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Adsorption and Destruction of the G-Series Nerve Agent Simulant Dimethyl Methylphosphonate on Zinc Oxide

Organophosphorus chemical warfare agents (CWAs) are extremely toxic compounds that are nominally mitigated with gas mask filtration employing metal oxide impregnated activated carbon filtration material. To develop more effective sorbents, it is important to understand the surface chemistry between these organophosphorus compounds and the individual components that make up these filtration materials. In this study, density functional theory (DFT) and Fourier transform infrared spectroscopy (FTIR) were employed to investigate the adsorption and decomposition mechanisms between a sarin simulant molecule, dimethyl methylphosphonate (DMMP), and zinc oxide, which is a component found in current filtration materials. Theoretical calculations show that DMMP readily adsorbs to a pristine and hydroxylated ZnO ($101\bar 0$) surface with average adsorption energies of 132 and 65 kJ mol –1 , respectively. Experimental diffuse reflectance fourier transform infrared spectroscopy (DRIFTS) reveals that ZnO adsorbs water and readily hydroxylates under ambient conditions, which can facilitate adsorption through hydrogen bonding of the P$=$O to ZnO surface hydroxyls. FTIR gas phase analysis also reveals that DMMP decomposes in the presence of ZnO nanoparticles (NPs) to produce methanol at room temperature. Assuming a fully hydroxylated surface of ZnO, DFT calculations reveal several plausible mechanisms for DMMP decomposition to form methanol with an activation energy barrier of 99.6 kJ mol –1 . Finally, on the basis of this energy barrier to decompose DMMP, a turnover frequency (TOF) of only 3.5 × 10 –7 s –1 is calculated assuming full coverage of DMMP on the ZnO nanoparticles tested. This value is qualitatively consistent with experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Recovery Conditions and Aggregation Mechanisms on the Chemical and Physical Properties of Hybrid Poplar and Corn Stover Lignins

Heterogeneity in the physical properties and processing behavior of lignins recovered from biorefining process streams can hinder their effective utilization and industrial valorization. This work investigates lignin recovery by acidification from alkaline pretreatment liquors of varying sources (corn stover and hybrid poplar), compositions, solid contents, and incubation temperatures prior to filtration. Recovered lignins were characterized for filtration performance, mass yield, chemical composition, particle size and morphology, and color. A transition temperature was identified corresponding to marked shifts in lignin physical properties and was a function of the solid content and liquor source. Filtration below this temperature yielded slow-filtering, dark, brittle lignins with smoother particle surfaces, whereas precipitation above this threshold yielded fast-filtering, lighter, powdery lignins with rougher particle surfaces. The impact of temperature and concentration on universal cluster aggregation mechanisms was proposed to explain the differences between lignin particle properties and filtration behavior.

Aggregation↗

Gadolinium Oxalate Solubility Measurements in Nitric Acid Solutions

HB-Line will begin processing Pu solutions during FY2012 that will involve the recovery of Pu using oxalate precipitation and filtration. After the precipitation and filtration processes, the filtrate solution will be transferred from HB-Line to H-Canyon. The presence of excess oxalate and unfiltered Pu oxalate solids in these solutions create a criticality safety issue if they are sent to H-Canyon without controls in H-Canyon. One approach involves H-Canyon receiving the filtrate solution into a tank that is poisoned with soluble gadolinium (Gd). Decomposition of the oxalate will occur within a subsequent H-Canyon vessel. The receipt of excess oxalate into the H-Canyon receipt tanks has the potential to precipitate a portion of the Gd poison in the receipt tanks. Because the amount of Gd in solution determines the maximum amount of Pu solids that H-Canyon can receive, H-Canyon Engineering requested that SRNL determine the solubility of Gd in aqueous solutions of 4-10 M nitric acid (HNO 3 ), 4-12 g/L Gd, and 0.15-0.25 M oxalic acid (H 2 C 2 O 4 ) at 25 C. The target soluble Gd concentration is 6 g/L. The data indicate that the target can be achieved above 6 M HNO 3 and below 0.25 M H 2 C 2 O 4 . For 6 M HNO 3 , 10.5 g/L and 7 g/L Gd are soluble in 0.15 M and 0.25 M H 2 C 2 O 4 , respectively. In 4 M HNO 3 , the Gd solubility drops significantly to 2 g/L and 0.25 g/L in 0.15 M and 0.25 M H 2 C 2 O 4 , respectively. The solubility of Gd at 8-10 M HNO 3 exceeds the solubility at 6 M HNO 3 . The data for 4 M HNO 3 showed good agreement with data in the literature. To achieve a target of 6 g/L soluble Gd in solution in the presence of 0.15-0.25 M oxalate, the HNO 3 concentration must be maintained at or above 6 M HNO 3 .

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

ISS Ambient Air Quality: Updated Inventory of Known Aerosol Sources

Spacecraft cabin air quality is of fundamental importance to crew health, with concerns encompassing both gaseous contaminants and particulate matter. Little opportunity exists for direct measurement of aerosol concentrations on the International Space Station (ISS), however, an aerosol source model was developed for the purpose of filtration and ventilation systems design. This model has successfully been applied, however, since the initial effort, an increase in the number of crewmembers from 3 to 6 and new processes on board the ISS necessitate an updated aerosol inventory to accurately reflect the current ambient aerosol conditions. Results from recent analyses of dust samples from ISS, combined with a literature review provide new predicted aerosol emission rates in terms of size-segregated mass and number concentration. Some new aerosol sources have been considered and added to the existing array of materials. The goal of this work is to provide updated filtration model inputs which can verify that the current ISS filtration system is adequate and filter lifetime targets are met. This inventory of aerosol sources is applicable to other spacecraft, and becomes more important as NASA considers future long term exploration missions, which will preclude the opportunity for resupply of filtration products.

ISS Air Quality↗

Development of Test Protocols for International Space Station Particulate Filters

Air quality control on the International Space Station (ISS) is a vital requirement for maintaining a clean environment for the crew and the hardware. This becomes a serious challenge in pressurized space compartments since no outside air ventilation is possible, and a larger particulate load is imposed on the filtration system due to lack of gravitational settling. The ISS Environmental Control and Life Support System (ECLSS) uses a filtration system that has been in use for over 14 years and has proven to meet this challenge. The heart of this system is a traditional High-Efficiency Particulate Air (HEPA) filter configured to interface with the rest of the life support elements and provide effective cabin filtration. The filter element for this system has a non-standard cross-section with a length-to-width ratio (LW) of 6.6. A filter test setup was designed and built to meet industry testing standards. A CFD analysis was performed to initially determine the optimal duct geometry and flow configuration. Both a screen and flow straighter were added to the test duct design to improve flow uniformity and face velocity profiles were subsequently measured to confirm. Flow quality and aerosol mixing assessments show that the duct flow is satisfactory for the intended leak testing. Preliminary leak testing was performed on two different ISS filters, one with known perforations and one with limited use, and results confirmed that the testing methods and photometer instrument are sensitive enough to detect and locate compromised sections of an ISS BFE.Given the engineering constraints in designing spacecraft life support systems, it is anticipated that non-industry standard filters will be required in future designs. This work is focused on developing test protocols for testing the ISS BFE filters, but the methodology is general enough to be extended to other present and future spacecraft filters. These techniques for characterizing the test duct and perform leak testing can be applied to conducting acceptance testing and inventory testing for future manned exploration programs with air revitalization filtration needs, possibly even for in-situ filter element integrity testing for extensively long-duration missions. We plan to address the unique needs for test protocols for crewed spacecraft particulate filters by preparing the initial version of a standard, to be documented as a NASA Technical Memorandum (TM).

Filtration↗

Development of High Strength HEPA Filters for Use in Demanding Air and Gas Streams - 17644

High-efficiency particulate air (HEPA) filters are used in a wide variety of applications, including the removal of radioactive particulate from process off-gas streams and the venting of waste storage containers. Porvair Filtration Group, specializing in the design and manufacture of robust filters in numerous industries, has worked to develop HEPA filter designs for use in such high-demand nuclear process-gas and air streams. Using the requirements of section FK of the American Society of Mechanical Engineers AG-1 Code on Nuclear Air and Gas Treatment (ASME AG-1) as a guide, Porvair Filtration Group has designed filters which can withstand upset conditions to include elevated temperatures, high relative humidity, high particle-loading, and an unconventionally high differential pressure across the filter media; while maintaining excellent removal efficiencies. The process by which Porvair Filtration Group has reached optimized designs was based upon an extended test and development program. Design, manufacture, and testing of flat sheet media samples, geometrically equivalent model filters, and full-scale prototypes was performed at several Porvair Filtration Group facilities located in the United States and the United Kingdom. The methods and results of this development program are outlined in the following paper. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tradeoffs among indoor air quality, financial costs, and CO 2 emissions for HVAC operation strategies to mitigate indoor virus in U.S. office buildings

Adapting building operation during the COVID-19 pandemic to improve indoor air quality (IAQ) while ensuring sustainable solutions in terms of costs and CO 2 emissions is challenging and limited in literature. Our previous study investigated different HVAC operation strategies, including increased filtration using MERV 10, MERV 13, or HEPA filters, as well as supplying 100% outdoor air into buildings for a system initially sized for MERV 10 filtration. This paper significantly extends that research by systematically analyzing the potential financial and environmental impact for different locations in the U.S. The previous medium office building system model is improved to account for operation in different climates. New evaluation metrics are created to consider the comprehensive impact of improving IAQ on costs and CO 2 emissions, using dynamic emission factors for electricity generation depending on the location. HVAC operation strategies are studied in five different locations across the United States, with distinct climates and electricity sources. In four of the five locations, MERV 13 filtration offers the best improvement in IAQ per increase in costs and emissions relative to MERV 10. The exception is the mildest climate of San Diego, where use of 100% outdoor air provides the best IAQ with a limited increase in costs and emissions. Finally, a system not sized for HEPA filtration can lead to increased costs and emissions without much improvement in IAQ.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Core–Shell Nanofibrous Materials with High Particulate Matter Removal Efficiencies and Thermally Triggered Flame Retardant Properties

Dust filtration is a crucial process for industrial waste gas treatment. Great efforts have been devoted to improve the performance of dust filtration filters both in industrial and fundamental research. Conventional air-filtering materials are limited by three key issues: (1) Low filtration efficiency, especially for particulate matter (PM) below 1 μm; (2) large air pressure drops across the filter, which require a high energy input to overcome; and (3) safety hazards such as dust explosions and fires. Here, we have developed a “smart” multifunctional material which can capture PM with high efficiency and an extremely low pressure drop, while possessing a flame retardant design. This multifunctionality is achieved through a core–shell nanofiber design with the polar polymer Nylon-6 as the shell and the flame retardant triphenyl phosphate (TPP) as the core. At 80% optical transmittance, the multifunctional materials showed capture efficiency of 99.00% for PM 2.5 and >99.50% for PM 10–2.5 , with a pressure drop of only 0.25 kPa (0.2% of atmospheric pressure) at a flow rate of 0.5 m s –1 . Furthermore, during direct ignition tests, the multifunctional materials showed extraordinary flame retardation; the self-extinguishing time of the filtrate-contaminated filter is nearly instantaneous (0 s/g) compared to 150 s/g for unmodified Nylon-6.

36 MATERIALS SCIENCE↗

MO-PIS-Exhibit Hall-01: Imaging: CT Dose Optimization Technologies I

Partners in Solutions is an exciting new program in which AAPM partners with our vendors to present practical “hands-on” information about the equipment and software systems that we use in our clinics. The imaging topic this year is CT scanner dose optimization capabilities. Note that the sessions are being held in a special purpose room built on the Exhibit Hall Floor, to encourage further interaction with the vendors. Dose Optimization Capabilities of GE Computed Tomography Scanners Presentation Time: 11:15 – 11:45 AM GE Healthcare is dedicated to the delivery of high quality clinical images through the development of technologies, which optimize the application of ionizing radiation. In computed tomography, dose management solutions fall into four categories: employs projection data and statistical modeling to decrease noise in the reconstructed image - creating an opportunity for mA reduction in the acquisition of diagnostic images. Veo represents true Model Based Iterative Reconstruction (MBiR). Using high-level algorithms in tandem with advanced computing power, Veo enables lower pixel noise standard deviation and improved spatial resolution within a single image. Advanced Adaptive Image Filters allow for maintenance of spatial resolution while reducing image noise. Examples of adaptive image space filters include Neuro 3-D filters and Cardiac Noise Reduction Filters. AutomA adjusts mA along the z-axis and is the CT equivalent of auto exposure control in conventional x-ray systems. Dynamic Z-axis Tracking offers an additional opportunity for dose reduction in helical acquisitions while SmartTrack Z-axis Tracking serves to ensure beam, collimator and detector alignment during tube rotation. SmartmA provides angular mA modulation. ECG Helical Modulation reduces mA during the systolic phase of the heart cycle. SmartBeam optimization uses bowtie beam-shaping hardware and software to filter off-axis x-rays - minimizing dose and reducing x-ray scatter. The DICOM Radiation Dose Structured Report (RDSR) generates a dose report at the conclusion of every examination. Dose Check preemptively notifies CT operators when scan parameters exceed user-defined dose thresholds. DoseWatch is an information technology application providing vendor-agnostic dose tracking and analysis for CT (and all other diagnostic x-ray modalities) SnapShot Pulse improves coronary CTA dose management. VolumeShuttle uses two acquisitions to increase coverage, decrease dose, and conserve on contrast administration. Color-Coding for Kids applies the Broselow-Luten Pediatric System to facilitate pediatric emergency care and reduce medical errors. FeatherLight achieves dose optimization through pediatric procedure-based protocols. Adventure Series scanners provide a child-friendly imaging environment promoting patient cooperation with resultant reduction in retakes and patient motion. Philips CT Dose Optimization Tools and Advanced Reconstruction Presentation Time: 11:45 ‘ 12:15 PM The first part of the talk will cover “Dose Reduction and Dose Optimization Technologies” present in Philips CT Scanners. The main Technologies to be presented include: DoseRight and tube current modulation (DoseRight, Z-DOM, 3D-DOM, DoseRight Cardiac) Special acquisition modes Beam filtration and beam shapers Eclipse collimator and ClearRay collimator NanoPanel detector DoseRight will cover automatic tube current selection that automatically adjusts the dose for the individual patient. The presentation will explore the modulation techniques currently employed in Philips CT scanners and will include the algorithmic concepts as well as illustrative examples. Modulation and current selection technologies to be covered include the Automatic Current Selection component of DoseRight, ZDOM longitudinal dose modulation, 3D-DOM (combination of longitudinal and rotational dose modulation), Cardiac Dose right (an ECG based dose modulation scheme), and the DoseRight Index (DRI) IQ index. The special acquisition modes covers acquisition techniques such as prospective gating that is designed to reduce exposure to the patient through the Cardiac Step and Shoot scan mode. This mode can substitute the much higher dose retrospective scan modes for certain types of cardiac imaging. The beam filtration and beam shaper portion will discuss the variety of filtration and beam shaping configurations available on Philips scanners. This topic includes the x-ray beam characteristics, tube filtration as well as dose compensator characteristics. The Eclipse collimator, ClearRay collimator and the NanoPanel detector portion will discuss additional technologies specific to wide coverage CT that address some of the unique challenges encountered and techniques employed to optimize image quality and optimize dose utilization. The Eclipse collimator reduces extraneous exposure by actively blocking the radiation tails at either end of helical scans that do not contribute to the image generation. The ClearRay collimator and the NanoPanel detector optimize the quality of the signal that reaches the detectors by addressing the increased scattered radiation present in wide coverage and the NanoPanel detector adds superior electronic noise characteristics valuable when imaging at a low dose level. The second part of the talk will present “Advanced Reconstruction Technologies” currently available on Philips CT Scanners. The talk will cover filtered back projection (FBP), iDose4 and Iterative Model Reconstruction (IMR). Each reconstruction method will include a discussion of the algorithm as well as similarities and differences between the algorithms. Examples illustrating the merits of each algorithm will be presented, and techniques and metrics to characterize the performance of each type of algorithm will be presented. The Filtered Back projection portion will discuss and provide a brief summary of relevant standard image reconstruction techniques in common use, and discuss the common tradeoffs when using the FBP algorithm. The iDose4 portion will present the algorithms used for iDose4 as well the different levels. The meaning of different levels of iDose4 available will be presented and quantified. Guidelines for selection iDose4 parameters based on the imaging need will be explained. The different image quality goals available with iDose4 and specifically how iDose4 enables noise reduction, spatial resolution improvement or both will be explained. The approaches to leveraging the benefits of iDose4 such as improved spatial resolution, decreased noise, and artifact prevention will be described and quantified; and measurements and metrics behind the improvements will be presented. The image quality benefits in specific imaging situations as well as how to best combine the technology with other dose reduction strategies to ensure the best image quality at a given dose level will be presented. Insight into the IMR algorithm as well as contrast to the iDose4 techniques and performance characteristics will be discussed. Metrics and techniques for characterizing this class of algorithm and IQ performance will be presented. The image quality benefits and the dose reduction capabilities of IMR will be explored. Illustrative examples of the noise reduction, spatial resolution improvement, and low contrast detectability improvements of the reconstruction method will be presented: clinical cases and phantom measurements demonstrating the benefits of IMR in the areas of low dose imaging, spatial resolution and low contrast resolution are discussed and the technical details behind the measurements will be presented compared to both iDose4 and traditional filtered back projection (FBP)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Gadolinium Oxalate Solubility Measurements in Nitric Acid Solutions

HB-Line will begin processing Pu solutions during FY2012 that will involve the recovery of Pu using oxalate precipitation and filtration. After the precipitation and filtration processes, the filtrate solution will be transferred from HB-Line to H-Canyon. The presence of excess oxalate and unfiltered Pu oxalate solids in these solutions create a criticality safety issue if they are sent to H-Canyon without controls in H-Canyon. One approach involves H-Canyon receiving the filtrate solution into a tank that is poisoned with soluble gadolinium (Gd). Decomposition of the oxalate will occur within a subsequent H-Canyon vessel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Atmospheric Tracer Depletion Testing for Unfiltered Air In-Leakage Determination at the Wolf Creek Nuclear Power Plant

Atmospheric Tracer Depletion tests were conducted at the Wolf Creek Nuclear Power Plant to quantify the unfiltered in-leakage (UI) into the Control Room (CR), Control Building (CB), and Equipment Rooms (ER) at the Wolf Creek Nuclear Power Plant. Wolf Creek has two independent charcoal filter Emergency Ventilation Systems (EVS) that can be used to purify air entering the control building and control room. The Bravo System contains a filtration system in Room 1501 in the Auxiliary Building for the Control Room and another filtration system (FGK02B) on Elevation 2016 for the Control Building. The Alpha system contains a filtration system in Room 1512 in the Auxiliary Building for the Control Room and another filtration system (FGK02A) on Elevation 2016 for the Control Building. The Atmospheric Tracer Depletion (ATD) test is a technique to measure in-leakage using the concentration of perfluorocarbon compounds that have a constant atmospheric background. These levels are present in the Control Room and Control Building under normal operating conditions. When air is supplied by either of the EVS, most of the PFTS are removed by the charcoal filters. If the concentrations of the PFTs measured in protected areas are the same as the levels at the output of the EVS, the in-leakage of outside air into the protected area would be zero. If the concentration is higher in the protected area than at the output of the filter system, there is in-leakage and the in-leakage can be quantified by the difference. Sampling was performed using state-of-the-art Brookhaven Atmospheric Tracer Samplers (BATS) air sampling equipment and analysis performed on Brookhaven National Laboratory (BNL) dedicated PFT analytical systems. In the Alpha test two tracers PMCH and mcPDCH were used to determine in-leakage into the control building. The analytical system was tuned to maximize sensitivity after initial analysis of the Alpha test. The increased sensitivity permitted accurate quantification of five isomers of the PFT PDCH (mtPDCH, pcPDCH, otPDCH, mcPDCH, and ptPDCH). These isomers were quantified in the low concentration samples in the Alpha test and in all samples in the Bravo test. The best estimates of UI (Rui) for the four zones are provided in Table ES-1. For the CB, this estimate averages the four tracers at the four elevations. For the CR, this estimate uses the four sampling units located in the Control Room.

54 ENVIRONMENTAL SCIENCES↗

Atmospheric Tracer Depletion Testing for Unfiltered Air In-Leakage Determination at the Wolf Creek Nuclear Power Plant

Atmospheric Tracer Depletion tests were conducted at the Wolf Creek Nuclear Power Plant to quantify the unfiltered in-leakage (UI) into the Control Room (CR), Control Building (CB), and Equipment Rooms (ER) at the Wolf Creek Nuclear Power Plant. Wolf Creek has two independent charcoal filter Emergency Ventilation Systems (EVS) that can be used to purify air entering the control building and control room. The Bravo System contains a filtration system in Room 1501 in the Auxiliary Building for the Control Room and another filtration system (FGK02B) on Elevation 2016 for the Control Building. The Alpha system contains a filtration system in Room 1512 in the Auxiliary Building for the Control Room and another filtration system (FGK02A) on Elevation 2016 for the Control Building.The Atmospheric Tracer Depletion (ATD) test is a technique to measure in-leakage using the concentration of perfluorocarbon compounds that have a constant atmospheric background. These levels are present in the Control Room and Control Building under normal operating conditions. When air is supplied by either of the EVS, most of the PFTS are removed by the charcoal filters. If the concentrations of the PFTs measured in protected areas are the same as the levels at the output of the EVS, the in-leakage of outside air into the protected area would be zero. If the concentration is higher in the protected area than at the output of the filter system, there is in-leakage and the in-leakage can be quantified by the difference.Sampling was performed using state-of-the-art Brookhaven Atmospheric Tracer Samplers (BATS) air sampling equipment and analysis performed on Brookhaven National Laboratory (BNL) dedicated PFT analytical systems. In the Alpha test two tracers PMCH and mcPDCH were used to determine in-leakage into the control building. The analytical system was tuned to maximize sensitivity after initial analysis of the Alpha test. The increased sensitivity permitted accurate quantification of five isomers of the PFT PDCH (mtPDCH, pcPDCH, otPDCH, mcPDCH, and ptPDCH). These isomers were quantified in the low concentration samples in the Alpha test and in all samples in the Bravo test.The best estimates of UI (Rui) for the four zones are provided in Table ES-1. For the CB, this estimate averages the four tracers at the four elevations. For the CR, this estimate uses the four sampling units located in the Control Room.

54 ENVIRONMENTAL SCIENCES↗

Characterization of Tank 9H Dissolution Batches in Support of Tank Closure Cesium Removal (TCCR) 1A Batch 1 Preparations

Savannah River Remediation (SRR) is currently preparing the first batch of material to be processed through the Tank Closure Cesium Removal (TCCR) 1A system. The feed for TCCR 1A will consist of dissolved saltcake from Tank 9H. Two batches of salt (Batch 1A and Batch 1B) have been dissolved in Tank 9H and subsequently transferred to Tank 10H to prepare Batch 1 for TCCR 1A. Savannah River National Laboratory (SRNL) received samples from each batch of dissolved salt prior to transfer for characterization. SRNL received both a surface and a variable depth sample from Batches 1A and 1B. In both cases no solids were observed in the surface sample, but were observed in the depth sample. For Batch 1A the variable depth sample was only slightly cloudy, while for Batch 1B the variable depth sample contained a significant amount (10.14 wt%) of solids. The solids were determined to be primarily aluminum containing phases, with only a small fraction (0.22 wt%) being sludge solids. In general, the samples from Batch 1A were more concentrated salt solutions than Batch 1B, with sodium concentrations of 8.53 and 8.57 M for the surface and filtered depth samples in Batch 1A, respectively. The sodium concentrations in Batch 1B samples ranged from 4.27 M for the surface sample to 7.57 M for the depth sample filtrate, indicating some stratification within the tank. The 137 Cs activity as well as the total Cs concentration in the filtered Batch 1A depth sample were approximately double the activity and concentration measured in the filtrate from the Batch 1B depth sample. The total Cs concentration in the Batch 1A depth sample filtrate was 22.4 mg/L, while for the Batch 1B depth sample filtrate the total Cs concentration was calculated to be 12.0 mg/L. These Cs concentrations are significantly higher than was measured in Batches 1-3 from Tank 10H dissolved saltcake which was previously processed through the original TCCR unit.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Produced Water and Waste Heat-aided Blowdown Water Treatment: Using Chemical and Energy Synergisms for Value Creation

The project objective was to develop a cooling blowdown water (BDW) treatment process utilizing produced water (PW) and low-grade heat to maximize water reuse and saleable by-product generation while reducing chemical and energy footprints of the treatment. The proposed treatment process consists of mixing, softening, organics and suspended solids removal, reverse osmosis (RO), thermal desalination, and brine electrolysis. BDW samples collected from a local coal-fired power plant and PW samples from two shale gas production wells were used in this study. Each treatment unit was first designed and tested to quantify its treatment efficiency, and its chemical and energy requirements. In addition, a process model was developed and model simulations were conducted based on the experimental results and literature data to optimize the treatment process. A techno-economic analysis was conducted to quantify chemical and energy savings as well as production of 10-lb brine as a saleable product. With the field-collected BDW and PW samples, mixing experiments determined a volumetric mixing ratio 10:1 (BDW:PW) resulted in the best performance of multivalent ions removal and largest chemical savings for softening. Softening of the BDW/PW mixtures using alkaline chemicals (Na 2 CO 3 and NaOH) achieved 95%-100% removal of scaling-forming cations (Ca, Mg, Fe, Ba, Sr) and 60% of silicon, and 10% of total organic carbon (TOC). The mixing and softening treatments yielded an effluent with total dissolved solids (TDS) concentration of 23 g/L. Activated carbon (AC) filtration removed TOC to a low level (< 3 mg/L) and further removed remaining scale-forming divalent metals and silica from the softened water. The AC filtration resulted in a slight reduction of TDS from 23 g/L to 20 g/L, leaving behind only mostly monovalent ions (i.e., sodium and chloride) in the filtered water. These pretreatments yielded a feed water that met the criteria of the downstream reverse osmosis (RO) to prevent membrane fouling. A cross-flow RO system was used to further concentrate the TDS of the AC effluent. Various factors including TDS, pH, and applied pressure were examined and optimal conditions were determined for the co-treatment process. An integrated process consisting of mixing, softening, AC filtration and RO was used to treat a continuous flow (0.25 – 1.2 L/min, or 0.07 – 0.32 gpm) and successfully generated RO permeate as product water (TDS < 0.5 g/L) for reuse in cooling operation, and a concentrate (TDS ~ 45 g/L) to be further treated in a thermal desalination unit. These flow rates meet the FOA’s criterion of 0.01 – 1 gpm. Overall, the co-treatment of BDW/PW allowed shorter ramp-up time compared to treatment of BDW alone. It resulted in 40% and 55% savings of Na 2 CO 3(s) and NaOH, respectively, compared to treating the BDW and PW individually for the same level of softening. The co-treatment also resulted in a 29% energy saving compared to treatment of BDW only for the level of TDS concentration. A thermal desalination system was designed using CFD simulations and manufactured in the WVU Innovation Hub for further treatment of the RO concentrate to generate 10-lb brine. The system has a design flow rate of 2 gpm and has been successfully tested. A bench-scale brine electrolysis system was developed for on-site generation of chlorine/hypochlorite (Cl 2 /OCl - ) and caustic soda (NaOH) as useful chemicals for the co-treatment process. Using salt solutions (0.5 M and 1 M), the system achieved faradaic efficiencies of 93%-97% and 70%-77% for caustic soda and chlorine/hypochlorite generation, respectively. An economic analysis showed that the electricity costs for on-site generation of these chemicals were significantly lower than the chemical prices offered by suppliers. An industrial-scale process model consisting of mixing, softening, AC filtration, RO, thermal desalination, and brine electrolysis was developed using the Aspen Plus V9 in conjunction with Aspen Custom Modeler V9. The model serves as a solvable Aspen Plus model and as basis to form the costing infrastructure. In addition, techno-economic analysis considering capital, operating, and transportation costs was conducted. An optimization solution showed that produced water for mixing is still advantageous in low quantities. The optimum solution approaches a leveled cost of water (LCW) of 2 $/m 3 which becomes cost competitive with nominal water treatment prices.

20 FOSSIL-FUELED POWER PLANTS↗

Evaporative coolers and wildfire smoke exposure: a climate justice issue in hot, dry regions

Low-income families in dry regions, including in the Southwestern United States, frequently cool their homes with evaporative ("swamp") coolers (ECs). While inexpensive and energy efficient compared to central air conditioners, ECs pull unfiltered outdoor air into the home, creating a health hazard to occupants when wildfire smoke and heat events coincide. A community-engaged research project to reduce wildfire smoke in homes was conducted in California's San Joaquin Valley in homes of Spanish-speaking agricultural workers. A total of 88 study participants with ECs were asked about their level of satisfaction with their EC and their willingness to pay for air filtration. About 47% of participants reported dissatisfaction with their EC, with the most frequently reported reason being that it brings in dust and air pollution. Participants were highly satisfied with air cleaners and air filters that were offered to them free-of-charge. However, a willingness to pay analysis showed that air filtration solutions would not be adopted without significant subsidies; furthermore, air filtration would be an ongoing cost to participants due to the need to regularly replace filters. Short-term filtration solutions for EC users are feasible to implement and may reduce smoke exposure during wildfire events. Such solutions would need to be offered at low-or no-cost to reduce barriers to adoption. Longer term solutions include prioritizing homes with ECs in wildfire smoke exposed regions for replacement with air cooling technologies that provide clean air. Because ECs are disproportionately in low-income homes, addressing smoke intrusion through these devices is an environmental justice issue.

Solomon, Gina M↗

Transpulmonary passage of venous air emboli

Twenty-seven paralyzed anesthetized dogs were embolized with venous air to determine the effectiveness of the pulmonary vasculature for bubble filtration or trapping. Air doses ranged from 0.05 to 0.40 ml/kg min in 0.05-ml increments with ultrasonic Doppler monitors placed over arterial vessels to detect any microbubbles that crossed the lungs. Pulmonary vascular filtration of the venous air infusions was complete for the lower air doses ranging from 0.05 to 0.30 ml/kg min. When the air doses were increased to 0.35 ml/kg min, the filtration threshold was exceeded with arterial spillover of bubbles occurring in 50 percent of the animals and reaching 71 percent for 0.40 ml/kg min. Significant elevations were observed in pulmonary arterial pressure and pulmonary vascular resistance. Systemic blood pressure and cardiac output decreased, whereas left ventricular end-diastolic pressure remained unchanged. The results indicate that the filtration of venous bubbles by the pulmonary vasculature was complete when the air infusion rates were kept below a threshold value of 0.30 ml/kg min.

Butler, B. D.↗

Rotating Reverse-Osmosis for Water Purification

A new design for a water-filtering device combines rotating filtration with reverse osmosis to create a rotating reverse- osmosis system. Rotating filtration has been used for separating plasma from whole blood, while reverse osmosis has been used in purification of water and in some chemical processes. Reverse- osmosis membranes are vulnerable to concentration polarization a type of fouling in which the chemicals meant not to pass through the reverse-osmosis membranes accumulate very near the surfaces of the membranes. The combination of rotating filtration and reverse osmosis is intended to prevent concentration polarization and thereby increase the desired flux of filtered water while decreasing the likelihood of passage of undesired chemical species through the filter. Devices based on this concept could be useful in a variety of commercial applications, including purification and desalination of drinking water, purification of pharmaceutical process water, treatment of household and industrial wastewater, and treatment of industrial process water. A rotating filter consists of a cylindrical porous microfilter rotating within a stationary concentric cylindrical outer shell (see figure). The aqueous suspension enters one end of the annulus between the inner and outer cylinders. Filtrate passes through the rotating cylindrical microfilter and is removed via a hollow shaft. The concentrated suspension is removed at the end of the annulus opposite the end where the suspension entered.

Lueptow, RIchard M.↗

Mars Atmosphere Effects on Arc Welds: Phase 1

NASA has been unprecedented in achieving its goals related to space exploration and furthering the understanding of our solar system. In keeping with this trend, NASA's current mission is to land a team of astronauts on Mars and return them safely to Earth. In addition to comprising much of the structure and life support systems that will be brought to Mars for the habitat and vehicle, titanium and aluminum can be found and mined on Mars and may be used when building structures.Where metals are present, there will be a need for welding capabilities. For welds that need to be made quickly and are located far from heavy resistance or solid state welding machinery, there will be a need for basic arc welding. Arc welding has been a major cornerstone of manufacturing throughout the 20th century, and the portability and capability of gas tungsten arc welding (GTAW) will be necessary for repair, manufacturing, and survival on Mars. The two primary concerns for welding on Mars are that the Martian atmosphere contains high levels of carbon dioxide (CO2), and the atmospheric pressure is much lower than it is on Earth. The high levels of CO2 in the Martian atmosphere may dissociate and produce oxygen in the arc and therefore increase the risk of oxidation. For simplification, atmospheric pressure will not be taken into account for this experiment. For survival on Mars during this mission, the life support and water filtration systems must be kept operational at all times. In order to ensure that water filtration systems can be repaired in the event of an emergency, it is very important to have the capability to weld. The Orion capsule and Mars lander must also remain operational throughout the duration of the mission to ensure the safe return of the astronauts on the mission to Mars. A better understanding of welding in a Mars environment is important to ensure that repair welds are possible if the Orion capsule/Mars lander or water filtration system is damaged at any point while on the surface of Mars. The Orion capsule is made primarily of AA2219-T87, and the water filtration system is primarily Ti-6Al-4V, so the effect of the Mars environment on welding those materials must be known to reduce potential mission risk. GTAW is a portable process that can weld a versatile group of metals, so it has many potential applications for welding on Mars. Thus, missions to colonize Mars will depend on the capability to weld a strong, leak-tight joint. Metals are also likely to be used in support structures made of a lightweight and durable material. For this reason, it is important to understand the implications of welding in a Mars environment. A comparison of the Martian and terrestrial atmospheres are provided in table 1. Based on the elemental compositions, simulation of the Martian atmosphere can be made using primarily CO2 gas.

Courtright, Z. S.↗