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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Continuous motion scan ptychography: Characterization for increased speed in coherent x-ray imaging

Ptychography is a coherent diffraction imaging (CDI) method for extended objects in which diffraction patterns are acquired sequentially from overlapping coherent illumination spots. The object’s complex transmission function can be reconstructed from those diffraction patterns at a spatial resolution limited only by the scattering strength of the object and the detector geometry. Most experiments to date have positioned the illumination spots on the sample using a move-settle-measure sequence in which the move and settle steps can take longer to complete than the measure step. We describe here the use of a continuous “fly-scan” mode for ptychographic data collection in which the sample is moved continuously, so that the experiment resembles one of integrating the diffraction patterns from multiple probe positions. This allows one to use multiple probe mode reconstruction methods to obtain an image of the object and also of the illumination function. We show in simulations, and in x-ray imaging experiments, some of the characteristics of fly-scan ptychography, including a factor of 25 reduction in the data acquisition time. This approach will become increasingly important as brighter x-ray sources are developed, such as diffraction limited storage rings.

43 PARTICLE ACCELERATORS↗
DOE OSTI2015

Paleotemperatures at the lunar surfaces from open system behavior of cosmogenic 38 Ar and radiogenic 40 Ar

The simultaneous diffusion of both cosmogenic 38 Ar and radiogenic 40 Ar from solid phases is controlled by the thermal conditions of rocks while residing near planetary surfaces. Combined observations of 38 Ar/ 37 Ar and 40 Ar/ 39 Ar ratios during stepwise degassing analyses of neutron-irradiated Apollo samples can distinguish between diffusive loss of Ar due to solar heating of the rocks and that associated with elevated temperatures during or following impact events; the data provide quantitative constraints on the durations and temperatures of each process. From sequentially degassed 38 Ar/ 37 Ar ratios can be calculated a spectrum of apparent 38 Ar exposure ages versus the cumulative release fraction of 37 Ar, which is particularly sensitive to conditions at the lunar surface typically over ~106–108 year timescales. Due to variable proportions of K- and Ca-bearing glass, plagioclase and pyroxene, with variability in the grain sizes of these phases, each sample will have distinct sensitivity to, and therefore different resolving power on, past near-surface thermal conditions. Furthermore, we present the underlying assumptions, and the analytical and numerical methods used to quantify the Ar diffusion kinetics in multi-phase whole-rock analyses that provide these constraints.

58 GEOSCIENCES↗
DOE OSTI2024

Oxygen vacancies in niobium pentoxide as a source of two-level system losses in superconducting niobium

We identify a major source of quantum decoherence in three-dimensional superconducting radio-frequency (SRF) resonators and two-dimensional transmon qubits composed of oxidized niobium: oxygen vacancies in the niobium pentoxide, which drive two-level system (TLS) losses. By probing the effect of sequential in situ vacuum-baking treatments on the rf performance of bulk Nb SRF resonators and on the oxide structure of a representative Nb sample using TOF SIMS, we find a nonmonotonic evolution of cavity quality factor Q 0 , which correlates with the interplay of Nb 2 O 5 vacancy generation and oxide-thickness reduction. We localize this effect to the oxide itself and present the insignificant role of diffused interstitial oxygen in the underlying Nb by regrowing the oxide via wet oxidation, which reveals a mitigation of aggravated TLS losses. We hypothesize that such vacancies in the pentoxide serve as magnetic impurities and are a source of TLS-driven rf loss.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

Correlated prompt fission data in transport simulations

Detailed information on the fission process can be inferred from the observation, modeling and theoretical understanding of prompt fission neutron and γ-ray observables. Beyond simple average quantities, the study of distributions and correlations in prompt data, e.g., multiplicity-dependent neutron and γ-ray spectra, angular distributions of the emitted particles, n -n, n - γ, and γ - γ correlations, can place stringent constraints on fission models and parameters that would otherwise be free to be tuned separately to represent individual fission observables. The FREYA and CGMF codes have been developed to follow the sequential emissions of prompt neutrons and γ rays from the initial excited fission fragments produced right after scission. Both codes implement Monte Carlo techniques to sample initial fission fragment configurations in mass, charge and kinetic energy and sample probabilities of neutron and γ emission at each stage of the decay. This approach naturally leads to using simple but powerful statistical techniques to infer distributions and correlations among many observables and model parameters. The comparison of model calculations with experimental data provides a rich arena for testing various nuclear physics models such as those related to the nuclear structure and level densities of neutron-rich nuclei, the γ-ray strength functions of dipole and quadrupole transitions, the mechanism for dividing the excitation energy between the two nascent fragments near scission, and the mechanisms behind the production of angular momentum in the fragments, etc. Beyond the obvious interest from a fundamental physics point of view, such studies are also important for addressing data needs in various nuclear applications. The inclusion of the FREYA and CGMF codes into the MCNP6.2 and MCNPX - PoliMi transport codes, for instance, provides a new and powerful tool to simulate correlated fission events in neutron transport calculations important in nonproliferation, safeguards, nuclear energy, and defense programs. Here, this review provides an overview of the topic, starting from theoretical considerations of the fission process, with a focus on correlated signatures. It then explores the status of experimental correlated fission data and current efforts to address some of the known shortcomings. Numerical simulations employing the FREYA and CGMF codes are compared to experimental data for a wide range of correlated fission quantities. The inclusion of those codes into the MCNP6.2 and MCNPX - PoliMi transport codes is described and discussed in the context of relevant applications. The accuracy of the model predictions and their sensitivity to model assumptions and input parameters are discussed. Lastly, a series of important experimental and theoretical questions that remain unanswered are presented, suggesting a renewed effort to address these shortcomings.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2019

New Insights in the Quench Mechanisms in Nitrogen Doped Cavities

This paper will cover a systematic study of the quench in nitrogen doped cavities: three cavities were sequentially treated/reset with different doping recipes which are known to produce different levels of quench field. Analysis of mean free path and TMAP coupled with sample analysis reveals new insights on the physics of the premature quench in nitrogen doped cavities; new recipes demonstrate the possibility to increase quench fields well beyond 30 MV/m.

43 PARTICLE ACCELERATORS↗
DOE OSTI2025

Oxygen Vacancies in Niobium Pentoxide as a Source of Two-Level System Losses in Superconducting Niobium

We identify a major source of quantum decoherence in three-dimensional superconducting radio-frequency (SRF) resonators and two-dimensional transmon qubits composed of oxidized niobium: oxygen vacancies in the niobium pentoxide, which drive two-level system (TLS) losses. By probing the effect of sequential in situ vacuum-baking treatments on the rf performance of bulk Nb SRF resonators and on the oxide structure of a representative Nb sample using TOF SIMS, we find a nonmonotonic evolution of cavity quality factor Q0, which correlates with the interplay of Nb2O5 vacancy generation and oxide-thickness reduction. We localize this effect to the oxide itself and present the insignificant role of diffused interstitial oxygen in the underlying Nb by regrowing the oxide via wet oxidation, which reveals a mitigation of aggravated TLS losses. We hypothesize that such vacancies in the pentoxide serve as magnetic impurities and are a source of TLS-driven rf loss.

Bafia, Daniel P. [Fermilab]↗
DOE OSTI2022

Measuring Very Low Radiation Doses in PTFE for Nuclear Forensic Enrichment Reconstruction

Every country that has made nuclear weapons has used uranium enrichment. Despite the centrality of this technology to international security, there is still no reliable physical marker of past enrichment that can be used to perform forensic verification of historically produced weapons. We show that the extremely low radioactivity from uranium alpha emissions during enrichment leaves detectable and irreversible calorimetric signatures in the common enrichment gasket material PTFE, allowing for historical reconstruction of past enrichment activities at a sensitivity better than one weapon's quantity of highly enriched uranium. Fast scanning calorimetry also enables the measurement of recrystallization enthalpies of sequentially microtomed slices, confirming the magnitude and the type of radiation exposure while also providing a detection of tampering and a method for analyzing field samples useful for treaty verification. This work opens the door for common items to be turned into precise dosimeters to detect the past presence of radioactivity, nuclear materials, and related activities with high confidence.

Connick, Rachel↗
DOE OSTI2018

Quantitative Prediction of Uranium Speciation and Amidoxime Binding in Seawater from Advanced Simulation Techniques

The goal of this project was to quantitatively predict stability of uranium species and thermochemistry of uranium binding with amidoxime ligands in realistic seawater conditions. The specific aims of the project were: (i) determine the stable species of uranium and its solvation structure in realistic seawater conditions; also speciation and solvation of uranium's major competing species in seawater, vanadium; (ii) accurately predict the free energies (and thereby stability constants) of binding between uranium and amidoxime; (iii) accurately predict the reaction enthalpies and entropies of binding between uranium and amidoxime as well as between vanadium and amidoxime. Main results and conclusions are as follows. First-principles molecular dynamic simulations found that the structure of the Ca 2 UO 2 (CO 3 ) 3 complex is very stable and that one Ca ion binds to the center UO 2 (CO 3 ) 3 4- anion stronger than the other Ca ion. This finding suggests that using time-resolved EXAFS spectra may confirm the asymmetry in binding of the two Ca ions in the aqueous Ca 2 UO 2 (CO 3 ) 3 complex. To consider the common ions, solvation of the Ca 2 UO 2 (CO 3 ) 3 complex in seawater was simulated by classical molecular dynamics simulation. It was found that the structure of the Ca 2 UO 2 (CO 3 ) 3 complex is very stable in the model seawater. A Na+ ion was found to be closely associated with the Ca 2 UO 2 (CO 3 ) 3 complex by indirectly interacting with one axial oxygen atom of the UO 2 group bridged by a water molecule. In addition, the Na + ion interacts closely with one Ca 2+ ion than the other. The present simulations revealed the key role of common ions such as Na + in impacting the solvation, structure, and apparent charge of the Ca 2 UO 2 (CO 3 ) 3 complex in seawater. The sequential processes of UO 2 2+ binding with the three CO 3 2- groups and the two Ca 2+ ions in pure water and in 0.1 M NaCl were simulated by classical molecular dynamics with both the non-constrained brute-force approach and umbrella sampling. The simulated free energies show excellent agreement with the experiment. The coordination structures of UO 2 (CO 3 ) 3 4- and CaUO 2 (CO 3 ) 3 2- were found to be significantly affected by the presence of Na + ions, leading to a monodentate binding of a carbonate group to U and a water molecule entering the first coordination shell of U. To shed light on the binding between uranyl and glutardiamidoxime (H 2 B), an important model and state-of-the-art ligand for seawater uranium extraction, a suite of computational methods was employed. From molecular dynamics (MD) simulations, it was found that the binding configurations of B 2- with uranyl favor the twofold distorted η 2 binding between the oximate ends (C=N-O-) and U, while HB - prefers the chelating mode for the oximate end with the neutral end being solvated by water. The free energies of sequential ligand binding to form UO 2 B, [UO 2 B 2 ] 2- , and [UO 2 (HB)B] - were simulated with umbrella sampling and very good agreement with the experimental values was achieved, which corroborates the structural insights into the binding mode. State-of-the-art polymeric sorbents employ both amidoximate and carboxylate groups on the side chains to achieve optimal U uptake and selectivity, so we simulated the binding of a model amidoximate–carboxylate bifunctional ligand with uranyl. Classical MD and free-energy simulations in 0.5 M NaCl showed that the carboxylate group binds first to uranyl, leading to a loose intermediate state, and then, the amidoximate group binds, resulting in a more stable and tight chelate state. Binding of the second bifunctional ligand follows a similar process, and the two ligands prefer a trans configuration around the uranyl group. The simulated free energies indicate that the two bifunctional ligands bind with uranyl 14 kcal/mol stronger than the two ligands with only amidoximate groups, confirming an important synergy between amidoximate and carboxylate groups in binding uranyl.

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

Anisotropic structure and optical engineering of strontium titanate and zirconia responding to sequential hydrogen and helium irradiation

Unraveling the correlation between strain engineering with anisotropic optical properties via nanoscale defects gradually evolved into a strategy for fundamental studies and technological applications, yet it remains understudied in functional complex oxides compared to metals and semiconductors. Here, the methodology of strain engineering for the determination of the lattice parameters, parallel/normal to the sample surface, in the individual layers of single-crystalline superlattices is derived, which is based on analysis of high-angle X-ray diffraction measurements in combination with diffraction reciprocal space mapping. With modeling that takes into account the effect of elastic properties, two elastically anisotropic materials, SrTiO 3 and ZrO 2 , have been compared in terms of defect-induced elastic strain caused by individual and sequential H + and He 2+ irradiation. The anisotropic lattice swelling with corresponding refractive index, and obstructive behavior of elastic strain recovery are demonstrated in SrTiO 3 , while approaching strain behaviors accompanied by isotropic refractive index distribution in both orientations are confirmed in ZrO 2 . Under sequential He 2+ /H + irradiation, pre-existing He-vacancy complexes acted as vacancy traps, preferentially capturing H + clusters to induce lattice distortion and enhance absorption. Nanohardness increments (ΔH) calculated by the DBH model matched nanoindentation results, confirming that sequential irradiation generated higher indentation yield stress than individual irradiations.

Anisotropic expansion↗
DOE OSTI2018

The F-t-Pj-RG method: An adjacent-rolling-windows based steady-state detection technique for application to kinetic Monte Carlo simulations

A window-based steady-state detection algorithm has been developed for application to kinetic Monte Carlo simulation data. The algorithm, termed F-t-Pj-RG sequentially applies an F-test, a t-test, and a projection test on adjacent windows of the data while rolling (or shifting) and growing the windows when any of the tests fail. In aggregate, the algorithm is able to (a) automatically reject the warm-up period as not being at steady-state, as well as (b) determine an appropriate window size for converged statistics when sampling the data, which is necessary for detection of steady-state, and (c) detect steady-state within a particular tolerance. The last step, the projection test, is actually an oscillating-slope projection test, and is performed on j sequential data windows (i.e., more than two adjacent windows). It requires more than simply being within the user defined tolerance: the oscillating-slope projection test includes a condition that the slope must oscillate around zero when 2, which is an additional indication of steady-state. When all three tests are passed, the F-t-Pj test is passed, indicating that the prerequisites of steady-state detection have been met and also that conditions consistent with the definition of steady-state have been realized. This algorithm is applied to a variety of data sets that correspond to the diverse type of data trends that can be produced by kinetic Monte Carlo simulations. The algorithm is shown to be robust in its ability to handle differing functional forms, and is able to detect steady-state with low computational cost. Finally, the low computational cost of this method and its robustness towards varied data trends make it suitable for on-the-fly use in kinetic Monte Carlo simulations.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

A fast particle-based approach for calibrating a 3-D model of the Antarctic ice sheet

We consider the scientifically challenging and policy-relevant task of understanding the past and projecting the future dynamics of the Antarctic ice sheet. The Antarctic ice sheet has shown a highly nonlinear threshold response to past climate forcings. Triggering such a threshold response through anthropogenic greenhouse gas emissions would drive drastic and potentially fast sea level rise with important implications for coastal flood risks. Previous studies have combined information from ice sheet models and observations to calibrate model parameters. These studies have broken important new ground but have either adopted simple ice sheet models or have limited the number of parameters to allow for the use of more complex models. These limitations are largely due to the computational challenges posed by calibration as models become more computationally intensive or when the number of parameters increases. Here, we propose a method to alleviate this problem: a fast sequential Monte Carlo method that takes advantage of the massive parallelization afforded by modern high-performance computing systems. We use simulated examples to demonstrate how our sample-based approach provides accurate approximations to the posterior distributions of the calibrated parameters. The drastic reduction in computational times enables us to provide new insights into important scientific questions, for example, the impact of Pliocene era data and prior parameter information on sea level projections. These studies would be computationally prohibitive with other computational approaches for calibration such as Markov chain Monte Carlo or emulation-based methods. We also find considerable differences in the distributions of sea level projections when we account for a larger number of uncertain parameters. For example, based on the same ice sheet model and data set, the 99th percentile of the Antarctic ice sheet contribution to sea level rise in 2300 increases from 6.5 m to 13.1 m when we increase the number of calibrated parameters from three to 11. With previous calibration methods, it would be challenging to go beyond five parameters. Here, this work provides an important next step toward improving the uncertainty quantification of complex, computationally intensive and decision-relevant models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Atomistic thermodynamics and kinetics of dicalcium silicate dissolution

Low-temperature cement manufacturing has garnered academic and industrial attention for its low environmental footprints. However, the sluggish hydration kinetics of the resultant cement affects their early-age strength development. This motivates fundamental studies to unravel the mechanistic picture of the dissolution process and discover science-informed pathways to accelerate hydration. Standard atomistic simulations seldomly exceed a microsecond making them impractical to study slow dissolution processes. We are using rare event sampling techniques, we provide the mechanistic picture of Ca 2+ ion dissolution from a kink site on the dicalcium silicate surface. The Ca 2+ ion dissolution is comprised of two sequential stages: breaking restraints from the kink sites to form a ledge adatom and detaching from the ledge/terrace adatom sites into the solution. The first and second stages feature free energy barriers of ~63 kJ/mol and ~ 29 kJ/mol respectively, making the first stage the rate-limiting step of the entire Ca 2+ dissolution kinetics. Using the reactive flux method, the rate and equilibrium constants for each reaction step are calculated, which yield the Ca 2+ ion activity of ~1.03 × 10 -5 . The diffusion calculations indicate that the surface effects lower the self-diffusion coefficient of Ca 2+ ions at the solid-water interface.

36 MATERIALS SCIENCE↗
NASA NTRS1977

The radiation history of material returned by the Soviet automatic stations Luna 16 and Luna 20, according to track studies

Fission tracks formed by the vH (very heavy) nuclei group of solar and galactic cosmic rays have been studied in silicate minerals of the lunar regolith returned by the Luna 16 and Luna 20 unmanned spacecraft. It is shown that the material in the Luna 16 core sample, from a typical mare region of the lunar surface, has undergone stronger irradiation by cosmic rays than material returned a highland region by Luna 20. A low-irradiation component (about 10 percent of the total number of crystals) has been found in the Luna 20 core sample materials, which can possibly be attributed to material added to the main bulk of the regolith in the formation of the crater Apollonius C. From the track density distribution of crystals, as a function of depth in the regolith core sample, it follows that the process of formation of the upper layer of the regolith, both for the lunar mare and for the highland region, includes sequential layering of finely crushed crystalline matter and subsequent mixing of it by micrometeorite bombardment. A portion of the crystals with a very high track density may be a component added to the lunar surface from outer space.

Kashkarov, L. L.↗
NASA NTRS2008

Efficient Simulation Budget Allocation for Selecting an Optimal Subset

We consider a class of the subset selection problem in ranking and selection. The objective is to identify the top m out of k designs based on simulated output. Traditional procedures are conservative and inefficient. Using the optimal computing budget allocation framework, we formulate the problem as that of maximizing the probability of correc tly selecting all of the top-m designs subject to a constraint on the total number of samples available. For an approximation of this corre ct selection probability, we derive an asymptotically optimal allocat ion and propose an easy-to-implement heuristic sequential allocation procedure. Numerical experiments indicate that the resulting allocatio ns are superior to other methods in the literature that we tested, and the relative efficiency increases for larger problems. In addition, preliminary numerical results indicate that the proposed new procedur e has the potential to enhance computational efficiency for simulation optimization.

Chen, Chun-Hung↗
DOE OSTI2017

Anaerobic digestion of solid agroindustrial waste in semi-continuous mode: Evaluation of mono-digestion and co-digestion systems

Highlights: • Agroindustrial waste were co-digested with an artificial organic fraction. • Variations in organic loading rate and hydraulic retention time were studied. • Sequential feeding of the substrates based on their seasonality was investigated. • Co-digestion resulted in higher methane yields compared with mono-digestion. • Applying sequential feeding led to a more equilibrated system operation. - Abstract: The present study aimed at investigating the anaerobic digestion of four agroindustrial waste, namely cotton gin waste, winery waste, olive pomace and juice industry waste, in semi-continuous mode, conducting mono-digestion and co-digestion assays, using an artificial organic fraction sample as co-substrate. These assays were divided into two groups, in which different conditions were applied. Group I investigated the variation in two operational parameters, i.e. the organic loading rate (OLR) and the hydraulic retention time (HRT), while in Group II, the assays were fed with different substrates in a sequential order. Results showed more elevated specific methane yields for co-digestion assays compared with mono-digestion assays. Maximum yields were achieved at an OLR of 1.0 gVS/(L·d) and a HRT reduced to half of the initial. Further reduction of the HRT coupled to an increase of the OLR generally caused a significant decrease of specific methane yields, as well as one case of severe overloading, i.e. the mono-digestion of juice industry waste, which resulted in instability and ultimately system failure. Sequential feeding with different substrates led to a more equilibrated operation, especially for co-digestion systems, with higher specific methane yields being observed during the phases corresponding to winery waste and juice industry waste substrates. Overall more positive results were obtained in the cases in which the latter substrates were fed to the reactors at process startup.

09 BIOMASS FUELS↗
DOE OSTI2021

Pressure-Driven Sequential Lattice Collapse and Magnetic Collapse in Transition-Metal-Intercalated Compounds Fe x NbS 2

Volume collapse under high pressure is an intriguing phenomenon involving subtle interplay between lattice, spin, and charge. The two most important causes of volume collapse are lattice collapse (low-density to high-density) and magnetic collapse (high-spin to low-spin). Herein we report the pressure-driven sequential volume collapses in partially intercalated Fe x NbS 2 (x = 1/4, 1/3, 1/2, 2/3). Because of the distinct interlayer atomic occupancy, the low-iron-content samples exhibit both lattice and magnetic collapses under compression, whereas the high-iron-content samples exhibit only one magnetic collapse. Therefore, theoretical calculations indicate that the low-pressure volume collapses for x = 1/4 and x = 1/3 are lattice collapses, and the high-pressure volume collapses for all four samples are magnetic collapses. The magnetic collapse involving the high-spin to low-spin crossover of Fe2+ has also been verified by in situ X-ray emission measurements. Integrating two distinct volume collapses into one material provides a rare playground of lattice, spin, and charge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Automated pipeline framework for processing of large-scale building energy time series data

Commercial buildings account for one third of the total electricity consumption in the United States and a significant amount of this energy is wasted. Therefore, there is a need for “virtual” energy audits, to identify energy inefficiencies and their associated savings opportunities using methods that can be non-intrusive and automated for application to large populations of buildings. Here we demonstrate virtual energy audits applied to large populations of buildings’ time-series smart-meter data using a systematic approach and a fully automated Building Energy Analytics (BEA) Pipeline that unifies, cleans, stores and analyzes building energy datasets in a non-relational data warehouse for efficient insights and results. This BEA pipeline is based on a custom compute job scheduler for a high performance computing cluster to enable parallel processing of Slurm jobs. Within the analytics pipeline, we introduced a data qualification tool that enhances data quality by fixing common errors, while also detecting abnormalities in a building’s daily operation using hierarchical clustering. We analyze the HVAC scheduling of a population of 816 buildings, using this analytics pipeline, as part of a cross-sectional study. With our approach, this sample of 816 buildings is improved in data quality and is efficiently analyzed in 34 minutes, which is 85 times faster than the time taken by a sequential processing. The analytical results for the HVAC operational hours of these buildings show that among 10 building use types, food sales buildings with 17.75 hours of daily HVAC cooling operation are decent targets for HVAC savings. Overall, this analytics pipeline enables the identification of statistically significant results from population based studies of large numbers of building energy time-series datasets with robust results. These types of BEA studies can explore numerous factors impacting building energy efficiency and virtual building energy audits. This approach enables a new generation of data-driven buildings energy analysis at scale.

36 MATERIALS SCIENCE↗
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↗