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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Californium-252 production at the High Flux Isotope Reactor - I: Validation study using campaign data

This paper presents a series of 252 Cf production validation and code-to-code comparison studies performed based on data from the production campaigns at the High Flux Isotope Reactor (HFIR). These studies support efforts to convert HFIR from using highly enriched uranium (HEU) fuel to low-enriched uranium (LEU) fuel. HFIR must maintain its world-class performance and missions following this conversion, and because 252 Cf is a vital neutron-emitting radioisotope used for a variety of high-impact applications (e.g., reactor startup, cancer treatment), the ability to efficiently produce 252 Cf must be preserved. In this work, the HFIRCON, Shift, ORIGEN, and TCOMP codes were deployed, and several sets of data libraries were investigated to better understand the calculation codes and the data biases. As-loaded target composition data, as-run irradiation history data, and post-irradiation measurements from recent multi-cycle irradiation campaigns of the HEU core were used to validate and determine methodology biases. Further, the findings demonstrated a good agreement, with results falling within 3 standard deviations of measurements. This paper lays the ground work for the second paper, which evaluates and compares 252 Cf production and safety metrics with the HEU core and a proposed LEU core.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2024

Investigating Mountain Watershed Headwater‐To‐Groundwater Connections, Water Sources, and Storage Selection Behavior With Dynamic‐Flux Particle Tracking

Abstract Climate change will impact mountain watershed streamflow both directly—with changing precipitation amounts and variability—and indirectly—through temperature shifts altering snowpack, melt, and evapotranspiration. To understand how these complex processes will affect ecosystem functioning and water resources, we need tools to distinguish connections between water sources (rain/snowmelt), groundwater storage, and exit fluxes (streamflow/evapotranspiration), and to determine how these connections change seasonally and as climate shifts. Here, we develop novel watershed‐scale approaches to understand water source, storage, and exit flux connections using a dynamic‐flux particle tracking model (EcoSLIM) applied in California's Cosumnes Watershed, which connects the Sierra Nevada and Central Valley. This work develops new visualizations and applications to provide mechanistic understanding that underpins the interpretation of isotopic field data at watershed scales to distinguish sources, flow paths, residence times, and storage selection. In our simulations, streamflow comes primarily from snow‐derived water while evapotranspiration generally comes from rain. Most streamflow starts above 1,000 m while evapotranspiration is sourced relatively evenly across the watershed and is generally younger than streamflow. Modeled streamflow consists primarily of water sourced from precipitation in the previous 5 years but before the current water year, while ET consists primarily of water from precipitation in the current water year. ET, and to a lesser extent streamflow, are both younger than water in groundwater storage. However, snowmelt‐derived streamflow preferentially discharges older water from snow‐derived storage. Dynamic‐flux particle tracking and new approaches presented here enable novel model‐tracer comparisons in large‐scale watersheds to better understand watershed behavior in a changing climate.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1993

Collision cross sections and diffusion parameters for H and D in atomic oxygen

Modeling the behavior of H and D in planetary exospheres requires detailed knowledge of the differential scattering cross sections for all of the important neutral-neutral and ion-neutral collision processes affecting these species over their entire ranges of interaction energies. In the upper atmospheres of Earth, Venus, and other planets as well, the interactions of H and D with atomic oxygen determine the rates of diffusion of escaping hydrogen isotopes through the thermosphere, the velocity distributions of exospheric atoms that encounter the upper thermosphere, the lifetimes of exospheric orbiters with periapsides near the exobase, and the transfer of momentum in collisions with hot O. The nature of H-O and D-O collisions and the derivation of a data base consisting of phase shifts and the differential, total, and momentum transfer cross sections for these interactions in the energy range 0.001 - 10 eV are discussed. Coefficients of mutual diffusion and thermal diffusion factors are calculated for temperatures of planetary interest.

Hodges, R. R., Jr.↗
NASA NTRS2009

Evolved Gas Measurements Planned for the Lower Layers of the Gale Crater Mound with the Sample Analysis at Mars Instrument Suite

The lower mound strata of Gale Crater provide a diverse set of chemical environments for exploration by the varied tools of the Curiosity Rover of the Mars Science Laboratory (MSL) Mission. Orbital imaging and spectroscopy clearly reveal distinct layers of hydrated minerals, sulfates, and clays with abundant evidence of a variety of fluvial processes. The three instruments of the MSL Sample Analysis at aMars (SAM) investigation, the Quadrupole Mass Spectrometer (QMS), the Tunable Laser Spectrometer (TLS), and the Gas Chromatograph (GC) are designed to analyze either atmospheric gases or volatiles thermally evolved or chemically extracted from powdered rock or soil. The presence or absence of organic compounds in these layers is of great interest since such an in situ search for this type of record has not been successfully implemented since the mid-60s Viking GCMS experiments. However, regardless of the outcome of the analysis for organics, the abundance and isotopic composition of thermally evolved inorganic compounds should also provide a rich data set to complement the mineralogical and elemental information provided by other MSL instruments. In addition, these evolved gas analysis (EGA) experiments will help test sedimentary models proposed by Malin and Edgett (2000) and then further developed by Milliken et al (2010) for Gale Crater. In the SAM EGA experiments the evolution temperatures of H2O, CO2, SO2, O2, or other simple compounds as the samples are heated in a helium stream to 1000 C provides information on mineral types and their associations. The isotopic composition of O, H, C, and S can be precisely determined in several evolved compounds and compared with the present day atmosphere. Such SAM results might be able to test mineralogical evidence of changing sedimentary and alteration processes over an extended period of time. For example, Bibring et al (2006) have suggested such a major shift from early nonacidic to later acidic alteration. We will illustrate through a variety of evolved gas experiments implemented under SAM-like gas flow and temperature ramp conditions on terrestrial analog minerals on high fidelity Sam breadboards the type of chemical information we expect SAM to provide.

Mahaffy, Paul↗
DOE OSTI2023

The Zonal Patterns in Late Quaternary Tropical South American Precipitation

Speleothem oxygen isotope records (δ 18 O) of tropical South American rainfall in the late Quaternary show a zonal “South American Precipitation Dipole” (SAPD). The dipole is characterized by opposing east-west precipitation anomalies compared to the present—wetter in the east and drier in the west at the mid-Holocene (~7 ka), and drier in the east and wetter in the west at the Last Glacial Maximum (~21 ka). However, the SAPD remains enigmatic because it is expressed differently in western versus eastern δ18O records and isotope-enabled climate model simulations usually misrepresent the magnitude and/or spatial pattern of δ 18 O change. Here, we address the SAPD enigma in two parts. First, we re-interpret the δ 18 O data to account for upwind rainout effects that are known to be pervasive in tropical South America, but are not always considered in Quaternary paleoclimate studies. Our revised interpretation reconciles the δ 18 O data with cave infiltration and other proxy records, and indicates that the centroid of tropical South American rainfall has migrated zonally over time. Second, using an energy balance model of tropical atmospheric circulation, we hypothesize that zonal migration of the precipitation centroid can be explained by regional energy budget shifts, such as changing Saharan albedo associated with the African Humid Period, that have not been modeled in previous SAPD studies. This hypothesis of a migrating precipitation centroid presents a new framework for interpreting δ18O records from tropical South America and may help explain the zonal rainfall anomalies that predate the late Quaternary.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Data from: "Warming of alpine tundra enhances belowground production and shifts community towards resource acquisition traits"

This archive contains data used to draw conclusions in “Warming of alpine tundra enhances belowground production and shifts community towards resource acquisition traits”, by Yang et al. 2020. Data were collected on Niwot Ridge, in an alpine meadow within the Alpine Treeline Warming Experiment (ATWE) field sites in Colorado, USA. Samples were also processed in the U.S. Geological Survey Forest and Rangeland Ecosystem Science Center, in Boise, Idaho. File formats in this archive include comma-separated values (.csv), portable document format (.pdf), Microsoft Excel (.xlsx), and two types of geospatial files: keyhole markup language (.kml), and ESRI shapefiles (.shp). Leaf scans are .jpg images, and root scans are .tiff/.tif images.The .csv files can be opened using R, Microsoft Excel, or any simple text-editing software such as TextEdit and Notepad. Microsoft Excel files can be opened using Microsoft Excel, and .pdf files can be opened with Adobe Acrobat Reader, Preview, or other compatible programs. Scanned images can be opened using any photo and/or picture viewing software.The .kml file can be opened using Google Earth and Google Maps, and the shapefiles can be opened by any programs compatible with shapefiles, such as the ArcGIS Desktop suite, and QGIS.------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Measures of belowground net primary productivity (BNPP) are required to understand whether aboveground net primary production (ANPP) changes reflect changes in allocation or are indicative of a whole plant NPP response. Plant functional traits provide a key way to scale from the individual plant to the community level, and provide insight into drivers of NPP responses to environmental change. We used infrared heaters to warm an alpine plant community at Niwot Ridge, Colorado, and applied supplemental water to compensate for soil water loss induced by warming. We measured ANPP, BNPP, and leaf and root functional traits across treatments after 5 years of continuous warming. Community-level ANPP and total NPP (ANPP + BNPP) did not respond to heating or watering, but BNPP increased in response to heating. Heating decreased community-level leaf dry matter content and increased total root length, indicating a shift in strategy from resource conservation to acquisition in response to warming.

13C/12C isotope ratio↗
DOE OSTI2022

DOE new players Carbon cycle (2016-2021)

The overarching scientific goals of our multidisciplinary grant was to further expand understanding about the key microorganisms (players), metabolic strategies (processes), and interspecies relationships (interactions) involved in the formation and oxidation of methane in the environment. This research applied novel environmental metagenomics, transcriptomics, and proteomic techniques, state-of-the-art analytical imaging, stable isotope geochemistry, and reaction-transport modeling to address these goals and develop an ‘ecosystems level’ understanding of the factors which regulate microbial methane cycling in anoxic sedimentary ecosystems. For decades, it was believed that the obligate step in methanogenesis catalyzed by methyl coenzyme M reductase (Mcr) was limited to a specific branch of the archaeal Domain, formerly known as the Euryarchaeota. Less than a decade ago co-I Tyson’s team published a surprising metagenomic-based discovery of divergent Mcr genes in a novel uncultured phylum (Bathyarchaeota), catalyzing a major shift in thinking about the diversity of microorganisms that encode the potential for methane (or higher alkane) metabolism in anoxic environments (Evans et al., 2015). In our work here, we further expand on the groups of archaea harboring the genomic potential for methane or hydrocarbon metabolism using environmental metagenomics and new gene targeted bioinformatics techniques. We additionally advanced understanding about the terminal electron acceptors and metabolic potential supporting the anaerobic oxidation of methane (AOM) in terrestrial ecosystems, specifically focused on new lineages of ANME archaea capable of respiring manganese oxides with methane presumably using large extracellular multi-heme cytochrome complexes. New details about specific syntrophic mechanisms underlying the exchange of electrons during sulfate-coupled methane oxidation between ANME-2 archaea and their sulfate-reducing bacterial partners were also elucidated as part of this funded project. Through a series of experimental ‘omics and single cell stable isotope probing studies with incubated environmental sediment samples and a cultured model electrogenic microorganism combined with model-based predictions. Combined, this work provides strong support for the hypothesis of direct interspecies electron transfer (DIET) is the dominant syntrophic mechanism controlling the anaerobic oxidation of methane with sulfate over other proposed mechanisms and additionally illustrates important spatial constraints and the underlying physico-chemical factors influencing AOM syntrophic consortia structure for DIET and extracellular metal respiration. This collaborative multi-institutional project successfully advanced several of our milestone goals including the identification of new microbial players containing methyl coenzyme M reductases hypothesized to be central to methane or hydrocarbon cycling in anoxic environments and enhancing fundamental knowledge about the role extracellular electron transfer plays in the ecophysiology of methanotrophic archaea respiring metal oxides and in the physical and metabolic structuring of syntrophic interactions in methane-rich sedimentary ecosystems.

03 NATURAL GAS↗
DOE OSTI2020

Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel

We present here detailed mechanistic studies of electrocatalytic hydrogenation (ECH) in aqueous solution over skeletal nickel cathodes to probe the various paths of reductive catalytic C–O bond cleavage among functionalized aryl ethers relevant to energy science. Heterogeneous catalytic hydrogenolysis of aryl ethers is important both in hydrodeoxygenation of fossil fuels and in upgrading of lignin from biomass. The presence or absence of simple functionalities such as carbonyl, hydroxyl, methyl, or methoxyl groups is known to cause dramatic shifts in reactivity and cleavage selectivity between sp3 C–O and sp2 C–O bonds. Specifically, reported hydrogenolysis studies with Ni and other catalysts have hinted at different cleavage mechanisms for the C–O ether bonds in α-keto and α-hydroxy β-O-4 type aryl ether linkages of lignin. Our new rate, selectivity, and isotopic labeling results from ECH reactions confirm that these aryl ethers undergo C–O cleavage via distinct paths. For the simple 2-phenoxy-1-phenylethane or its alcohol congener, 2-phenoxy-1-phenylethanol, the benzylic site is activated via Ni C–H insertion, followed by beta elimination of the phenoxide leaving group. But in the case of the ketone, 2-phenoxyacetophenone, the polarized carbonyl π system apparently binds directly with the electron rich Ni cathode surface without breaking the aromaticity of the neighboring phenyl ring, leading to rapid cleavage. Substituent steric and electronic perturbations across a broad range of β-O-4 type ethers create a hierarchy of cleavage rates that supports these mechanistic ideas while offering guidance to allow rational design of the catalytic method. Furthermore, on the basis of the new insights, the usage of cosolvent acetone is shown to enable control of product selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Carbon and hydrogen isotopic characterization of methane from wetlands and lakes of the Yukon-Kuskokwim Delta, Western Alaska

The results are reported of a study of the carbon and hydrogen isotopic composition of methane from tundra environments of the Yukon-Kuskokwin Delta of western Alaska. The delta C-13 value of diffusive methane emissions from wet meadow tundra of the Delta is -65.82 +/- 2.21 per mil (n=18). Detritus-rich sediments of tundra lakes are loaded with methane-rich gas bubbles during the warm season. Spatial trend is the major gas concentration and isotopic values of methane in these gas bubbles appear to reflect processes associated with production rate and mechanisms; high methane concentrations, lightest delta C-13 values, the heaviest delta D value occur in detritus-rich sediments isolated from emergent vegetation. Heavier delta C-13 and lighter delta D values in methane from heavily vegetated lake margins suggest a shift toward a larger role for acetate fermentation in association with aquatic plants and plant detritus. Bubble ebullition is estimated to account for up to 17 percent of total Delta methane emissions.

Martens, Christopher S.↗
DOE OSTI2022

The roles of three-nucleon force and continuum coupling in mirror symmetry breaking of oxygen mass region

With both three-nucleon force and continuum coupling included, we have developed a self-consistent ab initio Gamow shell model within the Gamow Hartree-Fock (GHF) basis obtained by the realistic interaction itself. With the chiral two-nucleon N 3 LO and three-nucleon N 2 LO interactions, the Gamow shell model has been applied to the mirror systems of Z = 8 neutron-rich isotopes and N = 8 proton-rich isotones, giving good agreements with data in binding energies, dripline positions and excitation spectra. The GHF calculated that the 0 ds/2 , 1 S1/2 and 1 p3/2 orbitals are resonances. The resonance states and their interplay with nonresonant continua play a crucial role in the descriptions of nuclei around driplines. Excitation spectra and Thomas-Ehrman shifts observed can be better described when both three-nucleon force and continuum coupling are considered in calculations. The three-nucleon force and continuum coupling produce a combined effect on the Thomas-Ehrman shift, e.g., for the 1/2 + resonance level of 19Na. The calculations help the understandings of related nuclear astrophysical processes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

An Evaluation of Actinide Reactivity with CO 2 , O 2 , and O 2 /He Gases using Inductively Coupled Plasma Tandem Mass Spectrometry: Application to Simultaneous Measurement of 241 Am/ 241 Pu Ratios in Unseparated Complex Matrices

Accurate actinide measurements are critical within the field of nuclear science. Traditional methods for actinide quantification require time-consuming sample processing prior to analysis. There is a need for rapid analytical techniques that still maintain a high degree of accuracy. In this work, actinide reactivity was assessed for multiple oxygen-containing reaction gases using quadrupole inductively coupled plasma tandem mass spectrometry (Q-ICP-MS/MS) to evaluate actinide analysis in complex sample matrices without analyte-matrix separation. A novel method was developed to measure 241 Am/ 241 Pu in complex sample matrices using O 2 /He reaction gas with no matrix removal or analyte pre-concentration. This inline method reduces matrix-derived polyatomic interferences that complicate traditional ICP-MS analyses by mass-shifting to 241 Am 16 O + and 241 Pu 16 O 2 + , allowing Am and Pu to be mass separated for simultaneous analysis. While mass shifting is efficient, a small portion of Am + (<1.3%) and Pu + (<1.4%) react to from AmO 2 + and PuO + , respectively. Therefore, a mass balance approach was used, in combination with reactivity determined from 242 Pu and 243 Am standard solutions, to correct for residual 241 PuO + and 241 AmO 2 + . The method was validated by measuring 241 Am/ 241 Pu in Pu isotope standards CRM-136 and CRM-137 (separated in March/April 1970 and February 2022, respectively) in both neat solutions and complex matrices containing diluted soil (NIST SRM 2711a, >1000 µg·g -1 ). Method detection limits of 15.9 and 9.6 fg·g -1 were determined for 241 Am and 241 Pu, respectively, and 241 Am/ 241 Pu ratios were measured with accuracies within <3.5%. In conclusion, this work presents the first direct analysis of 241 Am/ 241 Pu in unseparated complex matrices, advancing capabilities for rapid actinide measurements.

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

Simulations of the IR and Raman spectra of water confined in amorphous silica slit pores

Water in nano-scale confining environments is a key element in many biological, material, and geological systems. The structure and dynamics of the liquid can be dramatically modified under these conditions. Probing these changes can be challenging, but vibrational spectroscopy has emerged as a powerful tool for investigating their behavior. A critical, evolving component of this approach is a detailed understanding of the connection between spectroscopic features and molecular-level details. In this paper, this issue is addressed by using molecular dynamics simulations to simulate the linear infrared (IR) and Raman spectra for isotopically dilute HOD in D 2 O confined in hydroxylated amorphous silica slit pores. The effect of slit-pore width and hydroxyl density on the silica surface on the vibrational spectra is also investigated. The primary effect of confinement is a blueshift in the frequency of OH groups donating a hydrogen bond to the silica surface. This appears as a slight shift in the total (measurable) spectra but is clearly seen in the distance-based IR and Raman spectra. Analysis indicates that these changes upon confinement are associated with the weaker hydrogen-bond accepting properties of silica oxygens compared to water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

Eigenbrode, Jennifer L.↗
DOE OSTI2022

Recent progress in L-H transition studies at JET: Tritium, Helium, Hydrogen and Deuterium

In this report we present an overview of results from a series of L-H transition experiments undertaken at JET since the installation of the ITER-like-wall (JET-ILW), with Beryllium wall tiles and a Tungsten divertor. Tritium, Helium and Deuterium plasmas have been investigated. Initial results in Tritium show ohmic L-H transitions at low density and the power threshold for the L-H transition (P LH ) is lower in Tritium plasmas than in Deuterium ones at low densities, while we still lack contrasted data to provide a scaling at high densities. In Helium plasmas there is a notable shift of the density at which the power threshold is minimum (n e,min ) to higher values relative to Deuterium and Hydrogen references. Above n e,min (He) the L-H power threshold at high densities is similar for D and He plasmas. Transport modelling in slab geometry shows that in Helium neoclassical transport competes with interchange-driven transport, unlike in Hydrogen isotopes. Measurements of the radial electric field in Deuterium plasmas show that E r shear is not a good indicator of proximity to the L-H transition. Transport analysis of ion heat flux in Deuterium plasmas show a non-linearity as density is decreased below n e,min . Lastly, a regression of the JET-ILW Deuterium data is compared to the 2008 ITPA scaling law.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Assessing the Impact of Large Removable Beryllium Reflector Experiments on HFIR Performance and Safety Metrics

This study investigated the effect of various removable beryllium (RB) experiment configurations on High Flux Isotope Reactor (HFIR) metrics to address increasing interest in these facilities for materials and fuels irradiation research. The RB reflector contains eight large and four small irradiation experiment facilities that offer excellent neutron flux conditions to perform fission and fusion reactor materials and fuels irradiation research. This work aims to outline acceptable RB configurations based on safety, performance, and programmatic metrics. This study assessed experiment effects on reactivity, cycle length, fission rate density distributions, and neutron flux distributions using the Shift, HFIRCON, and SCALE ORIGEN codes. Initial evaluations focused on generic experiment materials including aluminum plugs, stainless steel plugs, molybdenum plugs, and aluminum plugs with gadolinium shields. Subsequent analyses of MiniFuel experiments were performed to evaluate a heterogenous experiment, consisting of a more complex geometry and bearing several materials, and to test the correlations developed with the generic materials on a real experiment. Furthermore, the effects of neutron poison concentrations in the standard beryllium plugs were evaluated. When assuming a reference RB configuration with eight large fresh beryllium plugs, perturbed configurations with three aluminum plugs, one stainless steel plug, one molybdenum plug, one gadolinium-shielded aluminum plug, and one MiniFuel experiment resulted in a cycle length reduction of less than 1.3 days, the current threshold before requiring additional approvals. Configurations with five aluminum plugs, one stainless steel plug, one molybdenum plug, one gadolinium-shielded aluminum plug, and two MiniFuel experiments meet the 1.3 day limit if irradiated beryllium plugs are considered. Fuel element fission rate density distributions remained within safety limits, with maximum local increases under 9%. Neutron flux calculations revealed large thermal flux depressions inside and around the perturbed RB facilities, while epithermal and fast neutron fluxes increased because of reduced neutron moderation by the perturbed materials. These findings provide valuable guidance for optimizing RB configurations to balance safety and performance at HFIR.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2024

Antecedent Hydrologic Conditions Reflected in Stream Lithium Isotope Ratios During Storms

Antecedent hydrological conditions are recorded through the evolution of dissolved lithium isotope signatures (δ 7 Li) by juxtaposing two storm events in an upland watershed subject to a Mediterranean climate. Discharge and δ 7 Li are negatively correlated in both events,but mean δ 7 Li ratios and associated ranges of variation are distinct between them. We apply a previously developed reactive transport model (RTM) for the site to these event-scale flow perturbations, but observed shifts in stream δ 7 Li are not reproduced. To reconcile the stability of the subsurface solute weathering profile with our observations of dynamic stream δ 7 Li signatures, we couple the RTM to a distribution of fluid transit times that evolve based on storm hydrographs. The approach guides appropriate flux-weighting of fluid from the RTM over a range of flow path lengths, or equivalently fluid residence times. This flux-weighted RTM approach accurately reproduces dynamic storm δ 7 Li-discharge patterns distinguished by the antecedent conditions of the watershed.

58 GEOSCIENCES↗
DOE OSTI2025

Environmental Controls on Water Vapor Deuterium Excess in the Coastal Boundary Layer: An Information Theory Perspective

We use information theory to quantify the environmental controls on water vapor deuterium excess (D-excess) in coastal Southern California from June 2023 through February 2024. Using Shannon entropy, mutual information (MI), and joint mutual information, metrics that capture both linear and nonlinear relationships, we identify the most informative variables and variable combinations governing D-excess across contrasting marine and continental regimes. Relative humidity with respect to sea surface temperature (RHS) is consistently the strongest individual predictor, explaining up to 27% of D-excess variability during marine conditions but only 10% in continental air masses. The Relative humidity(RHS) + sea surface temperature (SST) combination demonstrates synergistic effects, where their joint influence (explaining up to 36% of D-excess variability) exceeds what either variable achieves individually, confirming their coupled influence on deuterium excess. Wind direction complements RHS most effectively during continental conditions. The best three-variable combination (RHS + SST + Planetary Boundary Layer height) explains 38% of D-excess variability in marine air, while no combination exceeds 20% explanatory power during continental periods. Information theory shows that heteroscedasticity in D-excess relationships indicates regime shifts in controlling processes and quantifies fundamental constraints on predictor variables: some environmental factors like surface pressure or water vapor flux contain insufficient information content to explain D-excess variability regardless of their physical relevance. These results highlight the different predictability limits between marine and continental regimes, challenging the adequacy of linear models and providing a rigorous framework for quantifying the information content of isotope-climate relationships with implications for both modern and paleoclimate applications.

information theory↗
DOE OSTI2026

Exploring Local Vibrational Structure in Protein-Bound Chlorophyll a: Isotope-Enrichment Experiments and Electrostatic Analysis

Local chlorophyll (Chl) vibrations play an essential role in biological photosynthesis by facilitating rapid energy transfer between pigments. In research studies, they also provide a useful spectroscopic probe of the local protein environment that surrounds each pigment. However, measuring the complete vibrational absorption spectrum of a protein-bound Chl molecule is much more difficult than, for example, Chl in neat solvent due to overlap with protein vibrations that typically drown out Chl vibrational features. Resonance Raman and fluorescence spectroscopies provide a way around this problem for Franck–Condon active vibrations, but these often rely on cryogenic measurement conditions and fail to capture vibrational signatures from, e.g., ester-group vibrations that lack coupling to a convenient electronic transition. In the present contribution, we use 13 C-enrichment of the protein backbone to shift protein background signals to lower frequency, providing a largely clean spectral window in which to study local Chl a C═O stretch modes. A room-temperature absorption spectrum for Chl a in the water-soluble chlorophyll protein (WSCP) of Lepidium virginicum is thus extracted as a difference between protein-plus-pigment and protein-only vibrational spectra. Excellent agreement in the molecular fingerprint region with the vibrational spectrum of Chl a in organic solvents confirms that the resulting spectrum represents the response of the protein-bound Chl a molecule. Furthermore, the ester group resonance is observed to shift in response to the S53P mutation that eliminates a 17 3 ester group hydrogen bond from the protein environment. Finally, we analyze these experimental results using MD-based electrostatic analysis, finding that electric-field mapping at the C atom of the ester group provides a satisfactory explanation for the observed frequency shifts between organic solvent and protein environment. MD analysis further suggests that a red-shifted ester peak observed experimentally for the S53P mutant results from solvation of the 17 3 Chl ester group due increase water penetration into the Chl-binding pocket relative to wild-type WSCP. Here, we anticipate that these results will prove useful both for benchmarking future simulation work and as a reference for interpreting Chl vibrational spectra as a probe of pigment–protein interactions.

14 SOLAR ENERGY↗