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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Enhancements in laser-generated hot-electron production via focusing cone targets at short pulse and high contrast

We report on the increase in the accelerated electron number and energy using compound parabolic concentrator (CPC) targets from a short-pulse (~150 fs), high-intensity (>10 18 W/cm 2 ), and high-contrast (~10 8 ) laser-solid interaction. We report on experimental measurements using CPC targets where the hot-electron temperature is enhanced up to ~ 9 times when compared to planar targets. The temperature measured from the CPC target is (T e ) = 4.4 ± 1.3 MeV. Using hydrodynamic and particle in cell simulations, we identify the primary source of this temperature enhancement is the intensity increase caused by the CPC geometry that focuses the laser, reducing the focal spot and therefore increasing the intensity of the laser-solid interaction, which is also consistent with analytic expectations for the geometrical focusing.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2011

DEMONSTRATION OF THE GLYCOLIC-FORMIC FLOWSHEET IN THE SRNL SHIELDED CELLS USING ACTUAL WASTE

Glycolic acid was effective at dissolving many metals, including iron, during processing with simulants. Criticality constraints take credit for the insolubility of iron during processing to prevent criticality of fissile materials. Testing with actual waste was needed to determine the extent of iron and fissile isotope dissolution during Chemical Process Cell (CPC) processing. The Alternate Reductant Project was initiated by the Savannah River Remediation (SRR) Company to explore options for the replacement of the nitric-formic flowsheet used for the CPC at the Defense Waste Processing Facility (DWPF). The goals of the Alternate Reductant Project are to reduce CPC cycle time, increase mass throughput of the facility, and reduce operational hazards. In order to achieve these goals, several different reductants were considered during initial evaluations conducted by Savannah River National Laboratory (SRNL). After review of the reductants by SRR, SRNL, and Energy Solutions (ES) Vitreous State Laboratory (VSL), two flowsheets were further developed in parallel. The two flowsheet options included a nitric-formic-glycolic flowsheet, and a nitric-formic-sugar flowsheet. As of July 2011, SRNL and ES/VSL have completed the initial flowsheet development work for the nitric-formic-glycolic flowsheet and nitric-formic-sugar flowsheet, respectively. On July 12th and July 13th, SRR conducted a Systems Engineering Evaluation (SEE) to down select the alternate reductant flowsheet. The SEE team selected the Formic-Glycolic Flowsheet for further development. Two risks were identified in SEE for expedited research. The first risk is related to iron and plutonium solubility during the CPC process with respect to criticality. Currently, DWPF credits iron as a poison for the fissile components of the sludge. Due to the high iron solubility observed during the flowsheet demonstrations with simulants, it was necessary to determine if the plutonium in the radioactive sludge slurry demonstrated the same behavior. The second risk is related to potential downstream impacts of glycolate on Tank Farm processes. The downstream impacts will be evaluated by a separate research team. Waste Solidification Engineering (WSE) has requested a radioactive demonstration of the Glycolic-Formic Flowsheet with radioactive sludge slurry be completed in the Shielded Cells Facility of the SRNL. The Shielded Cells demonstration only included a Sludge Receipt and Adjustment Tank (SRAT) cycle, and not a Slurry Mix Evaporator (SME) cycle or the co-processing of salt products. Sludge Batch 5 (SB5) slurry was used for the demonstration since it was readily available, had been previously characterized, and was generally representative of sludges being processing in DWPF. This sample was never used in the planned Shielded Cells Run 7 (SC-7).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Defense Waste Processing Facility Simulant Chemical Processing Cell Studies for Sludge Batch 9

The Savannah River National Laboratory (SRNL) received a technical task request from Defense Waste Processing Facility (DWPF) and Saltstone Engineering to perform simulant tests to support the qualification of Sludge Batch 9 (SB9) and to develop the flowsheet for SB9 in the DWPF. These efforts pertained to the DWPF Chemical Process Cell (CPC). CPC experiments were performed using SB9 simulant (SB9A) to qualify SB9 for sludge-only and coupled processing using the nitric-formic flowsheet in the DWPF. Two simulant batches were prepared, one representing SB8 Tank 40H and another representing SB9 Tank 51H. The simulant used for SB9 qualification testing was prepared by blending the SB8 Tank 40H and SB9 Tank 51H simulants. The blended simulant is referred to as SB9A. Eleven CPC experiments were run with an acid stoichiometry ranging between 105% and 145% of the Koopman minimum acid equation (KMA), which is equivalent to 109.7% and 151.5% of the Hsu minimum acid factor. Three runs were performed in the 1L laboratory scale setup, whereas the remainder were in the 4L laboratory scale setup. Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles were performed on nine of the eleven. The other two were SRAT cycles only. One coupled flowsheet and one extended run were performed for SRAT and SME processing. Samples of the condensate, sludge, and off-gas were taken to monitor the chemistry of the CPC experiments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2010

MODELING THE IMPACT OF ELEVATED MERCURY IN DEFENSE WASTE PROCESSING FACILITY MELTER FEED ON THE MELTER OFF-GAS SYSTEM-PRELIMINARY REPORT

The Defense Waste Processing Facility (DWPF) is currently evaluating an alternative Chemical Process Cell (CPC) flowsheet to increase throughput. It includes removal of the steam-stripping step, which would significantly reduce the CPC processing time and lessen the sampling needs. However, its downside would be to send 100% of the mercury that comes in with the sludge straight to the melter. For example, the new mercury content in the Sludge Batch 5 (SB5) melter feed is projected to be 25 times higher than that in the SB4 with nominal steam stripping of mercury. This task was initiated to study the impact of the worst-case scenario of zero-mercury-removal in the CPC on the DWPF melter offgas system. It is stressed that this study is intended to be scoping in nature, so the results presented in this report are preliminary. In order to study the impact of elevated mercury levels in the feed, it is necessary to be able to predict how mercury would speciate in the melter exhaust under varying melter operating conditions. A homogeneous gas-phase oxidation model of mercury by chloride was developed to do just that. The model contains two critical parameters pertaining to the partitioning of chloride among HCl, Cl, Cl{sub 2}, and chloride salts in the melter vapor space. The values for these parameters were determined at two different melter vapor space temperatures by matching the calculated molar ratio of HgCl (or Hg{sub 2}Cl{sub 2}) to HgCl{sub 2} with those measured during the Experimental-Scale Ceramic Melter (ESCM) tests run at the Pacific Northwest National Laboratory (PNNL). The calibrated model was then applied to the SB5 simulant used in the earlier flowsheet study with an assumed mercury stripping efficiency of zero; the molar ratio of Cl-to-Hg in the resulting melter feed was only 0.4, compared to 12 for the ESCM feeds. The results of the model run at the indicated melter vapor space temperature of 650 C (TI4085D) showed that due to excessive shortage of chloride, only 6% of the mercury fed is expected to get oxidized, mostly as HgCl, while the remaining mercury would exist either as elemental mercury vapor (90%) or HgO (4%). Noting that the measured chloride level in the SB5 qualification sample was an order of magnitude lower than that used in the SB5 simulant, the degree of chloride shortage will be even greater. As a result, the projected level of HgCl in the actual SB5 melter exhaust will be even lower than 6% of the total mercury fed, while that of elemental mercury is likely to be greater than 90%. The homogeneous oxidation of mercury in the off-gas was deemed to be of primary importance based on the postulation that mercury and other volatile salts form submicron sized aerosols upon condensation and thus remain largely in the gas stream downstream of the quencher where they can deposit in the off-gas lines, Steam-Atomized Scrubbers (SAS), and High-Efficiency Mist Eliminator (HEME). Formation of these submicron semi-volatile salts in the condensate liquid is considered to be unlikely, so the liquid phase reactions were considered to be less important. However, subsequent oxidation of mercury in the liquid phase in the off-gas system was examined in a simplified model of the off-gas condensate. It was found that the condensate chemistry was consistent with further oxidation of elemental mercury to Hg{sub 2}Cl{sub 2} and conversion of HgO to chlorides. The results were consistent with the available experimental data. It should also be noted that the model predictions presented in this report do not include any physically entrained solids, which typically account for much of the off-gas carryover on a mass basis. The high elemental mercury vapor content predicted at the DWPF Quencher inlet means that physically entrained solids could provide the necessary surface onto which elemental mercury vapor could condense, thereby coating the solids as well as the internal surfaces of the off-gas system with mercury. Clearly, there are many process benefits to be gained by removing the steam-stripping step from the CPC cycle. The goal of this task was to study what adverse impact the zero-mercury-removal scenario would have on the DWPF melter off-gas system operation. It is stressed again that this study was intended to be scoping in nature, so the results presented in this report are preliminary. Any further substantiation of these results for actual implementation into the DWPF flowsheet would require an in-depth modeling study of all three reaction zones, including the aqueous-phase reactions in the quencher, OGCT, Steam Atomized Scrubber (SAS), and off-gas condenser with recirculated condensate, and the proof-of-principle experiments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2013

The Behavior of Environmentally Friendly Corrosion Preventative Compounds in an Aggressive Coastal Marine Environment

The shift to use environmentally friendly technologies throughout future space-related launch programs prompted a study aimed at replacing current petroleum and solvent-based Corrosion Preventive Compounds (CPCs) with environmentally friendly alternatives. The work in this paper focused on the identification and evaluation of environmentally friendly CPCs for use in protecting flight hardware and ground support equipment from atmospheric corrosion. The CPCs, while a temporary protective coating, must survive in the aggressive coastal marine environment that exists throughout the Kennedy Space Center, Florida. The different protection behaviors of fifteen different soft film CPCs, both common petroleum-based and newer environmentally friendly types, were evaluated on various steel and aluminum substrates. The CPC and substrate systems were subjected to atmospheric testing at the Kennedy Space Center's Beachside Atmospheric Corrosion Test Site, as well as cyclic accelerated corrosion testing. Each CPC also underwent physical characterization and launch-related compatibility testing . The initial results for the fifteen CPC systems are reported : Key words: corrosion preventive compound, CPC, spaceport, environmentally friendly, atmospheric exposure, marine, carbon steel, aluminum alloy, galvanic corrosion, wire on bolt.

Montgomery, Eliza L.↗
NASA NTRS2012

Environmentally Friendly Corrosion Preventative Compounds

The objective of the Ground Systems Development and Operations Program Environmentally Friendly Corrosion Protective Coatings and Corrosion Preventive Compounds (CPCs) project is to identify, test, and develop qualification criteria for the use of environmentally friendly corrosion protective coatings and CPCs for flight hardware and ground support equipment. This document is the Final Report for Phase I evaluations, which included physical property, corrosion resistance, and NASA spaceport environment compatibility testing and analysis of fifteen CPC types. The CPCs consisted of ten different oily film CPCs and five different wax or grease CPC types. Physical property testing encompassed measuring various properties of the bulk CPCs, while corrosion resistance testing directly measured the ability of each CPC material to protect various metals against corrosion. The NASA spaceport environment compatibility testing included common tests required by NASA-STD-6001, "Flammability, Odor, Offgassing, and Compatibility Requirements and Test Procedures for Materials in Environments that Support Combustion". At the end of Phase I, CPC materials were down-selected for inclusion in the next test phases. This final report includes all data and analysis of results obtained by following the experimental test plan that was developed as part of the project. Highlights of the results are summarized by test criteria type.

Preventative Compounds↗
DOE OSTI2018

Pseudo-dynamic Aspen Plus{sup R} Model of the Defense Waste Processing Facility - 18475

The Defense Waste Processing Facility (DWPF) at the Savannah River Site converts legacy high-level waste from the Cold War into borosilicate glass for permanent disposal in a geological repository. The waste sludge is chemically adjusted by the addition of acid, mixed with frit, and concentrated in the DWPF Chemical Process Cell (CPC) to ensure that the final glass has the desired properties. The resulting mixture is fed into the melter where the waste is melted and poured into stainless steel storage canisters. We present an Aspen Plus{sup R} model of the DWPF CPC, which is being developed to aid chemical processing decisions pertaining to the current flowsheet and to aid decisions regarding optimizing future processing. Given a waste feed composition with acid and frit additions, the model will predict the sludge and off-gas compositions throughout the processing, as well as the final melter feed composition. This allows different processing scenarios to be investigated easily, reducing the reliance on experimental testing, and hence saving time and money. The model has multiple potential applications, including calculating the acid and frit additions required to give acceptable glass properties, off-gas permitting, tracking mercury steam-stripped from the waste in the off-gas system, tracking flammable gases in the offgas system, investigating the effect of reducing air purges in the condensers, and general process optimization. The waste is processed in the CPC in batches, requiring dynamic simulation to track the time-dependent operations. Accurate modeling of the processing also requires calculations of phase and electrolyte chemical equilibria and parallel rate-dependent reactions. Due to existing technical limitations with dynamic simulation of the complex chemical system, we have adopted a pseudo-dynamic approach in which time intervals are treated as consecutive steady-state operations in Aspen Plus{sup R}. Thus, the model consists of ∼100 replicas of the processing vessel and its off-gas system, with the sludge output by one replica (representing one time interval) becoming the feed to the next (representing the next time interval). By examining the results from these replicas in sequence, one can see the time evolution of the model. This general approach can be used wherever simultaneous calculation of phase and electrolyte chemical equilibria in a dynamically evolving system is needed. In addition to describing the general structure and chemistry of the model, we present results from tests of the model against experimental data. These data are from laboratory-scale process simulations of the CPC with a nonradioactive waste sludge simulant. These tests include the model's predictions of the offgas composition, the sludge pH, and the final sludge composition. We will also discuss planned future developments of the model. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Toward control co-design of utility-scale wind turbines: Collective vs. individual blade pitch control

A large-eddy simulation framework has been coupled with controller modules to systematically investigate the impacts of collective (CPC) and individual (IPC) pitch control strategies on utility-scale wind turbine energy production and fatigue loads. Wind turbine components were parameterized using an actuator surface model to simulate the rotor blades and the turbine nacelle. The baseline CPC and IPC algorithms, consisting of single-input single-output proportional–integral controllers and two integral controllers, respectively, were incorporated into the numerical framework. A series of simulations were carried out to investigate the relative performance of the two controllers under various turbulent inflow conditions, spanning hub-height velocities of 7 to 14 m/s. The numerical simulation results of this study showed that, in comparison to the CPC, the IPC controller could successfully reduce the damage equivalent loads of utility-scale turbines at regions 2 and 3 of turbine operation by about 3% and 40%, respectively, without any penalty on the power production of the turbine. It was also shown that, despite its minor impact on the turbulence kinetic energy of the wake, the IPC controller did not influence the recovery of the turbine wake.

17 WIND ENERGY↗
DOE OSTI2010

The Impact of Radiotherapy Fields in the Treatment of Patients With Choroid Plexus Carcinoma

Purpose: To perform a comprehensive literature review and analysis of cases dealing with choroid plexus carcinoma (CPC) to determine the optimal radiotherapy (RT) treatment field. Methods and Materials: A PubMed search of English language articles from 1979 to 2008 was performed, yielding 33 articles with 56 patients who had available data regarding RT treatment field. The median age at diagnosis was 2.7 years (range, 1 month-53 years). Of 54 patients with data regarding type of surgery, 21 (38.9%) had complete resection. Chemotherapy was delivered to 27 (48%) as part of initial therapy. The RT treatment volume was the craniospinal axis in 38 (68%), whole brain in 9 (16%), and tumor/tumor bed in 9 (16%). Median follow-up for surviving patients was 40 months. Results: The 5-year overall survival and progression-free survival (PFS) rates were 59.5% and 37.2%, respectively. Complete resection (p = 0.035) and use of craniospinal irradiation (CSI; p = 0.025) were found to positively affect PFS. The 5-year PFS for patients who had CSI vs. whole brain and tumor/tumor bed RT were 44.2% and 15.3%. For the 19 patients who relapsed, 9 (47%) had a recurrence in the RT field, 6 (32%) had a recurrence outside the RT field, and 4 (21%) had a recurrence inside and outside the irradiated field. Conclusion: Patients with CPC who received CSI had better PFS compared with those receiving less than CSI. This study supports the use of CSI in the multimodality management of patients with CPC.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2012

Absolute Cavity Pyrgeometer to Measure the Absolute Outdoor Longwave Irradiance with Traceability to International System of Units, SI

This article describes a method of measuring the absolute outdoor longwave irradiance using an absolute cavity pyrgeometer (ACP), U.S. Patent application no. 13/049, 275. The ACP consists of domeless thermopile pyrgeometer, gold-plated concentrator, temperature controller, and data acquisition. The dome was removed from the pyrgeometer to remove errors associated with dome transmittance and the dome correction factor. To avoid thermal convection and wind effect errors resulting from using a domeless thermopile, the gold-plated concentrator was placed above the thermopile. The concentrator is a dual compound parabolic concentrator (CPC) with 180{sup o} view angle to measure the outdoor incoming longwave irradiance from the atmosphere. The incoming irradiance is reflected from the specular gold surface of the CPC and concentrated on the 11 mm diameter of the pyrgeometer's blackened thermopile. The CPC's interior surface design and the resulting cavitation result in a throughput value that was characterized by the National Institute of Standards and Technology. The ACP was installed horizontally outdoor on an aluminum plate connected to the temperature controller to control the pyrgeometer's case temperature. The responsivity of the pyrgeometer's thermopile detector was determined by lowering the case temperature and calculating the rate of change of the thermopile output voltage versus the changing net irradiance. The responsivity is then used to calculate the absolute atmospheric longwave irradiance with an uncertainty estimate (U{sub 95}) of {+-}3.96 W m{sup 02} with traceability to the International System of Units, SI. The measured irradiance was compared with the irradiance measured by two pyrgeometers calibrated by the World Radiation Center with traceability to the Interim World Infrared Standard Group, WISG. A total of 408 readings were collected over three different nights. The calculated irradiance measured by the ACP was 1.5 W/m{sup 2} lower than that measured by the two pyrgeometers that are traceable to WISG, with a standard deviation of {+-}0.7 W m{sup -2}. These results suggest that the ACP design might be used for addressing the need to improve the international reference for broadband outdoor longwave irradiance measurements.

14 SOLAR ENERGY↗
DOE OSTI2022

Effect of natural carbon filler on thermo-oxidative degradation of thermoplastic-based composites

Here thermo-oxidative degradation of thermoplastic-based composites filled with two types of carbon filler including bituminous (Pittsburgh No.8, P8) and sub-bituminous (Powder River Basin, PRB) coals were investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis. Oxidation induction time (OIT) and activation energy (AE) for coal plastic composites (CPCs), HDPE, and commercially available wood plastic composites (WPCs) were determined using isothermal and isoconversional kinetic methods. OIT values for CPC increased with coal content, indicating higher thermo-oxidative stability. AE values obtained using isothermal method were 52–116 kJ/mol for all CPC formulations, 32 kJ/mol for HDPE, and 33–114 kJ/mol for WPCs. AEs for CPCs obtained using isoconversional methods were not constant but rather dependent on the degree of degradation with CPC/ P8 coal possessing higher overall AE. Incorporating coal into HDPE increased thermo-oxidative stability of the resulting composite, indicating coal potentially acts as a natural primary and secondary antioxidant for polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Synthesis and Characterization of Elastomeric Heptablock Terpolymers Structured by Crystallization

We report the synthesis and characterization of fully saturated hydrocarbon block copolymer thermoplastic elastomers with competitive mechanical properties and attractive processing features. Block copolymers containing glassy poly(cyclohexylethylene) (C), elastomeric poly(ethylene-alt-propylene) (P), and semicrystalline poly(ethylene) (E) were produced in a CEC-P-CEC heptablock architecture, denoted XPX, by anionic polymerization and catalytic hydrogenation. The X blocks contain equal volume fractions of C and E, totaling 40%-60% of the material overall. All the XPX polymers are disordered above the melt temperature for E (T{sub m,E} {approx_equal} 95 C) as evidenced by SAXS and dynamic mechanical spectroscopy measurements. Cooling below T{sub m,E} results in crystallization of the E blocks, which induces microphase segregation of E, C, and P into a complex morphology with a continuous rubbery domain and randomly arranged hard domains as shown by TEM. This mechanism of segregation decouples the processing temperature from the XPX molecular weight up to a limiting value. Tensile mechanical testing (simple extension and cyclic loading) demonstrates that the tensile strength (ca. 30 MPa) and strain at break (>500%) are comparable to the behavior of CPC triblock thermoplastic elastomers of similar molecular weight and glass content. However, in the CPC materials, processability is constrained by the order-disorder transition temperature, limiting the applications of these materials. Elastic recovery of the XPX materials following seven cycles of tensile deformation is correlated with the fraction of X in the heptablock copolymer, and the residual strain approaches that of CPC when the fraction of hard blocks f{sub X} {le} 0.39.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The effect of structural changes on charge transfer states in a light-harvesting carotenoid-diaryl-porphyrin-C{sub 60} molecular triad

We present a detailed study of charge transfer (CT) excited states for a large number of configurations in a light-harvesting Carotenoid-diaryl-Porphyrin-C{sub 60} (CPC{sub 60}) molecular triad. The chain-like molecular triad undergoes photoinduced charge transfer process exhibiting a large excited state dipole moment, making it suitable for application to molecular-scale opto-electronic devices. An important consideration is that the structural flexibility of the CPC{sub 60} triad impacts its dynamics in solvents. Since experimentally measured dipole moments for the triad of ∼110 D and ∼160 D strongly indicate a range in structural variability in the excited state, studying the effect of structural changes on the CT excited state energetics furthers the understanding of its charge transfer states. We have calculated the variation in the lowest CT excited state energies by performing a scan of possible variation in the structure of the triad. Some of these configurations were generated by incrementally scanning a 360° torsional (dihedral) twist at the C{sub 60}-porhyrin linkage and the porphyrin-carotenoid linkage. Additionally, five different CPC{sub 60} conformations were studied to determine the effect of pi-conjugation and particle-hole Coulombic attraction on the CT excitation energies. Our calculations show that configurational changes in the triad induces a variation of ∼0.6 eV in CT excited state energies in the gas-phase. The corresponding calculated excited state dipoles show a range of 47 D–188 D. The absorption spectra and density of states of these structures show little variation except for the structures where the porphyrin and aryl conjugation is changed.

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

The role of chemical potential in compensation control in Si:AlGaN

Reduction in compensation in Si-doped Al-rich AlGaN is demonstrated via chemical potential control (CPC). The chemical potentials and the resulting formation energies of carbon on the nitrogen site (C N ) and cation vacancy complex with Si (V III + nSi III ) were related to growth variables through a thermodynamic supersaturation model, which quantitatively predicted the incorporation of C N and the generation of the V III + nSi III complex. The compensation “knee” behavior, i.e., decreasing conductivity with increasing Si incorporation beyond a certain concentration, was successfully controlled. The maximum free carrier concentration was improved by impeding the formation of V III + nSIi III complexes under III-richer conditions, while the impurity compensation by C N was reduced by making the growth environment N-richer. The results of Hall effect measurement and photoluminescence agreed well with quantitative theoretical predictions of the CPC model. Based on the developed model, the highest conductivity of 160 Ω -1 cm -1 with free carrier concentration of 3 × 10 19 cm -3 in Al 0.7 Ga 0.3 N ever reported was achieved on single crystal AlN substrates. The demonstrated predictive power of the CPC model should greatly reduce the empirical analysis or iterative experimentation that would otherwise be necessary.

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

Three-state harmonic models for photoinduced charge transfer

A widely used strategy for simulating the charge transfer between donor and acceptor electronic states in an all-atom anharmonic condensedphase system is based on invoking linear response theory to describe the system in terms of an effective spin-boson model Hamiltonian. Extending this strategy to photoinduced charge transfer processes requires also taking into consideration the ground electronic state in addition to the excited donor and acceptor electronic states. In this paper, we revisit the problem of describing such nonequilibrium processes in terms of an effective three-state harmonic model. We do so within the framework of nonequilibrium Fermi’s golden rule (NE-FGR) in the context of photoinduced charge transfer in the carotenoid–porphyrin–C 60 (CPC 60 ) molecular triad dissolved in explicit tetrahydrofuran (THF). To this end, we consider different ways for obtaining a three-state harmonic model from the equilibrium autocorrelation functions of the donor–acceptor, donor–ground, and acceptor–ground energy gaps, as obtained from all-atom molecular dynamics simulations of the CPC 60 /THF system. The quantum-mechanically exact time-dependent NE-FGR rate coefficients for two different charge transfer processes in two different triad conformations are then calculated using the effective three-state model Hamiltonians as well as a hierarchy of more approximate expressions that lead to the instantaneous Marcus theory limit. Our results show that the photoinduced charge transfer in CPC 60 /THF can be described accurately by the effective harmonic three-state models and that nuclear quantum effects are small in this system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Susceptibility of pESI positive Salmonella to treatment with biocide chemicals approved for use in poultry meat processing as compared to Salmonella without the pESI plasmid

Abstract Salmonella is a common cause of human foodborne illness, which is frequently associated with consumption of contaminated or undercooked poultry meat. Serotype Infantis is among the most common serotypes isolated from poultry meat products globally. Isolates of serotype Infantis carrying the pESI plasmid, the most dominant strain of Infantis, have been shown to exhibit oxidizer tolerance. Therefore, 16 strains of Salmonella with and without pESI carriage were investigated for susceptibility to biocide chemical processing aids approved for use in US poultry meat processing: peracetic acid (PAA), cetylpyridinium chloride (CPC), calcium hypochlorite, and sodium hypochlorite. Strains were exposed for 15 s to simulate spray application and 90 min to simulate application in an immersion chiller. All strains tested were susceptible to all concentrations of PAA, CPC, and sodium hypochlorite when applied for 90 min. When CPC, calcium hypochlorite, and sodium hypochlorite were applied for 15 s to simulate spray time, strains responded similarly to each other. However, strains responded variably to exposure to PAA. The variation was not statistically significant and appears unrelated to pESI carriage. Results highlight the necessity of testing biocide susceptibility in the presence of organic material and in relevant in situ applications.

Biotechnology & Applied Microbiology↗
DOE OSTI2016

Evaluation of NASA’s MERRA Precipitation Product in Reproducing the Observed Trend and Distribution of Extreme Precipitation Events in the United States

This study evaluates the performance of NASA's Modern-Era Retrospective Analysis for Research and Applications (MERRA) precipitation product in reproducing the trend and distribution of extreme precipitation events. Utilizing the extreme value theory, time-invariant and time-variant extreme value distributions are developed to model the trends and changes in the patterns of extreme precipitation events over the contiguous United States during 1979-2010. The Climate Prediction Center (CPC)U.S.Unified gridded observation data are used as the observational dataset. The CPC analysis shows that the eastern and western parts of the United States are experiencing positive and negative trends in annual maxima, respectively. The continental-scale patterns of change found in MERRA seem to reasonably mirror the observed patterns of change found in CPC. This is not previously expected, given the difficulty in constraining precipitation in reanalysis products. MERRA tends to overestimate the frequency at which the 99th percentile of precipitation is exceeded because this threshold tends to be lower in MERRA, making it easier to be exceeded. This feature is dominant during the summer months. MERRAtends to reproduce spatial patterns of the scale and location parameters of the generalized extreme value and generalized Pareto distributions. However, MERRA underestimates these parameters, particularly over the Gulf Coast states, leading to lower magnitudes in extreme precipitation events. Two issues in MERRA are identified: 1)MERRAshows a spurious negative trend in Nebraska andKansas, which ismost likely related to the changes in the satellite observing system over time that has apparently affected the water cycle in the central United States, and 2) the patterns of positive trend over theGulf Coast states and along the East Coast seem to be correlated with the tropical cyclones in these regions. The analysis of the trends in the seasonal precipitation extremes indicates that the hurricane and winter seasons are contributing the most to these trend patterns in the southeastern United States. The increasing annual trend simulated by MERRA in the Gulf Coast region is due to an incorrect trend in winter precipitation extremes.

54 ENVIRONMENTAL SCIENCES↗