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At least 361 records · Page 20

Reduced accrual of mineral-associated organic matter after two years of enhanced rock weathering in cropland soils, though no net losses of soil organic carbon

Abstract Enhanced rock weathering (ERW), the application of crushed silicate rock to soil, can remove atmospheric carbon dioxide by converting it to (bi) carbonate ions or solid carbonate minerals. However, few studies have empirically evaluated ERW in field settings. A critical question remains as to whether additions of crushed rock might positively or negatively affect soil organic matter (SOM)—Earth’s largest terrestrial organic carbon (C) pool and a massive reservoir of organic nitrogen (N). Here, in three irrigated cropland field trials in California, USA, we investigated the effect of crushed meta-basalt rock additions on different pools of soil organic carbon and nitrogen (i.e., mineral-associated organic matter, MAOM, and particulate organic matter, POM), active microbial biomass, and microbial community composition. After 2 years of crushed rock additions, MAOM stocks were lower in the upper surface soil (0–10 cm) of plots with crushed rock compared to unamended control plots. At the 2 sites where baseline pre-treatment data were available, neither total SOC nor SON decreased over the 2 years of study in plots with crushed rock or unamended control plots. However, the accrual rate of MAOM-C and MAOM-N at 0–10 cm was lower in plots with crushed rock vs. unamended controls. Before ERW is deployed at large scales, our results suggest that field trials should assess the effects of crushed rock on SOM pools, especially over multi-year time scales and in different environmental contexts, to accurately assess changes in net C and understand the mechanisms driving interactions between ERW and SOM cycling.

58 GEOSCIENCES↗

Electronic and Vibrational Contributions to the Bulk Stabilities of Trivalent 3d Transition Metal Oxyhydroxides from Electronic Structure Calculations

Any understanding of the thermodynamic driving forces active in the global cycles of earth abundant metals requires attendant knowledge of the bulk mineral free energies. This can be particularly challenging for metal (oxyhydr)oxide phases which at low temperature aqueous conditions can be produced at a variety of hydration states and particle sizes. Here we present high quality density functional theory calculations of the relative bulk stabilities of a geologically important family of polymorphic trivalent metal oxyhydroxide crystal structures MOOH (M=Cr, Al, Fe). To improve understanding of their relative stabilities we permute the metal cations into the various possible canonical structure types including goethite (isostructural to diaspore and bracewillite), lepidocrocite (isosctructural to boehmite), guyaniite, and grimaldiite. Electronic, vibrational, and magnetic contributions are considered on a consistent theoretical footing using hybrid functionals and converged plane-wave bases. We find the considered bulk structures to be thermodynamically degenerate within the precision of the available theory, despite the fact that the vibrational and magnetic contributions vary substantially among the cations. A significant conclusion is that Cr3+ supports strong hydrogen bonds, low O-H stretching frequencies and facile H movement relative to the other cations.

Prange, Micah P.↗

Population-level control of two manganese oxidases expands the niche for bacterial manganese biomineralization

Abstract The enzymatic oxidation of aqueous divalent manganese (Mn) is a widespread microbial trait that produces reactive Mn(III, IV) oxide minerals. These biominerals drive carbon, nutrient, and trace metal cycles, thus playing important environmental and ecological roles. However, the regulatory mechanisms and physiological functions of Mn biomineralization are unknown. This challenge arises from the common occurrence of multiple Mn oxidases within the same organism and the use of Mn oxides as indicators of combined gene activity. Through the detection of gene activation in individual cells, we discover that expression ofmnxGandmcoA, two Mn oxidase-encoding genes inPseudomonas putidaGB-1, is confined to subsets of cells within the population, with each gene showing distinct spatiotemporal patterns that reflect local microenvironments. These coordinated intra-population dynamics control Mn biomineralization and illuminate the strategies used by microbial communities to dictate the extent, location, and timing of biogeochemical transformations.

Biotechnology & Applied Microbiology↗

Predictive Understanding of Compound and Cascading Extremes and Their Impacts

We seek to answer the following questions: What interactions across spatial and temporal scales drive multivariate compound and cascading water cycle extremes, and how can we leverage understanding of such interactions to improve predictive understanding of these events and quantification of their impacts?

54 ENVIRONMENTAL SCIENCES↗

Ecosystems and Networks Integrated with Genes and Molecular Assemblies (ENIGMA) (Final Scientific/Technical Report, Subcontract Award No. 6953691)

The overarching objective the Baliga lab is to develop a mechanistic understanding of the field relevant metabolic processes underlying community partitioning of respiration pathways and physiological state shifts. In order to dissect how environmental perturbations influence microbial regulatory networks, we have constructed data-driven models that capture the dynamic interplay between abiotic and biotic factors during laboratory simulations. Specifically, we have developed multiple computational models (i.e., cMonkey2, EGRIN 2.0, and multiple genome-scale metabolic models) connecting environmental influence to genome-encoded regulatory programs. In addition, we have generated new tools such as Live Anaerobic Cell Sorting (LAnCS) and Fluidized Bed Reactors (FBRs) to investigate the dynamics of community partitioning of metabolic processes supporting sulfate or nitrate respiration, which are two critical activities observed from the field site at Oak Ridge National Labs (ORNL). This framework of connecting field phenomena with laboratory simulations and computational modeling has created the Environmental Simulations and Modelling (EnvSim) campaign within ENIGMA. The campaign, which spans multiple laboratories across ENIGMA and is led by the Baliga group, has established synthetic communities (SynComs) to discover, characterize, and dissect key microbial processes relevant to field observations, such as emissions of the greenhouse gas nitrous oxide (N 2 O). For example, the EnvSim campaign so far has deduced four potential mechanisms that may account for the N 2 O emissions at the FRC and are currently being investigated by labs across ENIGMA. Denitrification may be driven by complete denitrifiers, however, their NosZ enzymes, which catalyze the final step in denitrification by converting N 2 O to N 2 , may be sensitive at a lower pH. Additionally, the denitrification process could be partitioned among organisms and some may have pH-sensitive NosZ genes. Another factor contributing to variable N 2 O emissions relates to the metal co-factors involved in the denitrification pathway. For instance, excess Cu, Al, Mn, U, Ni, Co, Cu, and/or Cd may have inhibitory effects on multiple enzymatic steps during denitrification, while the enzymatic production of nitrite, the precursor of N 2 O, can be limited by the essential metal Mo. Lastly, abiotic production of N 2 O may occur as a result of chemodenitrification, in which metals like Fe, Mn, and some organic compounds can drive redox reactions that convert nitrogen cycle intermediates to N 2 O under the right conditions. Current investigations and analyses have generated multiple transcriptomic profiles aiding the refinement of new metabolic and gene regulatory network model for our denitrifying SynCom. In sum, the previous funding cycle has generated 33 peer-reviewed publications spanning predictive network biology to co-operativity of mutualistic interspecies interactions of evolved communities. Our integration of multiple omics datasets and the development of new network modelling tools has revealed important insights that can explain field observed phenomenon and generated new hypotheses to be investigated in the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the Impact of a Novel TBC Material on Heat Transfer in a Spark Ignition Engine through 3D CFD-FEA Co-Simulation Routine

Thermal barrier coatings (TBCs) have been of interest since the 1970s for application in internal combustion (IC) engines. Thin TBCs exhibit a temperature swing phenomenon wherein wall temperatures dynamically respond to the transient working-gas temperature throughout the engine cycle, thus reducing the temperature difference driving the heat transfer. Determining these varying wall temperatures is necessary to evaluate and study the effect of coatings on wall heat transfer. This study focuses on developing a 3D computational fluid dynamics (CFD)-finite element analysis (FEA) coupled simulation, or co-simulation, routine to determine the wall temperatures of a piston coated with a thin TBC layer subject to spark ignition combustion heat flux. A CONVERGE 3D-CFD model was used to simulate the combustion process in a single-cylinder, light-duty experimental spark ignition (SI) engine. Transient piston heat transfer analysis was conducted using ABAQUS, a FEA package, under the simulated combustion heat flux load. The effect of the temperature swing phenomenon due to this TBC layer was observed in a CFD simulation by implementing the FEA results as the piston thermal boundary conditions. The boundary conditions were passed between the CFD and FEA tools until a quasi-steady state solution was achieved. Furthermore, a reduction in wall heat transfer was observed due to a reduced temperature difference between the wall and the working gas.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

On Road vs. Off Road Low Load Cycle Comparison

Reducing criteria pollutants while reducing greenhouse gases is an active area of research for commercial on-road vehicles as well as for off-road machines. The heavy duty on-road sector has moved to reducing NOx by 82.5% compared to 2010 regulations while increasing the engine useful life from 435,000 to 650,000 miles by 2027 in the United States (US). An additional certification cycle, the Low Load Cycle (LLC), has been added focusing on part load operation having tight NOx emissions levels. In addition to NOx, the total CO2 emissions from the vehicle will also be reduced for various model years. The off-road market is following with a 90% NOx reduction target compared to Tier 4 Final for 130-560 kW engines along with greenhouse gas targets that are still being established. The off-road market will also need to certify with a Low Load Application Cycle (LLAC), a version of which was proposed for evaluation in 2021. Since the LLAC has not been finalized, this study is being conducted to compare and contrast the LLC for on-road with the LLAC for off-road as there might be some shared learnings. A US off-road production 2023 Fiat Powertrain 13L engine and aftertreatment system was chosen for this work. This engine is used in production for both off-road and on-road products, so it is a good choice for this study. The associated off-road aftertreatment system was aged for more relevant comparisons. The engine calibration was not altered for either of the low load cycles. This study shows that the cycles are quite different in nature as the market needs are different. The LLC includes a large fraction of operation at idle and lower speeds, representing products that use the engine primarily for motive power, where lower vehicle speed means a lower engine speed and load. The LLAC has more time and load spent at high speeds and slightly higher loads. The off-road products represented by this cycle often use the engine to drive auxiliary equipment which means higher parasitic loads and hand/fixed throttle. The comparison will include the use profiles, tailpipe NOx and greenhouse gas emissions (CO2, N2O).

McCarthy, James↗

First direct measurement of 59 Cu(p,α) 56 Ni: A step towards constraining the Ni-Cu cycle in the cosmos

Reactions on proton-rich nuclides drive the nucleosynthesis in core collapse supernovae (CCSNe) and in x-ray bursts (XRBs). CCSNe eject the nucleosynthesis products to the interstellar medium and hence are a potential inventory of p nuclei, whereas in XRBs nucleosynthesis powers the light curves. In both astrophysical sites the Ni-Cu cycle, which features a competition between 59 Cu(p,α) 56 Ni and 59 Cu(p,γ) 60 Zn, could potentially halt the production of heavier elements. Here, we report the first direct measurement of 59 Cu(p,α) 56 Ni using a reaccelerated 59Cu beam and a cryogenic solid hydrogen target. Furthermore, our results show that the reaction proceeds predominantly to the ground state of 56 Ni, and the experimental rate has been found to be lower than Hauser-Feshbach based statistical model predictions. New results hints that the νp process could operate at higher temperatures than previously inferred and therefore remains a viable site for synthesizing the heavier elements

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

A formal Fe III/V redox couple in an intercalation electrode

Iron redox cycling between low-valent oxidation states of Fe II and Fe III drives crucial processes in nature. The Fe II/III redox couple charge compensates the cycling of lithium iron phosphate, a positive electrode (cathode) for lithium-ion batteries. High-valent iron redox couples, involving formal oxidation higher than Fe III , could deliver higher electrochemical potentials and energy densities. However, because of the instability of high-valent Fe electrodes, they have proven difficult to probe and exploit in intercalation systems. Here, in this study, we report and characterize a formal Fe III/V redox couple by revisiting the charge compensation mechanism of (de)lithiation in Li 4 FeSbO 6 . Valence-sensitive experimental and computational core-level spectroscopy reveal a direct transition from Fe III (3d 5 ) to a negative-charge-transfer FeV (3d 5 L 2 ) ground state on delithiation, without forming Fe IV , or oxygen dimers. We identify that the cation ordering in Li 4 FeSbO 6 drives a templated phase transition to stabilize the unique Fe V species and demonstrate that disrupting cation ordering suppresses the Fe III/V redox couple. Exhibiting resistance to calendar aging, high operating potential and low voltage hysteresis, the Fe III/V redox couple in Li 4 FeSbO 6 provides a framework for developing sustainable, Fe-based intercalation cathodes for high-voltage applications.

Ramachandran, Hari [Stanford Univ., CA (United Sta↗

Quantifying the Influence of Jupiter on the Earth’s Orbital Cycles

A wealth of Earth-sized exoplanets will be discovered in the coming years, providing a large pool of candidates from which the targets for the search for life beyond the solar system will be chosen. The target selection process will require the leveraging of all available information in order to maximize the robustness of the target list and make the most productive use of follow-up resources. Here, we present the results of a suite of n-body simulations that demonstrate the degree to which the orbital architecture of the solar system impacts the variability of Earth’s orbital elements. By varying the orbit of Jupiter and keeping the initial orbits of the other planets constant, we demonstrate how subtle changes in solar system architecture could alter the Earth’s orbital evolution—a key factor in the Milankovitch cycles that alter the amount and distribution of solar insolation, thereby driving periodic climate change on our planet. The amplitudes and frequencies of Earth’s modern orbital cycles fall in the middle of the range seen in our runs for all parameters considered—neither unusually fast nor slow, neither large nor small. This finding runs counter to the “Rare Earth” hypothesis, which suggests that conditions on Earth are so unusual that life elsewhere is essentially impossible. Our results highlight how dynamical simulations of newly discovered exoplanetary systems could be used as an additional means to assess the potential targets of biosignature searches, and thereby help focus the search for life to the most promising targets.

79 ASTRONOMY AND ASTROPHYSICS↗

Tritium Producing Burnable Absorber Rod (TPBAR) Cutterhead Test Report

The Tritium Extraction Facility (TEF) Target Rod Preparation (TRP) Tritium Producing Burnable Absorber Rod (TPBAR) Cutterhead is a specialized remote tubing cutter used to breach TPBARs (approximately 0.381 inch outside diameter x 0.336 inch inside diameter 316 stainless steel tubing). The cutterhead was originally designed by an external engineering firm - RTS Wright Industries. The bearing housing and drive plate, the main drive components, are designed to be fabricated from Nitronic 60, an anti-galling stainless steel, and coated with Dicronite® (Tungsten Disulfide) lubricating coating. These parts have galled after a limited number of cycles, damaging the fine 3.25-32 UN threads which drive the system. In some cases, destructive sectioning is required to remove the failed parts from the cutterhead. Cutterheads have been fabricated by multiple machine shops, with some cutterheads failing very quickly and some lasting more than 1,000 cuts. In 2019, Emery Corporation, now Toner Machining Technologies (TMT) was contracted to fabricate four (4) new complete sets of cutterheads. The newly fabricated cutterheads have not been able to pass the required acceptance test without the bearing housing and drive plate threads galling. TMT has tried multiple sets of Nitronic 60 bearing housing and drive plates; all have galled after less than 10 cuts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Integrated Pumped Thermal and Liquid Air Energy Storage

Liquid air energy storage (LAES) and pumped thermal energy storage (PTES) are two closely related technologies that employ thermodynamic cycles to store electricity in the form of thermal energy. This chapter describes the integration of PTES and LAES in a single combined cycle (PT-LAES), where the PTES side provides the cold source required to drive the air liquefaction process. This presents several advantages compared to the separate cycles, including the partial or complete removal of cold stores, a higher energy density and the achievement of full air liquefaction. Notably, PT-LAES does not depend on external sources of heat or cold and thus constitutes a stand-alone system. As a result, PT-LAES can also be viewed as an advanced LAES cycle with full liquefaction.

Carnot batteries↗

Deletion of Re -citrate synthase allows for analysis of contributions of tricarboxylic acid cycle directionality to the growth of Heliomicrobium modesticaldum

ABSTRACT Heliomicrobium modesticaldum,a phototrophic member of the phylum Firmicutes and family Clostridiales, possesses most of the enzymes specific to the reductive tricarboxylic acid (rTCA) cycle, except for the key enzyme, ATP-citrate lyase. It is thought to utilize a split TCA cycle when growing on pyruvate as a carbon source, in which the oxidative TCA (oTCA) direction generates most of the 2-ketoglutarate, but some can be produced in the reductive direction. Although a typicalSi-citrate synthase gene is not found in the genome, it was suggested that gene HM1_2993, annotated as homocitrate synthase, actually encodesRe-citrate synthase, which would function as the initial enzyme of the oTCA cycle. We deleted this gene to test this hypothesis and, if true, see what effect severing access to the oTCA cycle would have on this organism. The endogenous CRISPR-Cas system was used to replace the open reading frame with a selectable marker. The deletion mutants could grow on pyruvate but were unable to grow phototrophically on acetate + CO 2 as carbon source. Growth on acetate could be rescued by the addition of different electron sources (formate or ascorbate), suggesting that the oTCA cycle is used to oxidize acetate to generate electrons required to drive the carboxylation of acetyl-CoA. The deletion mutants were capable of growing in acetate minimal media without additional organic supplements beyond formate, demonstrating that the rTCA cycle can be employed to support sufficient 2-ketoglutarate production in this organism, unlike citrate synthase mutants in several chemoheterotrophic organisms utilizing the oTCA cycle. IMPORTANCE Heliobacteria are a unique group of phototrophic bacteria that are obligate anaerobes and possess a rudimentary system to use light as a source of energy. They do not make oxygen or fix carbon dioxide. Here, we explore their fundamental carbon metabolism to understand the role and operation of the central TCA cycle. This work shows both the role and operation of this cycle under different growth modes and explains how these organisms can obtain electrons to drive their biosynthetic metabolism. This foundational knowledge will be crucial in the future when attempts are made to use this organism as a platform for oxygen-sensitive synthesis of compounds in an anaerobe that can use light as its energy source.

Biotechnology & Applied Microbiology↗

Diverse Thaumarchaeota Dominate Subsurface Ammonia-oxidizing Communities in Semi-arid Floodplains in the Western United States

Subsurface microbial communities mediate biogeochemical transformations that drive both local and ecosystem-level cycling of essential elements, including nitrogen. However, their study has been largely limited to the deep ocean, terrestrial mines, caves, and topsoils (< 30 cm). Here, we present regional insights into the microbial ecology of aerobic ammonia oxidation within the terrestrial subsurface of five semi-arid riparian sites spanning a 900-km N-S transect. We sampled sediments, profiled communities to depths of ≤10 m, and compared them to reveal trends regionally within and surrounding the Upper Colorado River Basin (CRB). The diversity and abundance of ammonia-oxidizing microbial communities were evaluated in the context of subsurface geochemistry by applying a combination of amoA (encoding ammonia monooxygenase subunit A) gene sequencing, quantitative PCR, and geochemical techniques. Analysis of 898 amoA sequences from ammonia-oxidizing archaea (AOA) and bacteria (AOB) revealed extensive ecosystem-scale diversity, including archaeal amoA sequences from four of the five major AOA lineages currently found worldwide as well as distinct AOA ecotypes associated with naturally reduced zones (NRZs) and hydrogeochemical zones (unsaturated, capillary fringe, and saturated). Overall, AOA outnumber AOB by 2- to 5000-fold over this regional scale, suggesting that AOA may play a prominent biogeochemical role in nitrification within terrestrial subsurface sediments.

54 ENVIRONMENTAL SCIENCES↗

Comparative study of two Saccharomyces cerevisiae strains with kinetic models at genome-scale

The parameterization of kinetic models requires measurement of fluxes and/or metabolite levels for a base strain and a few genetic perturbations thereof. Unlike stoichiometric models that are mostly invariant to the specific strain, it remains unclear whether kinetic models constructed for different strains of the same species have similar or significantly different kinetic parameters. This important question underpins the applicability range and prediction limits of kinetic reconstructions. To this end, herein we parameterize two separate large-scale kinetic models using K-FIT with genome-wide coverage corresponding to two distinct strains of Saccharomyces cerevisiae: CEN.PK 113-7D strain (model k-sacce306-CENPK), and growth-deficient BY4741 (isogenic to S288c; model k-sacce306-BY4741). The metabolic network for each model contains 306 reactions, 230 metabolites, and 119 substrate-level regulatory interactions. The two models (for CEN.PK and BY4741) recapitulate, within one standard deviation, 77% and 75% of the fitted dataset fluxes, respectively, determined by 13 C metabolic flux analysis for wild-type and eight single-gene knockout mutants of each strain. Strain-specific kinetic parameterization results indicate that key enzymes in the TCA cycle, glycolysis, and arginine and proline metabolism drive the metabolic differences between these two strains of S. cerevisiae. Our results suggest that although kinetic models cannot be readily used across strains as stoichiometric models, they can capture species-specific information through the kinetic parameterization process.

59 BASIC BIOLOGICAL SCIENCES↗

Static adhesion hysteresis in elastic structures

Adhesive interactions between elastic structures such as graphene sheets, carbon nanotubes, and microtubules have been shown to exhibit hysteresis due to irrecoverable energy loss associated with bond breakage, even in static (rate-independent) experiments. To understand this phenomenon, we start with a minimal theory for the peeling of a thin sheet from a substrate, coupling the local event of bond breaking to the nonlocal elastic relaxation of the sheet and show that this can drive static adhesion hysteresis over a bonding/debonding cycle. Using this model we quantify hysteresis in terms of the adhesion and elasticity parameters of the system. We find that this allows us to derive a scaling relation that preserves hysteresis at different levels of granularity while resolving a seeming paradox of lattice trapping in the continuum limit of a discrete fracture process. Finally, to verify our theory, we use new experiments to demonstrate and measure adhesion hysteresis in bundled microtubules.

36 MATERIALS SCIENCE↗

Real-Time Inventory Change Detection for the Protactinium Decay Inventory of the Molten Salt Breeder Reactor

This work presents a novel monitoring method for detecting material loss from the decay inventory of the molten salt breeder reactor (MSBR) by monitoring for changes to the system dynamics using an isotopic ratio. Here the isotopic masses in the decay inventory of a MSBR were simulated under several material loss scenarios. In each case, the ratio of 231 Pa to 233 Pa served as a sensitive and lasting indicator of material loss. This isotope ratio quickly decreased outside the normal range after a material loss, and the ratio remained depressed for several years after the loss. The dynamics of this ratio were driven by the periodic batch discard from the decay inventory every 220 days, which was specified in the MSBR design to periodically remove fission product buildup. For this method, isotopic ratios were found to be rapid and enduring indicators of inventory change if they comprise a pair with a short half-life (e.g., 233 Pa) and a long half-life (e.g., 231 Pa) relative to the effective half-life induced by the driving system process (e.g., the batch discard cycle). Using such an isotope pair enabled a method to monitor for changes to the effective half-life of the system and by extension changes to the system inputs and outputs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

High-throughput mapping of the phage resistance landscape in E. coli

Bacteriophages (phages) are critical players in the dynamics and function of microbial communities and drive processes as diverse as global biogeochemical cycles and human health. Phages tend to be predators finely tuned to attack specific hosts, even down to the strain level, which in turn defend themselves using an array of mechanisms. However, to date, efforts to rapidly and comprehensively identify bacterial host factors important in phage infection and resistance have yet to be fully realized. Here, we globally map the host genetic determinants involved in resistance to 14 phylogenetically diverse double-stranded DNA phages using two model Escherichia coli strains (K-12 and BL21) with known sequence divergence to demonstrate strain-specific differences. Using genome-wide loss-of-function and gain-of-function genetic technologies, we are able to confirm previously described phage receptors as well as uncover a number of previously unknown host factors that confer resistance to one or more of these phages. We uncover differences in resistance factors that strongly align with the susceptibility of K-12 and BL21 to specific phage. We also identify both phage specific mechanisms, such as the unexpected role of cyclic-di-GMP in host sensitivity to phage N4, and more generic defenses, such as the overproduction of colanic acid capsular polysaccharide that defends against a wide array of phages. Our results indicate that host responses to phages can occur via diverse cellular mechanisms. Our systematic and high-throughput genetic workflow to characterize phage-host interaction determinants can be extended to diverse bacteria to generate datasets that allow predictive models of how phage-mediated selection will shape bacterial phenotype and evolution. The results of this study and future efforts to map the phage resistance landscape will lead to new insights into the coevolution of hosts and their phage, which can ultimately be used to design better phage therapeutic treatments and tools for precision microbiome engineering.

59 BASIC BIOLOGICAL SCIENCES↗