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At least 919 records · Page 51

Integration of Omics into a New Comprehensive Rate Law for Competitive Terminal Electron-Accepting Processes in Reactive Transport Models: Application to N, Fe, S, and Contaminant Transformations in Stream and Wetland Sediments

Surface waters represent important sources of alternate energy and drinking water in the United States, and characterizing the biogeochemical processes that affect surface water quality is relevant to the DOE-BER mission. Sediment biogeochemical processes regulate the release of carbon (C), nutrients, and contaminants to surface waters and thus influence water quality. Sediment biogeochemical processes are dynamic and affected by the deposition and remobilization of solid material and changes in environmental conditions driven by water discharge variations. Wetlands are important natural filters of surface waters which may either trap, metabolize, or mobilize nutrients and contaminants. Despite their importance, biogeochemical processes regulating nutrient and contaminant release and C transformation in stream and wetland sediments cannot be predicted accurately by current mathematical models. These reactive transport models largely rely on detectable changes in geochemical conditions to activate metabolic processes, do not accurately account for the competition between microbial processes, and poorly constrain effects of hydrological perturbations on biogeochemical processes. In this BER-SBR exploratory project, metagenomic and geochemical signatures were combined to identify microbially-mediated redox processes in anaerobic stream and wetland sediments from the Savannah River Site (SRS, ANL SFA) and East Fork Poplar Creek (EFPC, ORNL SFA) that play important roles in C, uranium (U), and mercury (Hg) transformations. In addition, sediment incubations were conducted to examine the competition between anaerobic respiration processes Finally, new rate laws were developed for reactive transport models that rely on complementary metagenomic and geochemical signatures to identify the underlying anaerobic microbial processes in stream and wetland sediments, describe the competition between the dominant metabolic processes involved in nutrient release and U and Hg mobilization, and more accurately quantify carbon transformation and the response of microbial processes to changes in redox conditions associated with hydrological forcing. These rate laws were optimized in batch reactors with SRS wetland sediments, where iron and sulfate reduction dominate. Anaerobic carbon remineralization processes followed the expected thermodynamic sequence of microbial respiration with depth in both sediments, except that geochemical signals indicated that sulfate reduction was inactive in EFPC sediments and moderate in SRS wetland sediments. Estimates indicated that microbial iron reduction contributed to at least half of the production of reduced iron in these sediments. Incubations demonstrated that nitrate reduction, denitrification, and dissimilatory nitrate reduction to ammonium were active in the natural EFPC sediment and activated upon nitrate amendment in these nitrate-rich sediments. In turn, these processes were outcompeted by the addition of either iron oxides or sulfate as alternative terminal electron acceptors. Although geochemical products of sulfate reduction were not detected in the incubations, the abundance of sulfate reduction genes increased with depth in the sediment and was equally more pronounced in treatments amended with either iron oxides or sulfate. Simultaneously, anaerobic sulfide oxidizing bacteria coupling sulfide oxidation to DNRA (and not conventional denitrification) were apparently enriched over time, regardless of the treatments. These findings indicate that sulfate reduction is important in freshwater stream sediments and probably catalyzed by a cryptic sulfur cycle involving nitrogen species, in which the sulfur products from sulfate reduction are immediately removed by side reactions and not detectable by geochemical measurements alone. Similar experiments in SRS sediments, however, demonstrated little interaction between nitrogen and sulfur cycling microorganisms. Sulfate reduction was impacted by the addition of more thermodynamically favorable electron acceptors, suggesting either that iron-reducing microorganisms outcompeted sulfate-reducing microorganisms for organic substrate, depleting the stock of electron donor available for sulfate reduction, or that the cryptic sulfur cycle was shunted by the precipitation of FeS generated as a result of the abiotic reduction of iron oxides by dissolved sulfide. A diagnostic modeling exercise was conducted to further investigate the competition between terminal electron accepting processes. As conventional kinetic models typically do not account for cryptic cycles and used inaccurate formulations to describe competition between microbial communities, new metabolic rate laws were developed that explicitly express the electron acceptor-specific enzyme of each energetically favorable metabolic process based on gene abundance detected in the incubations. The model was tested with the sediment slurry incubation data to determine whether substrate competition could explain the decrease in sulfate reduction observed in the presence of iron oxide competitor. The model was able to reproduce geochemical concentrations really well in each treatment once the model was calibrated with the unamended control, suggesting that microbial competition was indeed driven by thermodynamic considerations. Overall, carbon remineralization processes and rates will be reproduced much more realistically with the new metabolic rate laws.

54 ENVIRONMENTAL SCIENCES↗

Heating and ablation of high- Z cryogenic pellets in high temperature plasmas

A kinetic model is developed here to determine the power deposition from energetic electrons into the neutral gas shield of an ablating high-Z pellet. For high-Z, the velocity distribution of the hot electrons is nearly isotropic, and we use this feature to develop solutions to the kinetic equation. In contrast to pre-existing models, we consider the effect of gyro-motion as well as elastic scattering of the hot electrons. Two limits are considered: when the gyro-frequency is much greater than the elastic collision frequency, the hot electrons diffuse longitudinally along the field lines as they slow down; but if the gyro-frequency is much less than the elastic collision frequency, the hot electrons diffuse radially. In both limits, it is possible to express the kinetic equation describing the hot electrons independently of the gas density profile, and therefore, the power deposition model is universal in this respect. The emphasis on elastic scattering yields an ablation rate which scales as Z -7/6 which is different than Z -2/3 shown in Sergeev et al (2006 Plasma Phys. Rep. 32 5). It is also demonstrated that the sheath potential required to maintain ambipolarity in the cloud scales as Z -1/3 . Fluid simulations yield ablation rates that scale with the four-thirds power of the pellet radius in agreement with [2].

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Rate-equation modelling and ensemble approach to extraction of parameters for viral infection-induced cell apoptosis and necrosis

We develop a theoretical approach that uses physiochemical kinetics modelling to describe cell population dynamics upon progression of viral infection in cell culture, which results in cell apoptosis (programmed cell death) and necrosis (direct cell death). Several model parameters necessary for computer simulation were determined by reviewing and analyzing available published experimental data. By comparing experimental data to computer modelling results, we identify the parameters that are the most sensitive to the measured system properties and allow for the best data fitting. Our model allows extraction of parameters from experimental data and also has predictive power. Using the model we describe interesting time-dependent quantities that were not directly measured in the experiment and identify correlations among the fitted parameter values. Numerical simulation of viral infection progression is done by a rate-equation approach resulting in a system of “stiff” equations, which are solved by using a novel variant of the stochastic ensemble modelling approach. The latter was originally developed for coupled chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulating Catalysis with Realistic Pellet Geometries Using Mesoflow: A Case Study of Catalytic Propane Dehydrogenation

We present a case study of catalytic propane dehydrogenation with our open-source multiphysics solver, Mesoflow. The solver was developed to simulate reactive flow coupled to heterogeneous catalytic reactions and deactivation in the context of complex, mesoscale geometry. The method leverages cartesian block-structured adaptive mesh refinement to capture realistic catalyst microstructural features acquired directly from X-ray computed tomography data. A kinetic model for propane dehydrogenation and catalyst deactivation was developed based on temporal analysis of products (TAP) reactor experiments. The TAP reactor experiments allow for precise characterization of intrinsic kinetic reaction steps which are implemented into Mesoflow simulations to model the spatial and temporal evolution of reactants, products, and catalyst active sites. The short-term and long-term deactivation behavior is studied by using XCT data collected from fresh and aged catalyst pellets, which exhibit different microstructural features. This study employs time-splitting algorithms to connect disparate reaction and flow timescales, enabling the simulations to achieve realistic deactivation timescales on the order of minutes while the flow time-scales for small particles (100 microns) are several milliseconds. We also introduce a flexible automated python script that writes the necessary files to construct a Mesoflow simulation from user-created chemical mechanisms. We will also introduce a few new features that are added to Mesoflow such as higher order schemes, implicit chemistry integrators and the ability to run on AMD and NVIDIA graphics-processing-units.

AMReX↗

Downstream Separation of Formic Acid with Anion-Exchange Resin from Electrocatalytic Carbon Dioxide (CO 2 ) Conversion: Adsorption, Kinetics, and Equilibrium Modeling

The electrocatalytic carbon dioxide reduction reaction (CO 2 RR) that produces liquid formic acid (FA) is one potential route to minimize the CO 2 concentration in the atmosphere by utilizing CO 2 as a feedstock. However, one of the main disadvantages of this route is the high energy demand required for purification through conventional distillation. This method of purification has been shown to result in a large carbon footprint in life-cycle analysis (LCA). Therefore, finding an alternative purification technique that can integrate with an electrochemical CO 2 RR process with the potential to lower the carbon footprint would be of great interest. Under the experimental conditions of the CO 2 RR, FA remains in its basic form as the formate anion in the catholyte. Anion exchange resins with their basic properties can separate the formate anion from the catholyte mixture as an alternative to energy intensive distillation. In this work, three anion exchange resins with increasing basicity order: Amberlite IRA-96 < Amberlite IRA-910 < Ambersep 900 are tested to separate FA in the presence of aqueous solution of potassium bicarbonate catholyte with varying levels of resin and FA. Kinetics and equilibrium studies data for the FA adsorption are interpreted using several kinetics and isotherm models. The kinetics data fit well with a pseudo-first-order model at high initial FA concentrations and a pseudo-second-order model at low initial FA concentrations. The experimental data can be best explained with the Freundlich isotherm model. The fitted results show that strongly basic Ambersep 900 is more effective at separating FA, with a maximum adsorption capacity of 336.7 mg/g compared to Amberlite IRA-96 (275.2 mg/g) and Amberlite IRA-910 (209.2 mg/g) in neutral water. However, weakly basic Amberlite IRA-96 (110.8 mg/g) can separate FA more efficiently from potassium bicarbonate catholyte than Amberlite IRA-910 (99.9 mg/g) and Ambersep 900 (40.0 mg/g). As a result, competitive adsorption occurs in the presence of potassium bicarbonate catholyte, but the formic acid adsorption capacity is still sufficient for adequate separation.

20 FOSSIL-FUELED POWER PLANTS↗

A Hamiltonian five-field gyrofluid model

A Lie-Poisson bracket is presented for a five-field gyrofluid model, thereby showing the model to be Hamiltonian. The model includes the effects of magnetic field curvature and describes the evolution of the electron and ion gyro-center densities, the parallel component of the ion and electron velocities, and the ion temperature. The quasineutrality property and Ampère's law determine, respectively, the electrostatic potential and magnetic flux. The Casimir invariants are presented, and shown to be associated with five Lagrangian invariants advected by distinct velocity fields. A linear, local study of the model is conducted both with and without Landau and diamagnetic resonant damping terms. Stability criteria and dispersion relations for the electrostatic and the electromagnetic cases are derived and compared with their analogs for fluid and kinetic models.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Modeling of inductively coupled plasma Ar/Cl{sub 2}/N{sub 2} plasma discharge: Effect of N{sub 2} on the plasma properties

A global kinetic model of Cl{sub 2}/Ar/N{sub 2} plasma discharge has been developed, which allows calculation of the densities and fluxes of all neutral and charged species considered in the reaction scheme, as well as the electron temperature, as a function of the operating conditions. In this work, the results from the global model are first compared to the calculations given by other models. Our simulation results are focused on the effect of nitrogen adding to the Cl{sub 2}/Ar plasma mixture, which impacts both neutral and charged species transport phenomena. The N{sub 2} percentage is varied to the detriment of Cl{sub 2} by keeping the total flow rates of Cl{sub 2} and N{sub 2} constant. In order to better understand the impact of N{sub 2} addition to the Cl{sub 2}/Ar gas mixture, the authors analyzed the output plasma parameters calculated from the model for different N{sub 2} flow rate percentages. Indeed, the simulation results show a decrease in electron density and an increase in electron temperature with increasing percentage of N{sub 2}. Particular attention is paid to the analysis of electronegativity, Cl{sub 2} and N{sub 2} dissociation, and positive ion to neutral flux ratio evolution by varying percentage of N{sub 2}. Such parameters have a direct effect on the etching anisotropy of the materials during the etching process.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Combining Computational Modeling with Reaction Kinetics Experiments for Elucidating the In Situ Nature of the Active Site in Catalysis

Microkinetic modeling based on density functional theory (DFT) derived energetics is important for addressing fundamental questions in catalysis. The quantitative fidelity of microkinetic models (MKMs), however, is often insufficient to conclusively infer the mechanistic details of a specific catalytic system. Here, this can be attributed to a number of factors such as an incorrect model of the active site for which DFT calculations are performed, deficiencies in the hypothesized reaction mechanism, inadequate consideration of the surface environment under reaction conditions, and intrinsic errors in the DFT exchange-correlation functional. Despite these limitations, we aim at developing a rigorous understanding of the reaction mechanism and of the nature of the active site for heterogeneous catalytic chemistries under reaction conditions. By achieving parity between experimental and modeling outcomes through robust parameter estimation and by ensuring coverage-consistency between DFT calculations and MKM predictions, it is possible to systematically refine the mechanistic model and, thereby, our understanding of the catalytic active site in situ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thin Water Films Enable Low-Temperature Magnesite Growth Under Conditions Relevant to Geologic Carbon Sequestration

Injecting supercritical CO2 (scCO2) into basalt formations for long-term storage is a promising strategy for mitigating CO2 emissions. Mineral carbonation can result in permanent entrapment of CO2; however, carbonation kinetics in thin H2O films in humidified scCO2 is not well understood. We investigated forsterite (Mg2SiO4) carbonation to magnesite (MgCO3) via amorphous magnesium carbonate (AMC; MgCO3·xH2O, 0.5 < x < 1), with the goal to establish the fundamental controls on magnesite growth rates at low H2O activity and temperature. Experiments were conducted at 25, 40, and 50 °C in 90 bar CO2 with a H2O film thickness on forsterite that averaged 1.78 ± 0.05 monolayers. In situ infrared spectroscopy was used to monitor forsterite dissolution and the growth of AMC, magnesite, and amorphous SiO2 as a function of time. Geochemical kinetic modeling showed that magnesite was supersaturated by two to three orders of magnitude and grew according to a zero-order rate law. The results indicate that the main drivers for magnesite growth are sustained high supersaturation coupled with low H2O activity, a combination of thermodynamic conditions not attainable in bulk aqueous solution. This improved understanding of reaction kinetics can inform subsurface reactive transport models for better predictions of CO2 fate and transport.

Kerisit, Sebastien N.↗

A portalino to the dark sector

“Portal” models that connect the Standard Model to a Dark Sector allow for a wide variety of scenarios beyond the simplest WIMP models. Kinetic mixing of gauge fields in particular has allowed a broad range of new ideas. However, the models that evade CMB constraints are often non-generic, with new mass scales and operators to split states and suppress indirect detection signals. Models with a “portalino”, a neutral fermion that marries a linear combination of a standard model neutrino and dark sector fermion and carries a conserved quantum number, can be simpler. This is especially interesting for interacting dark sectors; then the unmarried linear combination which we identify as the standard model neutrino inherits these interactions too, and provides a new, effective interaction between the dark sector and the standard model. These interactions can be simple Z' type interactions or lepton-flavor changing. Dark matter freezes out into neutrinos, thereby evading CMB constraints, and conventional direct detection signals are largely absent. The model offers different signals, however. The “portalino” mechanism itself predicts small corrections to the standard model neutrino couplings as well as the possibility of discovering the portalino particle in collider experiments. Possible cosmological and astroparticle signatures include monochromatic neutrino signals from annihilation, spectral features in high energy CR neutrinos as well as conventional signals of additional light species and dark matter interactions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Runaway electron seed formation at reactor-relevant temperature

Systematic variation of the pre-disruption core electron temperature (T e ) from 1 to 12 keV using an internal transport barrier scenario reveals a dramatic increase in the production of ‘seed’ runaway electrons (REs), ultimately accessing near-complete conversion of the pre-disruption current into sub-MeV RE current. Injected Ar pellets are observed to ablate more intensely and promptly as T e rises. At high T e , the observed ablation exceeds predictions from published thermal ablation models. Simultaneously, the thermal quench (TQ) is observed to significantly shorten with increasing T e —a surprising result. While the reason for the shorter TQ is not yet understood, candidate mechanisms include: insufficiently accurate thermal ablation models, enhanced ablation driven by the seed RE population, or significant parallel heat transport along stochastic fields. Kinetic modeling that self-consistently treats the plasma cooling via radiation, the induced electric field, and the formation of the seed RE is performed. Including the combined effect of the inherent dependence of hot-tail RE seeding on T e together with the shortened TQ, modeling recovers the progression towards near-complete conversion of the pre-disruption current to RE current as T e rises. Measurement of the HXR spectrum during the early current quench (CQ) reveals a trend of decreasing energy with pre-disruption T e . At the very highest T e (≈ 12 keV), ≈ 100% conversion of the thermal current to runaway current is found. The energy of this peculiar RE beam is inferred to be sub-MeV as it emits vanishingly few MeV hard x-rays (HXRs). These measurements demonstrate novel TQ dynamics as Te is varied and illustrate the limitations of treating the RE seed formation problem without considering the inter-related dependencies of the pellet ablation, radiative energy loss, and resultant variations of the TQ duration. Finally, if the observed shortening of the TQ with increasing T e extends to fusion-grade plasmas, than their propensity to form large quantities of RE seeds at high T e may be far worse than previously thought. Positively, the high T e scenario in DIII-D produces REs so prodigiously that it can serve as a meaningful new platform for demonstrating RE avoidance techniques.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

cDF Theory Software for mesoscopic modeling of equilibrium and transport phenomena

The approach is based on classical Density Functional Theory (cDFT) coupled with the Poisson-Nernst-Planck (PNP) transport kinetics model and quantum mechanical description of short-range interaction and elementary transport processes. The model we proposed and implemented is fully atomistic, taking into account pairwise short-range and manybody long-range interactions. But in contrast to standard molecular dynamics (MD) simulations, where long-range manybody interactions are evaluated as a sum of pair-wise atom-atom contributions, we include them analytically based on well-established theories of electrostatic and excluded volume interactions in multicomponent systems. This feature of the PNP/cDFT approach allows us to reach well beyond the length-scales accessible to MD simulations, while retaining the essential physics of interatomic interactions from first principles and in a parameter-free fashion.

Sushko, Maria↗

Efficient multistep arsenate removal onto magnetite modified fly ash

The modification of the fly ash (FA) by magnetite (M) was performed to obtain FAM adsorbent with improved adsorption efficiency for arsenate removal from water. The novel low cost adsorbents are characterized by liquid nitrogen porosimetry (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), Mössbauer spectroscopy (MB) and Fourier transform infrared (FTIR) spectroscopy. The optimal conditions and key factors influencing the adsorbent synthesis are assessed using the response surface method (RSM). The adsorption experiment was carried out in a batch system by varying the contact time, temperature, pH, and mass of the adsorbent. The adsorption capacity of the FAM adsorbent for As(V), calculated by Langmuir model, was 19.14 mg g−1. The thermodynamic parameters showed spontaneity of adsorption with low endothermic character. The kinetic data followed the pseudo-second-order kinetic model (PSO), and Weber-Morris model indicated intra-particle diffusion as rate limiting step. Alternative to low desorption capability of the FAM was found by five consecutive adsorption/magnetite precipitation processes which gave exhausted layered adsorbent with 65.78 mg g−1 capacity. This research also has shed light on the mechanism of As(V)-ion adsorption, presenting a promising solution for the valorization of a widely abundant industrial waste. © 2018 Elsevier Ltd.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active microbial biomass decreases, but microbial growth potential remains similar across soil depth profiles under deeply-vs. shallow-rooted plants

Climate-smart land management practices that replace shallow-rooted annual crop systems with deeply-rooted perennial plants can contribute to soil carbon sequestration. However, deep soil carbon accrual may be influenced by active microbial biomass and their capacity to assimilate fresh carbon at depth. Incorporating active microbial biomass, dormancy, and growth in microbially-explicit models can improve our ability to predict soil's capacity to store carbon. But, so far, the microbial parameters that are needed for such modeling are poorly constrained, especially in deep soil layers. Here, we used a lab incubation experiment and growth kinetics model to estimate how microbial parameters vary along 240 cm of soil depth in profiles under shallow- (soy) and deeply-rooted (switchgrass) plants 11 years after plant cover conversion. We also assessed resource origin and availability (total organic carbon, 14 C, extractable organic carbon, specific UV absorbance of K 2 SO 4 extractable organic C, total nitrogen, total dissolved nitrogen) along the soil profiles to examine associations between soil chemical and biological parameters. Even though root biomass was greater and rooting depth was deeper under switchgrass than soy, resource availability and microbial growth parameters were generally similar between vegetation types. Instead, depth significantly influenced soil chemical and biological parameters. For example, resource availability and total and relative active microbial biomass decreased with soil depth. Decreases in the relative active microbial biomass coincided with increased lag time (response time to external carbon inputs) along the soil profiles. Even at a depth of 210–240 cm, microbial communities were activated to grow by added resources within a day. Maximum specific growth rate decreased to a depth of 90 cm and then remained consistent in deeper layers. Our findings show that >10 years of vegetation and rooting depth changes may not be long enough to alter microbial growth parameters, and suggest that at least a portion of the microbial community in deep soils can grow rapidly in response to added resources. Our study determined microbial growth parameters that can be used in microbially-explicit models to simulate carbon dynamics in deep soil layers.

14C↗

Validation of anisotropic electron fluid closure through in situ spacecraft observations of magnetic reconnection

A valid fluid model for electrons in collisionless space plasmas is desirable for understanding the structure and evolution of magnetic reconnection geometries. Additionally, such a fluid model would be useful for the simulation of systems too large to be tractable in a fully-kinetic model. Using MMS spacecraft observations, we provide direct confirmation of the Le 2009 equations of state for the electron pressure tensor during guide field reconnection and demonstrate how the closure can be applied in efficient numerical simulation, yielding new physical insight to the electron heating problem. Furthermore, we use the Le 2009 equations of state to predict a scaling of electron heating in the exhaust comparable to the available observational data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Reactivity Feedback Modeling in SAM

System Analysis Module (SAM) is being developed at Argonne National Laboratory as a modern system-level modeling and simulation tool for advanced non-light water reactor safety analyses. It utilizes the object-oriented application framework MOOSE to leverage the modern software environment and advanced numerical methods. The capabilities of SAM are being extended to enable the transient modeling, analysis, and design of various advanced nuclear reactor systems. This report presents the development of Point-Kinetics modeling and reactivity feedback mechanisms in SAM. It also presents a new capability for predicting the thermal expansion in various structural components by coupling SAM with an external thermomechanics module (Tensor Mechanics) from the MOOSE framework.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

A Predictive Transient Model of the TREAT-SIRIUS Experiments

To support experiments modeling and transient analysis of the NASA-sponsored SIRIUS experiments in the Transient Reactor Test Facility (TREAT), an innovative predictive transient model has been developed to simulate various transient experiments. The developed model is based on a new approach that utilizes steady-state Monte Carlo calculations along with a surrogate model based on polynomial regression to determine the core reactivity. The reactivity is supplied to an exact point kinetics model that determines the reactor power, and it is coupled to an adiabatic feedback model to determine the fuel average temperature. In this work, the newly developed model is introduced along with validation test results considering SIRIUS-1 experiments at different power levels. The initial test results show a very good agreement with experimental data at different power levels, which indicates that the model can be used to predict the power of other transient tests.

42 ENGINEERING↗