Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “SURFACE CONTAMINATION”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 811 records · Page 45

Coupled Transport, Reactivity, and Mechanics in Fractured Shale Caprocks

Abstract Shales are low‐permeability caprocks that confine fluid, such as CO 2 , nuclear waste, and hydrogen, in storage formations. Stress‐induced fractures in shale caprocks provide pathways for fluid to leak and potentially contaminate fresh water aquifers. Fractured shales are also increasingly considered as resources for CO 2 sequestration, enhanced geothermal, and unconventional energy recovery. Injecting reactive fluids into shales introduces chemical disequilibrium, causing an onset of a series of dissolution, precipitation, and fines mobilization mechanisms. The reactions have rapid kinetics and significant impact on porosity and permeability; consequently, flow and storage properties of caprocks. While previous research has explored the separate effects of these reactions, this study aims to uncover their simultaneous occurrence and collective influence. This study unveils these highly coupled transport and reactivity mechanisms by tracking and visualizing the reaction‐induced alterations in the matrix, microcracks, and fractures of shales over time. We conducted brine injection experiments sequentially at pH 4 and 2 in a naturally fractured Wolfcamp shale sample while simultaneously imaging the dynamic processes using X‐ray computed tomography (CT). CT images are validated by finer resolution images obtained using micro‐CT and scanning electron microscopy. We also tracked the sample permeability and fluid chemistry using brine permeability and inductively coupled plasma mass spectrometry, respectively. Findings show that fluid primarily flowed through fractures, dissolving reactive minerals and mobilizing fines on fracture surfaces. Dissolution of fracture asperities under confining stress resulted in the closing of fractures. Clogging in narrow fracture pathways, caused by fines accumulation, diverted fluid flow into matrix pores.

58 GEOSCIENCES↗

Evaluating seasonal and regional distribution of snowfall in regional climate model simulations in the Arctic

In this study, we investigate how the regional climate model HIRHAM5 reproduces the spatial and temporal distribution of Arctic snowfall when compared to CloudSat satellite observations during the examined period of 2007–2010. For this purpose, both approaches, i.e., the assessments of the surface snowfall rate (observation-to-model) and the radar reflectivity factor profiles (model-to-observation), are carried out considering spatial and temporal sampling differences. The HIRHAM5 model, which is constrained in its synoptic representation by nudging to ERA-Interim, represents the snowfall in the Arctic region well in comparison to CloudSat products. The spatial distribution of the snowfall patterns is similar in both identifying the southeastern coast of Greenland and the North Atlantic corridor as regions gaining more than twice as much snowfall as the Arctic average, defined here for latitudes between 66 and 81°N. Excellent agreement (difference less than 1%) in the Arctic-averaged annual snowfall rate between HIRHAM5 and CloudSat is found, whereas ERA-Interim reanalysis shows an underestimation of 45% and significant deficits in the representation of the snowfall rate distribution. From the spatial analysis, it can be seen that the largest differences in the mean annual snowfall rates are an overestimation near the coastlines of Greenland and other regions with large orographic variations as well as an underestimation in the northern North Atlantic Ocean. To a large extent, the differences can be explained by clutter contamination, blind zone or higher resolution of CloudSat measurements, but clearly HIRHAM5 overestimates the orographic-driven precipitation. The underestimation of HIRHAM5 within the North Atlantic corridor south of Svalbard is likely connected to a poor description of the marine cold air outbreaks which could be identified by separating snowfall into different circulation weather type regimes. By simulating the radar reflectivity factor profiles from HIRHAM5 utilizing the Passive and Active Microwave TRAnsfer (PAMTRA) forward-modeling operator, the contribution of individual hydrometeor types can be assessed. Looking at a latitude band at 72–73°N, snow can be identified as the hydrometeor type dominating radar reflectivity factor values across all seasons. The largest differences between the observed and simulated reflectivity factor values are related to the contribution of cloud ice particles, which is underestimated in the model, most likely due to the small sizes of the particles. The model-to-observation approach offers a promising diagnostic when improving cloud schemes, as illustrated by comparison of different schemes available for HIRHAM5.

54 ENVIRONMENTAL SCIENCES↗

Materials and Approaches for Mitigation of SOFC Cathode Degradation in SOFC Power Systems

Perovskites such as doped lanthanum manganite and cobaltite have been used successfully as a cathode material in SOFC power systems operating between 700-1000°C. The electrodes, however, remain prone to degradation in presence of Cr containing gas atmosphere under systems operating conditions. Cathode in SOFCs is considered as one of the largest contributors of electrochemical performance degradations, leading to significant increase in ohmic and non-ohmic losses as well as interfacial compound formation. These degradations are mostly irreversible due to permanent changes to chemical and morphological alterations in the electrodes, resulting in the blockage of triple phase boundary (TPB) sites and decrease in oxygen reduction reactions (ORR). Fundamental mechanistic understanding has been developed to elucidate the reaction pathways of electrode poisoning in electronically conducting electrodes (LSM) as well as mixed ionic and electronically conducting electrodes (LSCF). The overall goal of this program has been identification and development of cost effective solutions to mitigate electrode degradations under “real world” systems operating conditions. The overall technological innovations and impact from this work are: The research provides an understanding of the degradation mechanism and cost-effective approaches for implementation in SOFC systems; Develop mitigation processes utilizing low cost getters using conventional synthesis and fabrication route; Develop tailored high surface area powders and coatings for high Cr capture capacity under systems operating conditions; >Developed computational models to understand mechanistic behavior; Experimentally measure rate of Cr evaporation from chromia and alumina forming alloys under SOFC operating conditions; Developed conditions to minimize Cr evaporation from balance-of-plant alloys; This innovation will support the development of getter platform to capture both intrinsic and extrinsic impurities present in air; and, Applications under wide operating temperature range (500-900°C) as well for wide high-temperature electrochemical systems (SOFC, SOEC, and OTM). The work has been successfully developed, validated experimentally and implemented. Successful technology transfer of this knowledge with industrial partners has been accomplished and the getters have been independently tested and validated under their systems operating conditions. The innovation will also find application in related high temperature electrochemical systems such as OTM and SOEC for the prevention of Cr assisted performance degradation. The proposed approach for Cr capture can also be applied to oxy-combustion and other advanced combustion techniques for the reduction of Cr vapor in the exhaust gas stream. This fundamental knowledge gained also has led to the path forward for developing advanced getters for capturing more than one contaminant in air.

01 COAL, LIGNITE, AND PEAT↗

Pilot Testing of a Highly Efficient Pre-combustion Sorbent-based Carbon Capture System

TDA developed and demonstrated a highly efficient pre-combustion carbon capture system. The overall objective of this work was to develop a new sorbent-based pre-combustion carbon capture technology for Integrated Gasification Combined Cycle (IGCC) power plants. In this project our goal was to demonstrate the techno-economic viability of the new technology by 1) demonstrating it in large-scale slipstream tests, and 2) carrying out a high fidelity engineering and cost analysis. TDA’s process used an advanced physical adsorbent that selectively removes CO 2 from coal-derived synthesis gas above the dew point of the gas at temperatures as high as 300°C. The sorbent consists of a mesoporous carbon whose surface was grafted with functional groups that remove CO 2 via a well-known acid-base interaction. As documented in bench-scale experiments and field tests with actual coal gas, the sorbent achieved a very high capacity for CO 2 at temperatures as high as 300°C. The sorbent bound CO 2 more strongly than common physical adsorbents, providing the chemical potential needed for the high temperature operation. However, because CO 2 does not form a true covalent bond with the surface sites (as is the case with chemical absorbents), the sorbent regeneration could be carried out with only a very small energy input. The heat input to regenerate our sorbent was only 4.9 kcal per mol of CO 2 , which is much lower than that for chemical absorbents (e.g., 29.9 kcal/mol CO 2 for sodium carbonate) and was similar to the requirements of physical solvents (e.g., 4 kcal/mol CO 2 for Selexol TM ). Because the sorbent operates above the dew point of the synthesis gas (unlike the Selexol TM process), a higher power cycle efficiency can be achieved. With previous DOE/NETL funding (Contract No. DE-FE-0000469), we demonstrated the techno-economic viability of the technology in bench-scale tests and slipstream demonstrations at the National Carbon Capture Center (NCCC), Wilsonville, Alabama and Wabash River IGCC plant in Terra Haute, Indiana. We demonstrated a stable working CO 2 capacity for over 11,650 cycles with simulated synthesis gas. We also evaluated its performance with actual synthesis gas in two test campaigns at the Wabash River IGCC Plant, Terre Haute, IN and the National Carbon Capture Center (NCCC), Wilsonville, AL. The slipstream tests clearly showed that the actual coal gas constituents and potential contaminants (e.g. trace metals, halides, tars) had no effect on the sorbent’s ability to remove CO 2 (the same sorbent beds were used in both field tests with no sign of deactivation for 2,000 cycles with over 26,750 SCF of gas treated). As expected, due to the high temperature CO 2 removal capability and low energy needed to regenerate the sorbent, the power cycle efficiency with our process was greater than 34% on a higher heating value (HHV) basis; in comparison, the same IGCC plant equipped with the Selexol TM solvent for carbon capture can only achieve 31.4% HHV efficiency. The capital cost for an IGCC system with TDA’s process is estimated as $2,417/kW e , which is 12% lower than that of the IGCC/ Selexol TM process. The levelized cost for electricity including the transport, storage and monitoring (TS&M) cost for CO 2 was calculated as $\$ $92.9/MWh (lowest reported to our knowledge), which is much better than the $105.2/MWh estimated for the IGCC/ Selexol TM process. In this project (DE-FE0013105), TDA Research, in collaboration with our partners Gas Technology Institute (GTI), Illinois Clean Coal Institute (ICCI), University of California, Irvine (UCI), University of Alberta (UOA), Siemens, NCCC and Sinopec advanced the technical maturity of the technology; scaling it up by a factor of 100. We optimized the reactor design using computational fluid dynamics (CFD); using adsorption modeling we improved the pressure swing adsorption (PSA) cycle sequence. We carried out two field test campaigns with a fully-equipped 0.1 MW e prototype unit (for a total of 844 hours) using actual synthesis gas to prove the viability of the new technology. A successful 30 day (707 hrs) evaluation was completed at NCCC under air blown gasification conditions. We demonstrated 97.3% carbon capture at 1,500 SLPM, 93% carbon capture at 1,800 SLPM, and 90% carbon capture at 2,100 SLPM in the NCCC tests. We also demonstrated the system for 137 hours at a Sinopec petrochemical plant under oxygen blown gasification, demonstrating 86% carbon capture at 2,660 SLPM. In collaboration with University of California, Irvine (UCI), we completed a techno-economic analysis (TEA) for TDA’s warm gas cleanup technology integrated to IGCC power plant. The net plant efficiencies (on a coal HHV basis) for the warm gas cleanup cases were estimated to be 34.0% for E-GasTM gasifier, 34.4% for GE gasifier, 33.4 for the Shell gasifier and 34.2 for the TRIG TM gasifier (Cases 2, 4, 6 and 8 in this study) with a catalytic combustor for CO 2 purification, which are significantly higher than those for the Cold Gas Case, or an increase of as much as 12% in the heat rate for Case 2, 6% for Case 4, 9% for Case 6, and 9% for Case 8. The 1st year cost of electricity with the transport, storage and monitoring (TS&M) costs for the CO 2 included was $\$ $129.2/MWh for the E-GasTM gasifier Warm Gas Cleanup Case, $\$ $131.9/MWh for the GE gasifier Warm Gas Cleanup Case, $\$ $146.8/MWh for the Shell Gasifier Warm Gas Cleanup Case, and $\$ $129.9/MWh for the TRIG TM gasifier Warm Gas Cleanup Case. For comparison, the costs for the baseline Cold Gas CO 2 removal with Selexol for the different gasifiers were: $\$ $146.6/MWh for the E-Gas TM gasifier, $\$ $142.2/MWh for the GE gasifier, $\$ $159.0/MWh for the Shell gasifier and $\$ $144.3/MWh for the TRIG TM gasifier. In summary, the costs for our system were 7 to 12% lower than the corresponding Cold Gas Cleanup cases. The results of this techno-economic analysis suggested that TDA’s high temperature PSA-based Warm Gas Clean-up Technology can make a substantial improvement in the IGCC plant thermal performance for achieving near zero CO 2 emissions for E-Gas TM , GE, Shell and TRIG TM gasifier based IGCC power plants. The capital expenses were estimated to be lower than that of Selexol’s™. Taken together, the higher net plant efficiency and lower capital and operating costs resulted in substantial reduction in the cost of carbon capture for the IGCC plant equipped with TDA’s high temperature PSA-based carbon capture system. Finally, in collaboration with Gas Technology Institute (GTI) we completed the environmental health and safety assessment for TDA’s warm gas carbon capture technology.

01 COAL, LIGNITE, AND PEAT↗

Is Genetic Engineering a Route to Enhance Microalgae-Mediated Bioremediation of Heavy Metal-Containing Effluents?

Contamination of the biosphere by heavy metals has been rising, due to accelerated anthropogenic activities, and is nowadays, a matter of serious global concern. Removal of such inorganic pollutants from aquatic environments via biological processes has earned great popularity, for its cost-effectiveness and high efficiency, compared to conventional physicochemical methods. Among candidate organisms, microalgae offer several competitive advantages; phycoremediation has even been claimed as the next generation of wastewater treatment technologies. Furthermore, integration of microalgae-mediated wastewater treatment and bioenergy production adds favorably to the economic feasibility of the former process—with energy security coming along with environmental sustainability. However, poor biomass productivity under abiotic stress conditions has hindered the large-scale deployment of microalgae. Recent advances encompassing molecular tools for genome editing, together with the advent of multiomics technologies and computational approaches, have permitted the design of tailor-made microalgal cell factories, which encompass multiple beneficial traits, while circumventing those associated with the bioaccumulation of unfavorable chemicals. Previous studies unfolded several routes through which genetic engineering-mediated improvements appear feasible (encompassing sequestration/uptake capacity and specificity for heavy metals); they can be categorized as metal transportation, chelation, or biotransformation, with regulation of metal- and oxidative stress response, as well as cell surface engineering playing a crucial role therein. This review covers the state-of-the-art metal stress mitigation mechanisms prevalent in microalgae, and discusses putative and tested metabolic engineering approaches, aimed at further improvement of those biological processes. Finally, current research gaps and future prospects arising from use of transgenic microalgae for heavy metal phycoremediation are reviewed.

Ranjbar, Saeed (ORCID:0000000256518605)↗

Full Scale HEPA Filter Encapsulation in Ultra-High-Performance Grout - Proof of Concept

The Hanford Tank Waste Treatment and Immobilization Plant (WTP) currently being constructed to treat radioactive waste, includes vitrification facilities for both the high-level waste (HLW) and low activity waste (LAW) fractions. Operation of the WTP will produce contaminated high-efficiency particulate air filters (HEPA), as part of the solid secondary waste (SSW) stream. The HEPA filters receive off-gas from the vessel vent header and primary off-gas treatment system in LAW Facility and remove particulate contaminants including 99 Tc and 129 I salts. The current disposal method for HEPA filters is encapsulation in metal containers using cementitious material (CM) and disposal in the Integrated Disposal Facility (IDF). Results from the 2017 IDF Performance Assessment (PA) WRPS (2018) demonstrated that while compliance is maintained for the 1000 year compliance period mandated by DOE O 435.1 and its accompanying manual, release of constituents from the HEPA filters result in exceedance of the performance objective imposed as the groundwater regulatory limit at later times. For example, at about 1500 years post-closure, solid secondary waste (SSW), including HEPA filters is predicted to become a dominant contributor to 99 Tc release and over the 10,000-year sensitivity analysis period, SSW is the dominant contributor of 129 I release to the groundwater. The estimated release could potentially be reduced if the HEPA filters are not compacted and waste containers could be distributed throughout a large space, thereby diluting the contaminant release. Additionally, a better cementitious material could be used to encapsulate the HEPA filters. One alternative method for disposal of contaminated HEPA filters is encapsulation of the filters in ultra high-performance grout (UHPG). UHPG is a variation of ultra-high-performance concrete (UHPC) is commonly used in the prestressed concrete industry for large structural members. Recent studies of UHPG show it has excellent properties for containing radionuclides such as 99 Tc and 129 I Nichols and Kaplan (2021). This report presents the results of the first attempt to encapsulate a clean, full-size HEPA filter in UHPG and evaluate the effectiveness of the immobilization process and final waste form. A full-scale proof-of-concept simulated waste form was prepared by encapsulating a HEPA filter in a 110-gallon stainless steel (SS) drum using UHPG. A change from Type I/II PC to Type 1L PLC was made after American Rock Products informed the team that they would no longer be using Type I/II by the end of 2024 and the northwest was phasing out Type I/II PC overall. Type I/II PC used in previous studies of UHPG for encapsulation (Nichols and Kaplan 2021). After the UHPG was cured both the scaled mockup and the full-scale simulated waste forms were sectioned for visual examination. UHPG completely encapsulated the filters and bonded to the external surfaces of materials comprising the filters. No cracks were observed in the sectioned waste forms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Improved precision in As speciation analysis with HERFD-XANES at the As K -edge: the case of As speciation in mine waste

High-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) is a spectroscopic method that allows for increased spectral feature resolution, and greater selectivity to decrease complex matrix effects compared with conventional XANES. XANES is an ideal tool for speciation of elements in solid-phase environmental samples. Accurate speciation of As in mine waste materials is important for understanding the mobility and toxicity of As in near-surface environments. In this study, linear combination fitting (LCF) was performed on synthetic spectra generated from mixtures of eight measured reference compounds for both HERFD-XANES and transmission-detected XANES to evaluate the improvement in quantitative speciation with HERFD-XANES spectra. The reference compounds arsenolite (As 2 O 3 ), orpiment (As 2 S 3 ), getchellite (AsSbS 3 ), arsenopyrite (FeAsS), kaňkite (FeAsO 4 ·3.5H 2 O), scorodite (FeAsO 4 ·2H 2 O), sodium arsenate (Na 3 AsO 4 ), and realgar (As 4 S 4 ) were selected for their importance in mine waste systems. Statistical methods of principal component analysis and target transformation were employed to determine whether HERFD improves identification of the components in a dataset of mixtures of reference compounds. LCF was performed on HERFD- and total fluorescence yield (TFY)-XANES spectra collected from mine waste samples. Arsenopyrite, arsenolite, orpiment, and sodium arsenate were more accurately identified in the synthetic HERFD-XANES spectra compared with the transmission-XANES spectra. In mine waste samples containing arsenopyrite and either scorodite or kaňkite, LCF with HERFD-XANES measurements resulted in fits with smaller R -factors than concurrently collected TFY measurements. The improved accuracy of HERFD-XANES analysis may provide enhanced delineation of As phases controlling biogeochemical reactions in mine wastes, contaminated soils, and remediation systems.

58 GEOSCIENCES↗

Molecular mechanisms and environmental adaptations of flagellar loss and biofilm growth of Rhodanobacter under environmental stress

Biofilms aid bacterial adhesion to surfaces via direct and indirect mechanisms, and formation of biofilms is considered as an important strategy for adaptation and survival in suboptimal environmental conditions. However, the molecular underpinnings of biofilm formation in subsurface sediment/groundwater ecosystems where microorganisms often experience fluctuations in nutrient input, pH, and nitrate or metal concentrations are underexplored. Here, we examined biofilm formation under different nutrient, pH, metal, and nitrate regimens of 16 Rhodanobacter strains isolated from subsurface groundwater wells spanning diverse levels of pH (3.5 to 5) and nitrates (13.7 to 146 mM). Eight Rhodanobacter strains demonstrated significant biofilm growth under low pH, suggesting adaptations for survival and growth at low pH. Biofilms were intensified under aluminum stress, particularly in strains possessing fewer genetic traits associated with biofilm formation, findings warranting further investigation. Through random barcode transposon-site sequencing (RB-TnSeq), proteomics, use of specific mutants, and transmission electron microscopy analysis, we discovered flagellar loss under aluminum stress, indicating a potential relationship between motility, metal tolerance, and biofilm growth. Comparative genomic analyses revealed the absence of flagella and chemotaxis genes and the presence of a putative type VI secretion system in the highly biofilm-forming strain FW021-MT20. In this study we identified genetic determinants associated with biofilm growth under metal stress in a predominant environmental genus, Rhodanobacter, and identified traits aiding survival and adaptation to contaminated subsurface environments.

59 BASIC BIOLOGICAL SCIENCES↗

Developing a pipeline to expand the genetic code of diverse bacteria for microbial engineering

Microbial biotechnologies are key to addressing grand challenges to promote human health, reverse carbon emissions, recycle mixed plastic waste, remediate contaminated soils, and achieve sustainable economies. Synthetic biology has enabled design of diverse microbes and their proteins for useful purposes, but the narrowness of the natural genetic code limits functional diversity (e.g., biosynthesis) of engineered microbes. The natural genetic code defines the fundamental rules of translating genetic information into proteins comprised of 22 ‘canonical’ amino acids. However, using a technique called genetic code expansion (GCE), the chemical properties and therefore functions of proteins can be transformed by incorporation of one or more of ~200 chemically diverse ‘non-canonical’ amino acids. The effective application of genetic code expansion in diverse microbes has the potential to revolutionize biotechnology. However, despite over 50 years of research and its transformative potential, the application of genetic code expansion has been limited to a handful of bacterial species. In this project, we will perform three tasks to both overcome the barriers that prevent wide spread adoption of GCE as molecular tool and demonstrate its potential for biotechnological applications. Specifically, we will (1) develop a genetic engineering methodology that will enable use of GCE in a broad range of bacterial hosts, (2) use high-throughput functional genomics methods to identify physiological responses to both genetic code expansion and exposure to non-canonical amino acids in three different bacteria, and (3) demonstrate an application of GCE by selectively incorporate non-canonical amino acids into surface displayed peptides such as those used for biomining.

59 BASIC BIOLOGICAL SCIENCES↗

Removable coatings: Thermal stability and decontamination of steel surfaces from 241 Am

This study presents a comparative analysis of several strippable materials for decontamination of steel surfaces from 241 Am. The strippable coatings were chosen to have a history of application, to be commercially available, easily handled and have different composition and formulation. Carbon steel and stainless steel surfaces (coupons) were utilized as the most representative industrial materials, and the experimental series were expanded to include the rusting treatment of these surfaces as it is common for decommissioned old nuclear facilities. The experiments followed the path of pre-screening of the strippable materials (easiness of application, peeling etc.), their characterization with Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), decontamination factors (DF) or removal efficiencies for different types of steel surfaces, and enhancement of the removal efficiencies of the select strippable coatings via amendment with EDTA. As a result, DF and removal efficiencies for stainless steel (both pristine and with rusting treatment) are higher than for pristine carbon steel, and decontamination factors and removal efficiencies are higher for pristine than for rusted carbon steel across all the coatings. It is also shown that EDTA amendment can improve DF and removal efficiency for a strippable coating (i.e., CC Strip), however other factors should also be considered. Thus, the coating CC Strip exhibited easiness in handling and high DF (up to 97% when EDTA-amended), but its drying period was the longest among the rest of the materials and its thermal decomposition indicates on a risk of intense release of heat in case of a fire event.

36 MATERIALS SCIENCE↗

Point defects and impurities in fluorite PuO 2

The native surface oxide of plutonium plays a critical role in ensuring the stability and safe storage of the underlying metal; consequently, understanding the role of defects and impurities in determining the properties of the oxide layer is critical. Here, in this study, we use hybrid density-functional theory calculations to evaluate the electronic structure and defect chemistry of PuO 2 , the most stable of the native oxide phases, including both native and extrinsic defects. We find that oxygen vacancies (𝑉 O ) form readily in PuO 2 , as do polarons. Electron polarons (𝜂 − ) are the lowest-energy acceptor species in PuO 2 , while the charge compensating donor species will shift from 𝑉 O under O-poor conditions to hole polarons (𝜂 + ) under O-rich conditions. Nitrogen and fluorine can substitute readily for oxygen atoms under O-poor conditions, while fluorine can also incorporate in an interstitial configuration (F$^−_i$) under more O-rich conditions. Carbon and chlorine incorporation in PuO 2 will be very limited. We also evaluate the kinetic barriers for oxygen-related defects, which we find to diffuse readily when present. Our results provide valuable insights into the critical role and variable chemistry of point defects and impurities in PuO 2 , which in turn have important implications for the safe storage of the underlying metal layer. In short, exposure of freshly prepared plutonium to reactive nitrogen- and fluorine-containing contaminants should be avoided, while carbon- or chlorine-containing contaminants are less likely to incorporate readily into the oxide.

Materials science↗

Influence of trace level As or Ni on pyrite formation kinetics at low temperature

Pyrite formation at low temperature during early diagenesis in (sub-)surface sediments is an essential step of Fe and S biogeochemical cycles and the presence of this ubiquitous mineral of surface environments is often used as an indicator of paleo-redox conditions. Pathways of pyrite formation are usually discussed in environmental settings by involving a variety of nanosized Fe-S mineralogical precursors as a function of the local geochemical conditions. However, the influence of trace element impurities such as Ni and As in the solution at the time of pyrite formation has been poorly studied, whereas specific chemical signatures of trace elements are commonly observed in sedimentary pyrites. Here, a better understanding of the impact of Ni and As incorporation at trace levels on pyrite formation is essential to help refining the use of these elements as paleo-redox indicators and to evaluate the role of pyrite as a sink regulating the biogeochemical cycle of potentially toxic trace elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Submicron immunoglobulin particles exhibit FcγRII-dependent toxicity linked to autophagy in TNFα-stimulated endothelial cells

In intravenous immunoglobulins (IVIG), and some other immunoglobulin products, protein particles have been implicated in adverse events. Role and mechanisms of immunoglobulin particles in vascular adverse effects of blood components and manufactured biologics have not been elucidated. We have developed a model of spherical silica microparticles (SiMPs) of distinct sizes 200–2000 nm coated with different IVIG- or albumin (HSA)-coronas and investigated their effects on cultured human umbilical vein endothelial cells (HUVEC). IVIG products (1–20 mg/mL), bare SiMPs or SiMPs with IVIG-corona, did not display significant toxicity to unstimulated HUVEC. In contrast, in TNFα-stimulated HUVEC, IVIG-SiMPs induced decrease of HUVEC viability compared to HSA-SiMPs, while no toxicity of soluble IVIG was observed. 200 nm IVIG-SiMPs after 24 h treatment further increased ICAM1 (intercellular adhesion molecule 1) and tissue factor surface expression, apoptosis, mammalian target of rapamacin (mTOR)-dependent activation of autophagy, and release of extracellular vesicles, positive for mitophagy markers. Toxic effects of IVIG-SiMPs were most prominent for 200 nm SiMPs and decreased with larger SiMP size. Using blocking antibodies, toxicity of IVIG-SiMPs was found dependent on FcγRII receptor expression on HUVEC, which increased after TNFα-stimulation. Similar results were observed with different IVIG products and research grade IgG preparations. In conclusion, submicron particles with immunoglobulin corona induced size-dependent toxicity in TNFα-stimulated HUVEC via FcγRII receptors, associated with apoptosis and mTOR-dependent activation of autophagy. Testing of IVIG toxicity in endothelial cells prestimulated with proinflammatory cytokines is relevant to clinical conditions. Our results warrant further studies on endothelial toxicity of sub-visible immunoglobulin particles.

59 BASIC BIOLOGICAL SCIENCES↗

Fate and transport of unruptured tri-structural isotropic (TRISO) fuel particles in the event of environmental release for advanced and micro reactor applications

Advanced nuclear reactor designs and advanced fuel types offer safety features that may reduce environmental consequences in an accident scenario when compared to conventional reactors and fuels. One advanced reactor fuel is tri-structural isotropic (TRISO) fuel particles which are approximately 0.9 mm in diameter. TRISO particle mobility, assuming the particle is unruptured and the encapsulated radionuclides are contained, was explored through a theoretical examination of mobility through atmospheric, soil and groundwater, surface water, and non-human biota transport pathways. TRISO particles are too large and dense to travel in the atmosphere except under extreme conditions. TRISO particles are too large to penetrate most soil profiles and so cannot be transported with groundwater. TRISO particles will settle out of the water column in surface waters but the transport will depend on the energy of the body of water and likelihood of extreme dispersion events. TRISO particles could be transported by non-human biota. The size of TRISO particles could allow them to be intentionally moved by non-human biota if they are ingested as a gastrolith or if they are mistaken for something in the organism’s diet. Generally, TRISO particles will have reduced environmental mobility compared to releases of radionuclides in the event of an accident in a conventional nuclear reactor. The extent of transport has implications in emergency planning zone designations and other considerations for licensing and deploying TRISO-fueled reactors. Finally, further research and experimental work exploring TRISO particle mobility is required to understand the full environmental mobility of TRISO particles.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Metagenome-assembled genomes from topsoils along a hillslope water gradient across early snowmelt to late summer in East River, CO

Drought is changing the American Mountain West at unprecedented rates with unknown consequences to soil microbiome composition and function. As a part of LBNL Watershed Science Focus Area (SFA), we investigated shifts in microbial community and transcriptional activity on a subalpine conifer-meadow transition zone throughout the summer of 2023 as soil dried down. This work took place in Crested Butte, CO on Snodgrass mountain, using a proxy for drought conditions.Here we present metagenome assembled genomes (MAGs) for the bacterial and archaeal community at 0-10cm from three sites along a hillslope water gradient across five timepoints from early snowmelt to late summer. 42 metagenomes were sequenced at Joint Genome Institute (JGI) and can be found under the JGI GOLD (Genomes Online Database) sequencing project Gs0166660. Metagenomes were assembled through an inhouse pipeline (see methods), binned using four autobinners (concoct, maxbin2, metabat2, and vamb) and consolidated using dastool. The consolidated bins from all metagenomes were pooled, filtered by completeness (>70%) and contamination (<10%), and dereplicated at 95% ANI using drep. This dataset (1) a zip file of 157 MAGs (as fasta files, Gs0166660_bins_tar.gz), (2) sample metadata file with sample IGSNs (International Generic Sample Numbers) (samples.csv), (3) bounding box coordinates for the sampled locations (Gs0166660.kml), (4) metagenome assembly and coassembly metadata file listing IMG/M (Integrated Microbial Genomes/Metagenomes) metagenome accessions linking samples to metagenomes (EastRiver_Drought_ESSDive_Metadata.csv), (5) location metadata file (locations.csv), (6) file-level metadata file (flmd.csv) and (7) data dictionary (dd.csv) file.This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

54 ENVIRONMENTAL SCIENCES↗

Pahute Mesa-Oasis Valley Hydrostratigraphic Framework Model for Corrective Action Units 101 and 102: Central and Western Pahute Mesa, Nye County, Nevada (Rev. 0)

A new, revised three-dimensional (3-D) hydrostratigraphic framework model (HFM) for the Central and Western Pahute Mesa Corrective Action Units 101 and 102 was completed in 2019. The initial (Phase I) model was completed in 2002 and was documented in A Hydrostratigraphic Model and Alternatives for the Groundwater Flow and Contaminant Transport Model of Corrective Action Units 101 and 102: Central and Western Pahute Mesa, Nye County, Nevada (BN, 2002). Subsequent flow and transport modeling revealed the need to collect additional data to reduce uncertainties. The Phase II data collection and characterization effort included extensive well drilling and testing activities, and rebuilding of the Phase I 3-D HFM, resulting in the Phase II HFM (NSTec, 2014). Further drilling (Well ER-20-12), data collection, and interpretive work (e.g., Thirsty Canyon Lineament [Wurtz and Day, 2018]) were incorporated into the Pahute Mesa-Oasis Valley (PM-OV) HFM. The PM-OV HFM incorporates the area of interest from the Phase II HFM and adds additional areas, primarily to the north and west with minor additions to the south and east. The new, expanded area matches the PM-OV groundwater basin as defined in Fenelon et al. (2016) and includes Pahute Mesa, a former nuclear testing area at the Nevada National Security Site; and Oasis Valley, a groundwater discharge area downgradient from contaminant source areas on Pahute Mesa. The data and information necessary to build the PM-OV HFM are provided in Navarro (2019). The PM-OV HFM will be used by hydrologic modelers who are tasked with developing a model to determine how contaminants are transported by groundwater flow in an area of complex geology. The model area is large (more than 6,250 square kilometers) and geologically complex, including Paleozoic- to Mesozoic-age structures (e.g., thrust faults, Thirsty Canyon Lineament), at least seven Tertiary-age calderas, several intrusive bodies, and many relatively recent basin-and-range normal faults. Investigators from the U.S. Geological Survey; National Security Technologies, LLC; National Laboratories; and U.S. Department of Energy contractors have organized the more than 300 volcanic units and other rocks in the model area into 77 hydrostratigraphic units (HSUs). The volcanic rocks are subdivided into 42 aquifers, 11 confining units, and 9 composite units (containing both aquifer and confining unit rocks). The underlying pre-Tertiary rocks were divided into 5 HSUs, comprising 2 aquifers and 3 confining units. The model also includes 1 alluvial aquifer unit, 8 intrusive confining units, and 1 granite confining unit. The model depicts the thickness, extent, and geometric relationships of these HSUs (“layers” in the model) along with all the major structural features that control them, including calderas and faults. The most substantive differences between the Phase II HFM and the PM-OVHFM include (1) addition of the new data and resulting revised interpretations from the additional area encompassed by the PM-OV groundwater basin; (2) incorporation of 16 new faults; (3) 12 boreholes from the northern extension; (4) 2 additional caldera-collapse collars; and (5) correlation of the simulated faulting and hydrostratigraphy in the eastern part of the model domain with the delineations represented in the neighboring Rainier Mesa-Shoshone Mountain HFM-Prime and Yucca Flat-Climax Mine HFM. All PM-OV HFM delineations were based on published and unpublished data from geophysical investigations, surface geologic maps, and drill-hole records. Phase II approached model uncertainty using the model-building software to test model configurations and hydrologic consequences using a range of values for parameters such as fault offset amounts and HSU elevations. The PM-OV HFM expands on this approach to encompass the entire PM-OV groundwater basin.

54 ENVIRONMENTAL SCIENCES↗

Tracking Radioactive Isotopes in HVAC and Application for Hot Cell Analyses - 20155

In recent years, the surge in the number of isotope production facilities under design has increased the need to analyze isotope migration in facility Heating, Ventilation, and Air Conditioning (HVAC) during normal operations and accident scenarios. These facilities are used to produce isotopes for medical, security, and industrial applications and as such are subject to license and regulatory requirements 10CFR20, 10CFR30, 10CFR50, and 10CFR70. GOTHIC, a general-purpose thermal-hydraulics software package, includes the ability to model isotopic tracers, radioactive decay and isotope migration as well as HEPA and charcoal filters for isotope retention. A GOTHIC model was developed by Zachry Nuclear Engineering (ZNE) to examine the effect of negative room pressure, HEPA filtration, and HVAC fluctuations on radiation areas, hot cells and gloveboxes. Radioactive tracers were used to simulate the concentration of spills within contaminated areas, track the migration of isotopes of interest, and determine the isotopic retention and buildup on facility HEPA filters. A variety of isotopes with concern to dose (e.g., Kr-85, Sr-90, I-131, etc.), including their decay and progeny, are included in the analysis. Negative pressures are maintained in the regions of interest by a representative central HVAC system equipped with a volumetric fan that exhausts to the environment after a series of isolation valves and HEPA filters. GOTHIC is an industry trusted tool for providing engineering solutions for a variety of applications, including fission product tracking, aerosol and particulate transport and ventilation assessments. The software provides an integrated analysis environment that includes a graphical user interface (GUI) for constructing analysis models, a numerical solver that includes parallel processing capabilities and a post-processor for evaluating simulation results. It solves the conservation equations for mass, momentum and energy for multicomponent, multi-phase flow in lumped parameter and multi-dimensional geometries (1, 2, or full 3D), including the effects of turbulence, diffusion and buoyancy. It has been developed and maintained under a Quality Assurance program in compliance with the requirements of 10CFR50 Appendix B and applicable portions of ASME NQA-1 since 1995. GOTHIC has been used for assessing both forced and natural convection conditions for a wide range of applications, including: - Tracking concentration of hazardous gases and chemicals for habitability and safety assessments - Determining ventilation and filtration requirements and optimizing location and arrangement of these systems - Room heat-up, including diverse and Flexible coping strategies for Extended Loss of AC Power (FLEX/ELAP) - Equipment Qualification (EQ) A distinctive feature of GOTHIC is the ability to track many different fields/substances in a simulation, including user defined tracer elements, in the liquid, vapor and droplet fields as well as surfaces and filters. This capability allows GOTHIC to model fission product transport and release or the removal of particulates or harmful toxins from exhaust gases using a spray scrubber or other types of filtration systems. GOTHIC also includes models for engineered equipment, such as fans, filters, charcoal filters, dryers/demisters, dampers, etc. The aerosols and other filtered material are removed or accumulated in these components. The range of aerosol and radiological applications that GOTHIC has been used for includes: - Source Term: Primary Coolant (Equilibrium) Activity; Non-Water Coolant Source/Leakage. - Conditions for Iodine Re-evolution: Sump/Suppression Pool Conditions and pH; - RWST Conditions and pH. - Isotope Removal Mechanisms: Containment Sprayed and Unsprayed Region Mixing; Charcoal Filter Heating due to Iodine decay. - Radionuclide Transport and Decay: Post-LOCA Release in containment; Transport between connected Compartments and vent systems; Groundwater transport of radionuclides. - Non-Newtonian Fluid modeling for sludge, waste tanks, etc. ADAMS ML071581053 (titled 'Best Practice Guidelines for the use of CFD in Nuclear Reactor Safety Applications') poses guidelines for applying single phase CFD codes in nuclear reactor safety problems and GOTHIC is listed as a 'tool for 3D flows' and 'dispersal and deposition of radionuclides.' The Nuclear Quality Assurance (NQA) pedigree of GOTHIC is an important aspect for applications in the nuclear industry. The fundamental tracer models (convective transport, molecular and turbulent diffusion, removal mechanisms, etc.) have been verified using analytical solutions and validated against applicable separate effects tests. Also, GOTHIC has been benchmarked to many integrated effects tests, including Phebus FP (Fission Product). GOTHIC gives good agreement for the buildup and decay of fission products in Phebus Test 3. The model developed by ZNE demonstrates GOTHIC's applicability and acceptability for use in analyzing the migration and retention of radioactive isotopes and their progeny in normal operation and accident scenario analyses for isotope production facilities, hot cells, and gloveboxes. The tracer activities calculated by GOTHIC can then be used in downstream radiation transport and shielding codes like RADTRAD-NAI{sup C}, MCNP{sup R}, and MicroShield{sup R} to determine on-site and of-site doses. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Hypothesis tests on Rayleigh wave radiation pattern shapes: a theoretical assessment of idealized source screening

SUMMARY Shallow seismic sources excite Rayleigh wave ground motion with azimuthally dependent radiation patterns. We place binary hypothesis tests on theoretical models of such radiation patterns to screen cylindrically symmetric sources (like explosions) from non-symmetric sources (like non-vertical dip-slip or non-VDS faults). These models for data include sources with several unknown parameters, contaminated by Gaussian noise and embedded in a layered half-space. The generalized maximum likelihood ratio tests that we derive from these data models produce screening statistics and decision rules that depend on measured, noisy ground motion at discrete sensor locations. We explicitly quantify how the screening power of these statistics increase with the size of any dip-slip and strike-slip components of the source, relative to noise (faulting signal strength) and how they vary with network geometry. As applications of our theory, we apply these tests to (1) find optimal sensor locations that maximize the probability of screening non-circular radiation patterns and (2) invert for the largest non-VDS faulting signal that could be mistakenly attributed to an explosion with damage, at a particular attribution probability. Finally, we quantify how certain errors that are sourced by opening cracks increase screening rate errors. While such theoretical solutions are ideal and require future validation, they remain important in underground explosion monitoring scenarios because they provide fundamental physical limits on the discrimination power of tests that screen explosive from non-VDS faulting sources.

58 GEOSCIENCES↗