezing Nucleation of Supercooled Liquids, Journal of the Atmospheric Sciences, 28, 402-409, 10.1175/1520-0469(1971)028<0402:qeoera>2.0.co;2, 1971.

4-stage DRUM aerosol collector (DA400),Ice nuclei,↗