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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.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Local cation order and ferrimagnetism in compositionally complex spinel ferrites

We present an exploration of a family of compositionally complex cubic spinel ferrites featuring combinations of Mg, Fe, Co, Ni, Cu, Mn, and Zn cations, systematically investigating the average and local atomic structures, chemical short-range order, magnetic spin configurations, and magnetic properties. All compositions result in ferrimagnetic average structures with extremely similar local bonding environments; however, the samples display varying degrees of cation inversion and, therefore, differing apparent bulk magnetization. Additionally, first-order reversal curve analysis of the magnetic reversal behavior indicates varying degrees of magnetic ordering and interactions, including potentially local frustration. Finally, reverse Monte Carlo modeling of the spin orientation demonstrates a relationship between the degree of cation inversion and the spin collinearity. Collectively, these observations correlate with differences in synthesis procedures. This work provides a framework for understanding magnetic behavior reported for “high-entropy spinels,” revealing many are likely compositionally complex oxides with differing degrees of chemical short-range order—not meeting the community established criteria for high or medium entropy compounds. Moreover, this work highlights the importance of reporting complete sample processing histories and investigating local to long-range atomic arrangements when evaluating potential entropic mixing effects and assumed property correlations in high entropy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In crystallo organometallic chemistry

X-ray crystallography is an invaluable tool in design and development of organometallic catalysis, but application typically requires species to display sufficiently high solution concentrations and lifetimes for single crystalline samples to be obtained. In crystallo organometallic chemistry relies on chemical reactions that proceed within the single-crystal environment to access crystalline samples of reactive organometallic fragments that are unavailable by alternate means. Furthermore, this highlight describes approaches to in crystallo organometallic chemistry including (a) solid–gas reactions between transition metal complexes in molecular crystals and diffusing small molecules, (b) reactions of organometallic complexes within the extended lattices of metal–organic frameworks (MOFs), and (c) intracrystalline photochemical transformations to generate reactive organometallic fragments. Application of these methods has enabled characterization of catalytically important transient species, including σ-alkane adducts of transition metals, metal alkyl intermediates implicated in metal-catalyzed carbonylations, and reactive M–L multiply bonded species involved in C–H functionalization chemistry. Opportunities and challenges for in crystallo organometallic chemistry are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Technology readiness assessment of magnetohydrodynamic stability control

The technology readiness level scale is revised with clear definitions for magnetohydrodynamic stability control technologies for magnetic confinement fusion. The definitions are in the form of a sentence with three dimensions, which are the system complexity, the test environment, and the cost. A clear and simple definition is sought after to make an assessment based on the evidence which is agreeable to the fusion energy development community. A sample technology readiness assessment (TRA) for the electron cyclotron current drive-based control of neoclassical tearing mode for ST Advanced Reactor, using the proposed scale, reveals that the risk of a TRA being misinterpreted is high, which can only be avoided with an understanding of the procedure described in this paper.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Earth microbial co-occurrence network reveals interconnection pattern across microbiomes

Microbial interactions shape the structure and function of microbial communities; microbial association networks in specic environments have been widely developed to explore these complex systems, but their wired pattern across microbiomes in various environments at the global scale remains unexplored. Here we have inferred an Earth microbial association network from a communal catalogue with 23,595 samples and 12,646 exact sequence variants from 14 environments in the Earth Microbiome Project dataset. Results: This non-random scale-free Earth microbial association network consisted of 8 taxonomy distinct modules linked with dierent environments, which featured environment specic microbial associations. Dierent topological features of subnetworks inferred from datasets trimmed into uniform size indicate distinct association patterns in the microbiomes of various environments. The proportions of specialist edges, which ranged from 43.0% to 65.7%, highlight that environmental specic microbial associations are essential features of microbiomes in various environments. Based on edge-overlap similarity, the microbiomes of various environments were clustered into two groups, which were mainly bridged by the microbiomes of plant and animal surface. Acidobacteria Gp2 and Nisaea were identied as hubs in most of subnetworks. Negative edges proportions ranged from 1.9% in the soil subnetwork to 48.9% the non-saline surface subnetwork, suggesting various environments experience distinct intensities of competition or niche dierentiation. Conclusion: This investigation provides a new resource for examining Earth microbial association patterns across environments and emphasizes the network perspective for comprehensively understanding unique microbiome features. Keywords: Association pattern; Earth microbiomes; Genelist edges; Network hubs; Negative associations; Specialist edges; Topological properties

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Wyoming CarbonSAFE: Advancing Commercialization of Low-Carbon Energy Technologies in Fossil-Rich Wyoming

Wyoming’s Powder River Basin (PRB) is the most prolific coal producer and exporter in the United States and the State of Wyoming’s largest oil-producing basin. In addition to being a leading energy producer, the PRB is the site of research programs whose aim is to develop and integrate low-carbon technologies into existing fossil fuel energy industries. Much of the PRB’s low-carbon research is focused around Dry Fork Station (DFS), which is the newest coal-fired power station in the western US. Currently, DFS hosts five carbon capture projects, including pilot-scale capture projects that utilize different capture technologies and a full front-end engineering and design (FEED) study, a commercial CO 2 pipeline for nearby CO 2 -enhanced oil recovery industry, and is also co-located with the Wyoming Integrated Test Center, which is a host facility for unconventional carbon utilization research (i.e. flue gas carbon-to-products innovations). DFS is also the host site for the Wyoming CarbonSAFE project. Wyoming CarbonSAFE, funded by the Department of Energy/National Energy Technology Laboratory, is a multi-phased program (currently in Phase II) whose core objective is developing and validating storage sites within a complex capable of storing 50 million metric tonnes of CO 2 over a 30 year project period using carbon capture, utilization and storage (CCUS). This paper will provide an overview of the project to-date, showing that CarbonSAFE goals are achievable with respect to geologic, environmental, regulatory, CO 2 source and economic conditions, and why the State of Wyoming offers one of the more favorable environments to advance the commercialization studies. In 2019, the project team designed and completed a ~10,000 foot stratigraphic test well just south of DFS. From this well, the team collected over 600 feet of core, fluid samples from target injection zones, and a full petrophysical log suite. In addition, legacy 2D seismic lines were acquired and a 3D seismic survey was acquired in the fall of 2020. The objective of these field activities has been to identify and characterize target storage reservoirs and associated caprock. This complex has several reservoirs that could meet commercial injection goals, and over 4000 feet of associated caprock. Simulations of site performance suggest that stacked injection provides the most effective storage strategy, and would necessitate several sites within the greater complex to meet final project injection goals. Other work within this project includes the development of a business-case around proximal fields with CO 2 -enhanced oil recovery potential and existing tax credits, assessment of regulatory conditions, including pore space ownership and Class VI injection well permitting requirements, implementation of a robust public outreach Electronic copy available at: https://ssrn.com/abstract=3821220 GHGT-15 McLaughlin 2 program, and surface site characterization activities that have focused on environmental factors. In the PRB and at DFS, the State of Wyoming and other entities have made carbon management a priority of its future energy industry by providing a regulatory and business framework that is favorable to advancing these technologies. These endeavors will become more realistic with the successful implementation of Wyoming CarbonSAFE, and its ability to secure and validate commercial-scale CCUS at the center of Wyoming’s premier low-carbon research efforts.

McLaughlin, Fred↗
DOE OSTI2022

Sample Preparation and Experimental Design for In Situ Multi-Beam Transmission Electron Microscopy Irradiation Experiments

We discuss the need to understand materials exposed to overlapping extreme environments such as high temperature, radiation, or mechanical stress. When these stressors are combined there may be synergistic effects that enable unique microstructural evolution mechanisms to activate. Understanding of these mechanisms is necessary for the input and refinement of predictive models and critical for engineering of next generation materials. The basic physics and underlying mechanisms require advanced tools to be investigated. The in situ ion irradiation transmission electron microscope (I 3 TEM) is designed to explore these principles. To quantitatively probe the complex dynamic interactions in materials, careful preparation of samples and consideration of experimental design is required. Particular handling or preparation of samples can easily introduce damage or features that obfuscate the measurements. There is no one correct way to prepare a sample; however, many mistakes can be made. The most common errors and things to consider are highlighted within. The I 3 TEM has many adjustable variables and a large potential experimental space, therefore it is best to design experiments with a specific scientific question or questions in mind. Experiments have been performed on large number of sample geometries, material classes, and with many irradiation conditions. The following are a subset of examples that demonstrate unique in situ capabilities utilizing the I 3 TEM. Au nanoparticles prepared by drop casting have been used to investigate the effects of single ion strikes. Au thin films have been used in studies on the effects of multibeam irradiation on microstructure evolution. Zr films have been exposed to irradiation and mechanical tension to examine creep. Ag nanopillars were subjected to simultaneous high temperature, mechanical compression, and ion irradiation to study irradiation induced creep as well. These results impact fields including: structural materials, nuclear energy, energy storage, catalysis, and microelectronics in space environments.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Mining Thermophile Photosynthesis Genes: A Synthetic Operon Expressing Chloroflexota Species Reaction Center Genes in Rhodobacter sphaeroides

Photosynthesis is the foundation of the vast majority of life systems, and is therefore the most important bioenergetic process on earth. The greatest diversity of photosynthetic systems is found in microorganisms. However, our understanding of the biophysical and biochemical processes that transduce light into chemical energy is derived from a relatively small subset of proteins from microbes that are amenable to cultivation, in contrast to the huge number of predicted proteins that catalyze the initial photochemical reactions deposited in databases, such as from metagenomics. We describe the use of a Rhodobacter sphaeroides laboratory strain for the expression of heterologous photosynthesis genes to demonstrate the feasibility of mining this resource, focusing on hot spring Chloroflexota gene sequences. Using a synthetic operon of genes, we produced a photochemically active complex of reaction center proteins in our biological system. We also present bioinformatic analyses of anoxygenic type II reaction center sequences from metagenomic samples collected from hot (42–90 °C) springs available through the JGI IMG database, to generate a resource of diverse sequences that are potentially adapted to photosynthesis at such temperatures. These data provide a view into the natural diversity of anoxygenic photosynthesis, through a lens focused on high-temperature environments. The approach we took to express such genes can be applied for potential biotechnology purposes as well as for studies of fundamental catalytic properties of these heretofore inaccessible protein complexes.

Chloroflexota↗
DOE OSTI2023

Robotic pendant drop: containerless liquid for μs-resolved, AI-executable XPCS

Abstract The dynamics and structure of mixed phases in a complex fluid can significantly impact its material properties, such as viscoelasticity. Small-angle X-ray Photon Correlation Spectroscopy (SA-XPCS) can probe the spontaneous spatial fluctuations of the mixed phases under various in situ environments over wide spatiotemporal ranges (10 −6 –10 3 s /10 −10 –10 −6 m). Tailored material design, however, requires searching through a massive number of sample compositions and experimental parameters, which is beyond the bandwidth of the current coherent X-ray beamline. Using 3.7-μs-resolved XPCS synchronized with the clock frequency at the Advanced Photon Source, we demonstrated the consistency between the Brownian dynamics of ~100 nm diameter colloidal silica nanoparticles measured from an enclosed pendant drop and a sealed capillary. The electronic pipette can also be mounted on a robotic arm to access different stock solutions and create complex fluids with highly-repeatable and precisely controlled composition profiles. This closed-loop, AI-executable protocol is applicable to light scattering techniques regardless of the light wavelength and optical coherence, and is a first step towards high-throughput, autonomous material discovery.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In Situ Methods for Metal-Flux Synthesis in Inert Environments

Flux growth synthesis is an advantageous synthetic method as it allows for the growth of single crystals of both congruently melting and metastable phases. The determination of synthetic parameters for the flux growth of new crystalline phases is complex as many factors and parameters need to be considered, such as purity and morphology of starting material and heating profile variables including maximum temperature, dwell time, cooling rate and flux removal temperature. In situ monitoring of crystallite growth can lead to elucidation of reaction intermediates and growth mechanisms. The determination of pivotal reaction parameters can revolutionize the way growth parameters are selected. In this work, we report a new sample environment and furnace apparatus for synchrotron in situ synthesis of crystalline materials, including flux grown intermetallics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

129 I, 99 Tc, And U Distribution Coefficients of Subsurface Sediments Collected from the Proposed Site of the Environmental Management Disposal Facility

Performance Assessment calculations were completed in 2020 to evaluate the Environmental Management Disposal Facility (EMDF), a proposed new low-level radioactive waste (LLW) disposal facility on the U.S. Department of Energy’s Oak Ridge Reservation (ORR). Among the large number of input parameters needed for such calculations, are distribution coefficients (K d values; radionuclide concentration solid:liquid ratio) that provide a measure of the tendency of radionuclides to bind to sediments. The objective of this study was to measure K d values of three radionuclides that may pose a disproportionately large amount of risk, U, 129 I and 99 Tc. The average I K d value for the 14 geological materials recovered from the proposed EMDF site was 37.8 mL/g and ranged from -1.8 to 140.9 mL/g. These values were consistent, but somewhat larger than previous measurements made with ORR sediments and were about an order of magnitude greater than those used in previous EMDF PA calculations. The median Tc K d value was 365.7 mL/g, much greater than previously reported using ORR geological materials. Five of the 14 tested geological materials sorbed large quantities of Tc, suggesting that the weakly sorbing Tc(VII) species had been reduced to the sparingly soluble Tc(IV) species. The five strongly sorbing sediments had apparent Tc solubility values of approximately <10 -8 mol/L. The median U K d value was 5,726 mL/g. All of the tested geological materials had large K d values, ranging from 625 to >10,208 mL/g. Among the sediment samples that exhibited strong U binding, the apparent solubility value was approximately <10 -9 mol/L. Based on sediment properties and general ORR geological considerations, it was proposed that much of the I and Tc retention could be attributed to the site materials exhibiting low pH (average pH = 4.94), low redox status, and/or the elevated levels of iron oxides, manganese oxides, and natural organic matter. Similarly, the extremely high U binding measured in these sediments may also be attributed to the low conditions of carbonates, which can complex and therefore solubilize uranyl in these tests due to the low pH, and also the relatively high concentrations of iron and organic coatings on these samples. An implication of this study is that the areas of the EMDF subsurface environment may have natural properties for attenuating I, Tc, and U movement, and potentially other radionuclides, thereby possibly reducing risk posed by burial of LLW at this site. This document is a revision of SRNL-STI-2021-00404, Revision 0 that includes new data describing U K d values and new I and Tc K d values for four Nolichucky sediments. These new results were integrated into the data presented in the original document.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

129 I, 99 Tc, and U Distribution Coefficients of Subsurface Sediments Collected from the Proposed Site of the Environmental Management Disposal Facility

Performance Assessment calculations were completed in 2020 to evaluate the Environmental Management Disposal Facility (EMDF), a proposed new low-level radioactive waste (LLW) disposal facility on the U.S. Department of Energy’s Oak Ridge Reservation (ORR). Among the large number of input parameters needed for such calculations, are distribution coefficients (K d values; radionuclide concentration solid: liquid ratio) that provide a measure of the tendency of radionuclides to bind to sediments. The objective of this study was to measure K d values of three radionuclides that may pose a disproportionately large amount of risk, U, iodine-129 ( 129 I) and technetium-99 ( 99 Tc). The average 129 I K d value for the 14 geological materials recovered from the proposed EMDF site was 37.8 mL/g and ranged from 0.45 to 140.9 mL/g. These values were consistent, but somewhat larger than previous measurements made with ORR sediments and were about an order of magnitude greater than those used in previous EMDF PA calculations. The median 99 Tc K d value was 365.7 mL/g, much greater than previously reported using ORR geological materials. Five of the 14 tested geological materials sorbed large quantities of 99 Tc, suggesting that the weakly sorbing 99 Tc(VII) species had been reduced to the sparingly soluble 99 Tc(IV) species. The five strongly sorbing sediments had apparent 99 Tc solubility values of approximately <10 -8 mol/L. The median U K d value was 5,726 mL/g. All of the tested geological materials had large K d values, ranging from 625 to >10,208 mL/g. Among the sediment samples that exhibited strong U binding, the apparent solubility value was approximately <10 -9 mol/L. Based on sediment properties and general ORR geological considerations, it was proposed that much of the 129 I and 99 Tc retention could be attributed to the site materials exhibiting low pH (average pH = 4.94), and/or the elevated levels of iron oxides, manganese oxides, and natural organic matter. Similarly, the extremely high U binding measured in these sediments may also be attributed to the low conditions of carbonates, which can complex and therefore solubilize uranyl in these tests due to the low pH, and also the relatively high concentrations of iron and organic coatings on these samples. An implication of this study is that the areas of the EMDF subsurface environment may have natural properties for attenuating 129 I, 99 Tc, and U movement, and potentially other radionuclides, thereby possibly reducing risk posed by burial of LLW at this site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Portable and Cost-Effective Device for Reliable Detection of Counterfeit and Non-compliant Refrigerants in Diverse Applications

Counterfeit refrigerants pose significant challenges to safety, system reliability, and operational effectiveness due to their harmful contaminants or incompatible chemical compositions. Utilizing these noncompliant products can lead to reduced efficiency, equipment failures, and expensive repairs. Additionally, heightened demand for alternative refrigerants during the industry's transition has created supply gaps, enabling counterfeit products to proliferate. Accurate detection and analysis tools are therefore essential to verify refrigerant authenticity and ensure system integrity in diverse applications. This paper presents the development of a portable device designed for reliable identification and detailed analysis of refrigerant composition. By integrating precision gas sampling, controlled pressure regulation, and automated sensor technology, the device not only detects deviations from standard refrigerant properties but also provides a comprehensive composition breakdown. Pre-calibrated sensors measure the refrigerant gas to identify specific concentrations and contaminants, with an intuitive LED-based indicator system ensuring quick interpretation of results. The user-friendly interface enables operators to select refrigerant types for targeted testing, further enhancing accuracy and usability for field technicians. Comprehensive testing was conducted on mildly flammable A2L refrigerants, showcasing the device’s robustness and adaptability in analyzing composition and detecting discrepancies. The device demonstrated consistent accuracy across a range of refrigerant samples, affirming its reliability in diverse operational environments. Its design minimizes contamination risks during sampling and provides detailed composition results within 90 seconds, ensuring efficient and precise analysis. With a projected price point under $150, the proposed solution delivers affordability alongside its lightweight portability and straightforward operation. Unlike complex and costly alternatives, such as gas chromatography systems, this device provides an accessible option for technicians, customs personnel, and industry operators in need of quick and effective refrigerant verification. Compatible with both current formulations and emerging refrigerant technologies, the device addresses critical counterfeit detection needs across a range of applications. By delivering accurate composition analysis and counterfeit identification, this innovation enhances system performance, safety, and operational reliability in crucial industries.

Cheekatamarla, Praveen [ORNL] (ORCID:0000000248827↗
DOE OSTI2021

Microsecond fingerprint stimulated Raman spectroscopic imaging by ultrafast tuning and spatial-spectral learning

Label-free vibrational imaging by stimulated Raman scattering (SRS) provides unprecedented insight into real-time chemical distributions. Specifically, SRS in the fingerprint region (400–1800 cm -1 ) can resolve multiple chemicals in a complex bio-environment. However, due to the intrinsic weak Raman cross-sections and the lack of ultrafast spectral acquisition schemes with high spectral fidelity, SRS in the fingerprint region is not viable for studying living cells or large-scale tissue samples. Here, we report a fingerprint spectroscopic SRS platform that acquires a distortion-free SRS spectrum at 10 cm -1 spectral resolution within 20 µs using a polygon scanner. Meanwhile, we significantly improve the signal-to-noise ratio by employing a spatial-spectral residual learning network, reaching a level comparable to that with 100 times integration. Collectively, our system enables high-speed vibrational spectroscopic imaging of multiple biomolecules in samples ranging from a single live microbe to a tissue slice.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Tunable and Robust Optical and Structural Properties of a Cooperative Squaraine-Dye Aggregate-DNA DX-DAE Tile System

Molecular excitons, which are excitations delocalized over multiple dyes in a wavelike manner, are of interest for a wide range of applications, including quantum information science. Numerous studies have templated a variety of synthetic dyes via a DNA scaffold to induce dye aggregation to create molecular excitons upon photoexcitation. Dye aggregate optical properties are critically dependent on relative dye geometry and local environment; therefore, an understanding of dye-dye and DNA-dye interactions is critical for advancing toward more complex DNA-dye systems. The extensively studied DNA Holliday junction (HJ) and less-studied double-crossover (DX) tile motif are fundamental test beds for designing complex and ultimately modular DNA-dye architectures. Here, we report the first study of single-linked squaraine dye aggregation and exciton delocalization on a larger and more stable (compared with the HJ) DX tile motif. We first highlight a few DNA-dye constructs that support single dyes and aggregates with distinct optical properties that are both tunable—through sample design, buffer conditions, and heat treatment—and robust to environment changes, including transfer to solid phase. Next, we assess several experimental and design considerations that demonstrate directed dye-driven assembly of a novel double-tile DNA configuration. Our results demonstrate that single-linked squaraine dyes templated to DX tiles provide a viable research path to design and evaluate dye aggregate networks that support exciton delocalization. We include herein the first report of exciton delocalization in the solid phase in a DNA-dye construct. Additionally, our findings indicate that dye aggregation impacts the assembly of the DNA-dye construct, and, in some cases, thereby cooperates with the DNA to determine a final robust system configuration. Finally, we show that a controlled annealing schedule can be employed to promote the homogeneous assembly of DNA-dye constructs. The findings in this study contribute to the understanding of DNA-dye systems and the relevant factors involved in their directed assembly to achieve specific constructs with desirable properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

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↗
DOE OSTI2023

Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale (Final Report)

This project titled “Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale” represents a collaborative effort between the University of Michigan (Jason Demers, PI) and Oak Ridge National Laboratory (Scott Brooks, co-I). Much has been learned about mercury (Hg) cycling in stream ecosystems, and East Fork Poplar Creek (EFPC) in particular, through decades of previous research. Nevertheless, some of the most fundamental questions regarding the sources of bioavailable Hg and its transformation to toxic methylmercury (MeHg) have remained unanswered. These fundamental questions include: (1) what are the sources and biogeochemical processes that lead to the input of dissolved Hg to stream water across critical subsurface interfaces within stream ecosystems, and EFPC in particular? and (2) what are the sources and biogeochemical processes that control the production and fate of bioaccumulative MeHg within stream ecosystems, and in EFPC in particular? To address these fundamental questions, our project aimed to couple laboratory experiments and field observations, both utilizing natural abundance Hg stable isotope techniques, to identify the processes responsible for generating mobile, bioavailable dissolved Hg from recalcitrant legacy sources within critical subsurface zones (e.g., streambed hyporheic zone, riparian floodplain subsurface). We used the isotopic signature of this bioavailable dissolved Hg to track its mobilization across these critical interfaces in order to link diffuse subsurface sources of dissolved Hg with increases in surface water dissolved Hg flux measured at the watershed scale. Additionally, our research aimed to determine the isotopic composition of MeHg within these same critical subsurface zones. We directly assessed the isotopic composition of MeHg within biota in order to gain insight into which subsurface sources of inorganic Hg and toxic MeHg are available for bioaccumulation within the EFPC ecosystem. Net fluxes of dissolved Hg along the flow path of EFPC were shown to vary spatially and temporally. In the Upper EFPC, within the Y12 boundary, stream water flux of dissolved Hg consistently decreased between the outfall and the downstream boundary of Y12 (57% ± 29%, 1SD). Within the Upper EFPC, an assessment of Hg isotopic composition suggested that losses were strongly reaction-driven, although isotopic diagnostics did not conform to any known processes. Downstream of Y12, in the upper reach of the Lower EFPC, dissolved Hg fluxes tended to increase during the dormant season (net gain of 11-120%), and decrease during the growing season (net loss of 23% +/- 18%, 1SD). In the downstream-most reach of Lower EFPC, dissolved Hg fluxes increased by 12-108% in 9 out of 10 monthly assessments. Overall, diffuse fluxes from the non-Y12 watershed accounted for 34% (+/- 17%, 1SD) of all dissolved Hg exported during base flow. Within Lower EFPC, an assessment of Hg isotopic composition was consistent with the contribution of diffuse Hg inputs from high-concentration hotspots within riparian floodplains and streambed hyporheic pore water. To investigate remobilization of recalcitrant Hg from legacy sediment sources, we developed procedures that coupled isotopic analysis with sequential extractions of streambed sediment. We found that the proportion of weakly-bound Hg within EFPC streambed sediment was relatively small, but could still account for a large proportion of the annual flux of dissolved Hg from EFPC. These sequential extractions also showed that this weakly-bound Hg fraction could be replenished from the much larger fraction of recalcitrant Hg in sediment. The isotopic composition of these weakly-bound and remobilized recalcitrant Hg fractions within the sediment was consistent with high-concentration dissolved Hg hotspots within hyporheic pore water. Thus, this research provided novel evidence that legacy mercury sources within streambed sediment could provide an ongoing contribution of dissolved Hg to surface waters. Finally, we developed new methods for the direct determination of the MeHg isotopic composition of organisms, which allowed a more direct evaluation of inorganic Hg and MeHg sources accumulating in the food web. We found that fish and aquatic invertebrates in both EFPC and a regional background site obtained inorganic Hg and MeHg from multiple isotopically distinct sources, including sediment, suspended particulates, and periphyton. Photodemethylation was found to be an important reaction influencing MeHg dynamics at both sites. However, the balance of microbial methylation and demethylation processes differed between the two streams, with fractionation resulting from methylation and demethylation processes being relatively in balance within the regional background site, whereas microbial methylation appeared to be dominant over microbial demethylation within the EFPC ecosystem. Broadly, the application of Hg isotopic analysis in this study led to numerous novel insights regarding the biogeochemical cycling of Hg in stream ecosystems. This research project promoted the development of two new approaches, including the coupling of sequential extractions with Hg isotopic analysis to assess remobilization of recalcitrant Hg within sediments, and a new method for the isotopic analysis of MeHg isolated from environmental samples. Both of these efforts represent advances in capacity for the field of mercury isotopic analysis and environmental assessment. Overall, this study demonstrates that the application of Hg stable isotope techniques continues to provide new insights into the biogeochemical cycling of Hg in complex aquatic environments, both within the EFPC and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

XANES reflects coordination change and underlying surface disorder of zinc adsorbed to silica

In this work, zinc K -edge X-ray absorption near-edge structure (XANES) spectroscopy of Zn adsorbed to silica and Zn-bearing minerals, salts and solutions was conducted to explore how XANES spectra reflect coordination environment and disorder in the surface to which a metal ion is sorbed. Specifically, XANES spectra for five distinct Zn adsorption complexes (Zn ads ) on quartz and amorphous silica [SiO 2(am) ] are presented from the Zn–water–silica surface system: outer-sphere octahedral Zn ads on quartz, inner-sphere octahedral Zn ads on quartz, inner-sphere tetrahedral Zn ads on quartz, inner-sphere octahedral Zn ads on SiO 2(am) and inner-sphere tetrahedral Zn ads on SiO 2(am) . XANES spectral analysis of these complexes on quartz versus SiO 2(am) reveals that normalized peak absorbance and K -edge energy position generally decrease with increasing surface disorder and decreasing Zn–O coordination. On quartz, the absorption-edge energy of Zn ads ranges from 9663.0 to 9664.1 eV for samples dominated by tetrahedrally versus octahedrally coordinated species, respectively. On SiO 2(am) , the absorption-edge energy of Zn ads ranges from 9662.3 to 9663.4 eV for samples dominated by tetrahedrally versus octahedrally coordinated species, respectively. On both silica substrates, octahedral Zn ads presents a single K -edge peak feature, whereas tetrahedral Zn ads presents two absorbance features. The energy space between the two absorbance peak features of the XANES K -edge of tetrahedral Zn ads is 2.4 eV for Zn on quartz and 3.2 eV for Zn on SiO 2(am) . Linear combination fitting of samples with a mixture of Zn ads complex types demonstrates that the XANES spectra of octahedral and tetrahedral Zn ads on silica are distinct enough for quantitative identification. These results suggest caution when deciphering Zn speciation in natural samples via linear combination approaches using a single Zn ads standard to represent sorption on a particular mineral surface. Correlation between XANES spectral features and prior extended X-ray absorption fine structure (EXAFS) derived coordination environments for these Zn ads on silica samples provides insight into Zn speciation in natural systems with XANES compatible Zn concentrations too low for EXAFS analysis.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Dynamics and lipid membrane coupling of the RAS-RAF complex revealed via multiscale simulations

To gain molecular and mechanistic insights into initiation of the RAS-RAF signaling cascade, we developed and used a combination of multiscale simulation and experimental approaches. The influence and impact of the membrane on RAS and RAF proteins is a factor we are just beginning to understand and appreciate in more detail. Molecular simulation is an ideal methodology to further study this complicated relationship between the membrane and associated proteins. Our previous work using Multiscale Machine-learned Modeling Infrastructure investigated different lipid compositions solely around the KRAS4b protein and the interplay between protein behavior and these membrane environments. Multiscale Machine-learned Modeling Infrastructure uses machine learning to couple adjacent simulation scales and has been efficiently scaled across some of the world’s largest high-performance computers. Recently, we have expanded this multiresolution framework to include the all-atom simulation scale and to incorporate the RAF RBDCRD domains. Here, we present the overall analysis results from this new simulation campaign comprising a mixture of RAS and RAF RBDCRD proteins. Approximately 35,000 coarse-grained and 10,000 all-atom molecular dynamics simulations were completed, sampled from a variety of protein/lipid composition configurations that were generated from a micron-scale continuum simulation containing hundreds of copies of the proteins. Our studies suggest that orientations of the RAS-RBDCRD complex on the membrane occupy distinct configurational states, and the spatial patterns of lipid arrangements around these different protein states are unique to each state. The extent and size of lipid “fingerprints” imposed on the membrane by the RAS-RBDCRD protein complex are significantly larger than observed for just the RAS protein on its own. These protein complexes strongly associate, but we do not observe statistically significant preferred protein-protein orientations. These observations indicate that spatial colocalization of RAS-RBDCRD proteins in the same vicinity may be assisted by specific membrane environments, acting to increase the probability of signaling complex formation.

Carpenter, Timothy S. [Lawrence Livermore National↗