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At least 1,351 records · Page 75

Simplified jet fuel reaction mechanism for lean burn combustion application

Successful modeling of combustion and emissions in gas turbine engine combustors requires an adequate description of the reaction mechanism. Detailed mechanisms contain a large number of chemical species participating simultaneously in many elementary kinetic steps. Current computational fluid dynamic models must include fuel vaporization, fuel-air mixing, chemical reactions, and complicated boundary geometries. A five-step Jet-A fuel mechanism which involves pyrolysis and subsequent oxidation of paraffin and aromatic compounds is presented. This mechanism is verified by comparing with Jet-A fuel ignition delay time experimental data, and species concentrations obtained from flametube experiments. This five-step mechanism appears to be better than the current one- and two-step mechanisms.

Lee, Chi-Ming↗

Nonlinear triggered lightning models for use in finite difference calculations

Two nonlinear triggered lightning models have been developed for use in finite difference calculations. Both are based on three species of air chemistry physics and couple nonlinearly calculated air conductivity to Maxwell's equations. The first model is suitable for use in three-dimensional modeling and has been applied to the analysis of triggered lightning on the NASA F106B Thunderstorm Research Aircraft. The model calculates number densities of positive ions, negative ions, and electrons as a function of time and space through continuity equations, including convective derivative terms. The set of equations is closed by using experimentally determined mobilities, and the mobilities are also used to determine the air conductivity. Results from the model's application to the F106B are shown. The second model is two-dimensional and incorporates an enhanced air chemistry formulation. Momentum conservation equations replace the mobility assumption of the first model. Energy conservation equations for neutrals, heavy ions, and electrons are also used. Energy transfer into molecular vibrational modes is accounted for. The purpose for the enhanced model is to include the effects of temperature into the air breakdown, a necessary step if the model is to simulate more than the very earliest stages of breakdown. Therefore, the model also incorporates a temperature-dependent electron avalanche rate. Results from the model's application to breakdown around a conducting ellipsoid placed in an electric field are shown.

Rudolph, Terence↗

Interspecific variation in the timing and magnitude of hydraulic redistribution in a forest with distinct water sources

Trees regulate water availability among their rooting strata through a nocturnal, passive transference of water known as hydraulic redistribution (HR). This study investigates differences in HR and groundwater use among common canopy species in longleaf pine (Pinus palustris Mill., Pinaceae) woodlands and explores environmental factors influencing HR. HR was estimated by sap flux of lateral roots and main stems of three mature canopy species (P. palustris, Quercus laevis Walter., Fagaceae and Quercus margarettae Ashe., Fagaceae). We used δ18O and δD of xylem water, soil water, and groundwater to determine water source. Finally, we related HR to environmental factors (Temperature, VWC, VPD) to better understand controls of HR dynamics. Pinus palustris had higher water use than either Quercus species, and also redistributed significantly more water as a nocturnal subsidy. HR fluxes were inversely related with mean nightly temperature and independent of shallow soil moisture. Stable isotope mixing models, based on δ 18 O and δD, indicated that all species have access to groundwater, but utilized shallow soil water in differing amounts when available. In systems with strong water potential gradients among soil strata, any species with access to a groundwater source is likely capable of HR; however, the magnitude of HR varies significantly by species, even among closely related taxa.

54 ENVIRONMENTAL SCIENCES↗

Arctic Tropospheric Ozone: Assessment of Current Knowledge and Model Performance

As the third most important greenhouse gas (GHG) after carbon dioxide (CO2) and methane (CH4), tropospheric ozone (O3) is also an air pollutant causing damage to human health and ecosystems. This study brings together recent research on observations and modeling of tropospheric O3 in the Arctic, a rapidly warming and sensitive environment. At different locations in the Arctic, the observed surface O3 seasonal cycles are quite different. Coastal Arctic locations, for example, have a minimum in the springtime due to O3 depletion events resulting from surface bromine chemistry. In contrast, other Arctic locations have a maximum in the spring. The 12 state-of-the-art models used in this study lack the surface halogen chemistry needed to simulate coastal Arctic surface O3 depletion in the springtime; however, the multi-model median (MMM) has accurate seasonal cycles at non-coastal Arctic locations. There is a large amount of variability among models, which has been previously reported, and we show that there continues to be no convergence among models or improved accuracy in simulating tropospheric O3 and its precursor species. The MMM underestimates Arctic surface O3 by 5 % to 15 % depending on the location. The vertical distribution of tropospheric O3 is studied from recent ozonesonde measurements and the models. The models are highly variable, simulating free-tropospheric O3 within a range of ±50 % depending on the model and the altitude. The MMM performs best, within ±8 % for most locations and seasons. However, nearly all models overestimate O3 near the tropopause (∼300 hPa or ∼8 km), likely due to ongoing issues with underestimating the altitude of the tropopause and excessive downward transport of stratospheric O3 at high latitudes. For example, the MMM is biased high by about 20 % at Eureka. Observed and simulated O3 precursors (CO, NOx, and reservoir PAN) are evaluated throughout the troposphere. Models underestimate wintertime CO everywhere, likely due to a combination of underestimating CO emissions and possibly overestimating OH. Throughout the vertical profile (compared to aircraft measurements), the MMM underestimates both CO and NOx but overestimates PAN. Perhaps as a result of competing deficiencies, the MMM O3 matches the observed O3 reasonably well. Our findings suggest that despite model updates over the last decade, model results are as highly variable as ever and have not increased in accuracy for representing Arctic tropospheric O3.

Arctic↗

A general theory of avian migratory connectivity

Birds exhibit a remarkable array of seasonal migrations. Despite much research describing migratory behaviour, the underlying forces driving how a species’ breeding and wintering populations redistribute each year, that is, migratory connectivity, remain largely unknown. Here, we test the hypothesis that birds migrate in a way that minimises energy expenditure while considering intraspecific competition for energy acquisition, by developing a modelling framework that simulates an optimal redistribution of individuals between breeding and wintering areas. Using 25 species across the Americas, we find that the model accurately predicts empirical migration patterns, and thus offers a general explanation for migratory connectivity based on first ecological and energetic principles. Our model provides a strong basis for exploring additional processes underlying the ecology and evolution of migration, but also a framework for predicting how migration impacts local adaptation across seasons and how environmental change may affect population dynamics in migratory species.

60 APPLIED LIFE SCIENCES↗

A probabilistic economic and environmental impact assessment of a cyanobacteria-based biorefinery

Microbial based biofuels represent a potential promising solution as an environmentally favorable transportation fuel. Cyanobacteria have many of the same advantages as microalgae: ability for rapid growth in otherwise non-arable regions, suitability for genetic engineering, and simple nutritional needs. Additionally, cyanobacteria can be engineered to secrete valuable co-products that can be harvested independent from the produced biomass. However, little work has been done to identify the processes and the economic and environmental impacts associated with a large-scale cyanobacteria-to-fuels facility. The present study is a concurrent techno-economic and life cycle assessment of a facility that generates fuels and methyl laurate, an oleochemical, from the cyanobacterial species Synechocystis sp. PCC 6803. Here, the biorefinery model includes all aspects of cultivation, separation of the secreted methyl laurate, biomass harvesting and fuel processing via hydrothermal liquefaction (HTL) of the dewatered biomass. The assessments leverage Monte Carlo analysis (MCA) to address uncertainty and variability inherent in the most significant input parameters, replacing them with probabilistic functions. For the facility configuration producing both fuels and the oleochemical co-product, the MCA average minimum fuel selling price (MFSP) is $\$2.47$ per decimeter (dm 3 ) or $\$9.34$ per gallon of gasoline equivalent (gge) with the corresponding average global warming potential determined to be 118 g CO 2 -eq-MJ -1 . The case producing only fuels results in an MCA average MFSP of $\$2.01$-(dm 3 ) -1 ($\$7.60$-gge -1 ) and an average environmental impact of 100 g CO 2 -eq-MJ -1 . These results are compared to static optimistic and conservative scenario analysis estimates, illustrating the over- and under-estimation of outcomes associated with non-stochastic methods. Suggested facility improvements include increases in pond productivity of both the biomass and methyl laurate oil production, as well as improvements to carbon utilization and bio-crude yield from HTL processing.

09 BIOMASS FUELS↗

Engineering microbial consortia with rationally designed cellular interactions

Synthetic microbial consortia represent a frontier of synthetic biology that promises versatile engineering of cellular functions. They are primarily developed through the design and construction of cellular interactions that coordinate individual dynamics and generate collective behaviors. Here we review recent advances in the engineering of synthetic communities through cellular-interaction programming. We first examine fundamental building blocks for intercellular communication and unidirectional positive and negative interactions. Here, we then recap the assembly of the building blocks for creating bidirectional interactions in two-species ecosystems, which is followed by the discussion of engineering toward complex communities with increasing species numbers, under spatial contexts, and via model-guided design. We conclude by summarizing major challenges and future opportunities of engineered microbial ecosystems.

42 ENGINEERING↗

Simulating combustion of a seven-component surrogate for a gasoline/ethanol blend including soot formation and comparison with experiments

Combustion of a seven-component surrogate for a research grade 87 octane gasoline mixed with 10% ethanol is investigated experimentally and numerically from the perspective of an isolated droplet burning under conditions that promote one-dimensional gas transport. The numerical analysis included a kinetic mechanism comprised of 398 species and 24,814 reactions and a soot model that accounted for nucleation, surface growth, coalescence/aggregation of soot particles, and luminous flame radiation. Measurements of droplet and flame diameters were made for an initial droplet diameter (D o ) of approximately 0.63 mm. The simulations agreed well with the measurements including the location of the soot shell. Preferential vaporization was revealed by simulations of the liquid concentrations in the droplet. Predicted peak soot volume fractions coincided with temperatures between 1300 K and 1400 K as a soot inception temperature. Simulations were also carried out for D o between 0.25 mm and 5 mm to explore the effect of radiation and D o on burning. Below 0.25 mm radiation was negligible and burning rates and flame temperatures converged to a single value. Increasing D o up to 1.8 mm lowered the burning rate with luminous radiation having a strong effect. When radiation was entirely removed from the model the burning rate was nearly constant. Above D o = 2 mm droplets extinguished almost immediately after ignition. The flame temperature decreased with increasing D o while it increased when radiation was omitted. As a result, the simulations show that soot precursors including polyaromatic hydrocarbons were concentrated around the soot shell.

42 ENGINEERING↗

Regular sensitivity computation avoiding chaotic effects in particle-in-cell plasma methods

Particle-in-cell (PIC) simulation methods are attractive for representing species distribution functions in plasmas. However, as a model, they introduce uncertain parameters, and for quantifying their prediction uncertainty it is useful to be able to assess the sensitivity of a quantity-of-interest (QoI) to these parameters. Such sensitivity information is likewise useful for optimization. However, computing sensitivity for PIC methods is challenging due to the chaotic particle dynamics, and sensitivity techniques remain underdeveloped compared to those for Eulerian discretizations. This challenge is examined from a dual particle–continuum perspective that motivates a new sensitivity discretization. Two routes to sensitivity computation are presented and compared: a direct fully-Lagrangian particle-exact approach provides sensitivities of each particle trajectory, and a new particle-pdf discretization, which is formulated from a continuum perspective but discretized by particles to take the advantages of the same type of Lagrangian particle description leveraged by PIC methods. Since the sensitivity particles in this approach are only indirectly linked to the plasma-PIC particles, they can be positioned and weighted independently for efficiency and accuracy. The corresponding numerical algorithms are presented here in mathematical detail. The advantage of the particle-pdf approach in avoiding the spurious chaotic sensitivity of the particle-exact approach is demonstrated for Debye shielding and sheath configurations. In essence, the continuum perspective makes implicit the distinctness of the particles, which circumvents the Lyapunov instability of the N -body PIC system. The cost of the particle-pdf approach is comparable to the baseline PIC simulation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The effects of ACRT on melt undercooling during the growth of CZT via the traveling heater method: Ekman versus Taylor-Görtler flows

For the first time, a comprehensive model for the traveling heater method, including detailed species transport and phase-change thermodynamics, is applied to understand the effects of accelerated crucible rotation (ACRT) on the growth of cadmium zinc telluride. Here, a rotation schedule that is designed from classical considerations does not completely mix the melt, rather undercooled regions of localized melt are swept periodically across the growth interface. Even without melt homogenization, these ACRT-driven flows disrupt the persistent undercooling that occurs during THM growth without rotation. An ACRT schedule designed to promote Ekman flows results in lower levels of melt undercooling than a schedule designed to promote Taylor-Görtler flows and greater mixing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Desorption of Phosphate from Iron-Bearing Soil Minerals by a Plant Secondary Metabolite

In soils, phosphorus readily adsorbs to the surfaces of ubiquitous iron (oxyhydr)oxide minerals, rendering it less accessible to plants and microorganisms. Plants have a number of strategies to access iron, among them the secretion of redox-active metabolites from their roots. Although these strategies likely increase the bioavailability of surface-adsorbed phosphorus through reductive dissolution, their effect on phosphorus cycling has not yet been investigated. We tested the ability of fraxetin, a coumarin-type redox-active metabolite produced by the model plant Arabidopsis thaliana and other dicotyledon plant species, to reductively solubilize phosphate from the surface of ferrihydrite. Our findings show that, at low and neutral pH, fraxetin increased aqueous phosphate concentrations under both oxic and anoxic conditions; at high pH, it was only effective in anoxic experiments. Additionally, a combination of liquid chromatography–mass spectrometry and spectroscopic methods demonstrated substantial fraxetin adsorption to the mineral surface but showed that iron reduction did not alter the mineral structure or change the nature of the chemical environment of the phosphorus atom over short time scales. These results provide evidence that the secretion of redox-active metabolites from roots is likely to be an effective phosphorus acquisition tactic in iron-rich soils.

36 MATERIALS SCIENCE↗

Preparation and Characterization of Model Homotopic Catalysts: Rh Adatoms, Nanoparticles, and Mixed Oxide Surfaces on Fe 3 O 4 (001)

The atomic-level characterization of active sites is essential to understanding the mechanisms behind catalytic reactions. In this study, using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), we follow the morphological changes of a model Rh catalysts supported on Fe 3 O 4 (001) as a function of temperature and Rh coverage. Here, we identify the preparation conditions leading to model catalysts containing homotopic or nearly homotopic Rh species bound as adatoms, small clusters, substitutional within the Fe 3 O 4 (001), and nanoparticles. Adsorbates such as CO and CO 2 are further subsequently used to characterize the properties of different Rh sites. Using temperature programmed desorption (TPD), we demonstrate that adatoms, clusters, and nanoparticles exhibit high-temperature CO desorption (250-600 K). Strong binding on such sites further allows for CO oxidation to CO 2 via the Mars-van-Krevelen mechanism. In contrast, CO 2 was found to interact weakly with all Rh sites. Differences in desorption temperature enable the use of CO and CO 2 as titration methods for nanoparticles and Fe 3 O 4 (001), respectively. A small quantity of CO 2 was found to be reduced to CO on Rh adatoms and clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neoclassical transport of tungsten ion bundles in total-f neoclassical gyrokinetic simulations of a whole-volume JET-like plasma

Here, the application of a bundling technique to model the diverse charge states of tungsten impurity species in total-f gyrokinetic simulations is demonstrated. The gyrokinetic bundling method strategically groups tungsten ions of similar charge, optimizing computational efficiency. The initial radial configuration of these bundles and their respective charges are derived from a coronal approximation and the quasi-neutrality of the plasma. A low-density JET H-mode like plasma is simulated using the neoclassical version of XGC across the entire plasma volume, spanning from the magnetic axis to the divertor. An accumulation of tungsten is observed at the pedestal top, as a result of low-Z tungsten ions moving inward from the scrape-off-layer into the core region and high-Z tungsten ions moving outward from the core into the pedestal. This organization of the fluxes cannot be captured by a single tungsten-ion simulation. Large up-down poloidal asymmetries of tungsten form in the pedestal and strongly influence the direction of neoclassical fluxes. The temperature screening effect and its correlation with asymmetries are analyzed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Resolving discrepancies in bang-time predictions for indirect-drive ICF experiments on the NIF: Insights from the Build-A-Hohlraum campaign

This study investigated discrepancies between measured and simulated x-ray drive in Indirect-Drive Inertial Confinement Fusion (ID-ICF) hohlraums at the National Ignition Facility. Despite advances in radiation-hydrodynamic simulations, a consistent “drive deficit” remains. Experimentally measured ID-ICF capsule bang-times are systematically 400–700 ps later than simulations predict. The Build-A-Hohlraum (BAH) campaign explored potential causes for this discrepancy by systematically varying hohlraum features, including laser entrance hole (LEH) windows, capsules, and gas fills. Overall, the agreement between simulated and experimental x-ray drive was found to be largely unaffected by these changes. The data allow us to exclude some hypotheses put forward to potentially explain the discrepancy. Errors in the local thermodynamic equilibrium (LTE) atomic modeling, errors in the modeling of LEH closure, and errors due to a lack of plasma species mix physics in simulations are shown to be inconsistent with our measurements. Instead, the data support the hypothesis that errors in NLTE emission modeling are a significant contributor to the discrepancy. X-ray emission in the 2–4 keV range is found to be approximately 30% lower than in simulations. This is accompanied by higher than predicted electron temperatures in the gold bubble region, pointing to errors in non-LTE modeling. Introducing an opacity multiplier of 0.87 on energy groups above 1.8 keV improves agreement with experimental data, reducing the bang-time discrepancy from 300 to 100 ps. These results underscore the need for refined NLTE opacity models to enhance the predictive power of hohlraum simulations.

Band emission↗

An Analytical Tool to Evaluate Defect Thermodynamics of (La,Ba)Fe1-xMxO3-δ Perovskites for Solid-Oxide Cell Applications

A modeling tool of the defect thermodynamics of (La,Ba)Fe1-xMxO3-δ perovskites which includes energetic information about oxygen vacancy formation, hydration, hydride formation, and charge disproportionation reactions has been developed1. This tool incorporates defect energies and entropies expressed as sixth order polynomial functions to allow refinements of the defect reaction equilibrium constants in the thermodynamic analysis. Calculation of (La,Ba)Fe1-xMxO3-δ Brouwer diagrams as a function of pO2/pH2O and pH2/H2O in a range of temperatures of interest is facilitated by this modeling tool. The results obtained can provide direct guidance how the electronic and ionic defect concentrations of the triple conducting perovskite materials can be used to optimize performance of solid oxide cells for energy applications. The impact of magnetic and electronic structures of the perovskites on the defect reaction energies and entropies as obtained from density function theory modeling and the role played by hydride defect species will also be discussed.

Lee, Yueh-Lin↗

Rapid SACR Observations of Convection at Bankhead National Forest (RAPID) Field Campaign Report

Improving our representation of convective cell processes requires better quantification of convective clouds throughout their entire life cycle. This includes gaining a clearer understanding of the controls on key convective cloud properties, such as updraft intensity, particle size distributions, rainfall rates, and hydrometeor species. Our inability to improve convective cloud process modeling stems, in part, from a limited understanding of convective cell properties, particularly given how rapidly these storms evolve. This lack of detailed observations in the most intense and organized convective storms is especially significant, as large errors remain in representing these clouds, which are critical for severe weather prediction and Earth system model performance. Cloud and precipitation radars are essential tools for studying cloud microphysics and dynamics, particularly in deeper convective clouds. The recent U.S. Department of Energy Atmospheric Radiation Measurement (ARM) User Facility’s third Mobile Facility (AMF3) Bankhead National Forest (BNF) deployment provides a unique opportunity to investigate important land–atmosphere interactions, as well as the environmental controls on deep convective cloud processes, in a location favorable for frequent convection. We operate the X/Ka-band Scanning ARM Cloud Radar (X/Ka SACR) using a scan strategy optimized to capture these rapidly evolving clouds and their properties, thereby improving studies of deep convective cloud processes. This effort is strengthened by a complementary and coordinated partnership with ongoing university and multi-agency radar activities collocated in north Alabama—a unique opportunity to examine clouds and precipitation from a lifetime-centric perspective.

54 ENVIRONMENTAL SCIENCES↗

Structural Polymorphism of Chitin and Chitosan in Fungal Cell Walls From Solid-State NMR and Principal Component Analysis

Chitin is a major carbohydrate component of the fungal cell wall and a promising target for novel antifungal agents. However, it is technically challenging to characterize the structure of this polymer in native cell walls. Here, we recorded and compared 13 C chemical shifts of chitin using isotopically enriched cells of six Aspergillus, Rhizopus, and Candida strains, with data interpretation assisted by principal component analysis (PCA) and linear discriminant analysis (LDA) methods. The structure of chitin is found to be intrinsically heterogeneous, with peak multiplicity detected in each sample and distinct fingerprints observed across fungal species. Fungal chitin exhibits partial similarity to the model structures of α- and γ-allomorphs; therefore, chitin structure is not significantly affected by interactions with other cell wall components. Addition of antifungal drugs and salts did not significantly perturb the chemical shifts, revealing the structural resistance of chitin to external stress. In addition, the structure of the deacetylated form, chitosan, was found to resemble a relaxed two-fold helix conformation. This study provides high-resolution information on the structure of chitin and chitosan in their cellular contexts. The method is applicable to the analysis of other complex carbohydrates and polymer composites.

59 BASIC BIOLOGICAL SCIENCES↗

Drug Resistance in Filarial Parasites Does Not Affect Mosquito Vectorial Capacity

Parasite drug resistance presents a major obstacle to controlling and eliminating vector-borne diseases affecting humans and animals. While vector-borne disease dynamics are affected by factors related to parasite, vertebrate host and vector, research on drug resistance in filarial parasites has primarily focused on the parasite and vertebrate host, rather than the mosquito. However, we expect that the physiological costs associated with drug resistance would reduce the fitness of drug-resistant vs. drug-susceptible parasites in the mosquito wherein parasites are not exposed to drugs. Here we test this hypothesis using four isolates of the dog heartworm (Dirofilaria immitis)—two drug susceptible and two drug resistant—and two vectors—the yellow fever mosquito (Aedes aegypti) and the Asian tiger mosquito (Ae. albopictus)—as our model system. Our data indicated that while vector species had a significant effect on vectorial capacity, there was no significant difference in the vectorial capacity of mosquitoes infected with drug-resistant vs. drug-susceptible parasites. Consequently, contrary to expectations, our data indicate that drug resistance in D. immitis does not appear to reduce the transmission efficiency of these parasites, and thus the spread of drug-resistant parasites in the vertebrate population is unlikely to be mitigated by reduced fitness in the mosquito vector.

59 BASIC BIOLOGICAL SCIENCES↗