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All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Evaluation of the Surface PM2.5 in Version 1 of the NASA MERRA Aerosol Reanalysis over the United States

We use surface fine particulate matter (PM2.5) measurements collected by the United States Environmental Protection Agency (US EPA) and the Interagency Monitoring of Protected Visual Environments (IMPROVE) networks as independent validation for Version 1 of the Modern Era Retrospective analysis for Research and Applications Aerosol Reanalysis (MERRAero) developed by the Global Modeling Assimilation Office (GMAO). MERRAero is based on a version of the GEOS-5 model that is radiatively coupled to the Goddard Chemistry, Aerosol, Radiation, and Transport (GOCART) aerosol module and includes assimilation of bias corrected Aerosol Optical Depth (AOD) from Moderate Resolution Imaging Spectroradiometer (MODIS) sensors on both Terra and Aqua satellites. By combining the spatial and temporal coverage of GEOS-5 with observational constraints on AOD, MERRAero has the potential to provide improved estimates of PM2.5 compared to the model alone and with greater coverage than available observations.Importantly, assimilation of AOD data constrains the total column aerosol mass in MERRAero subject to assumptions about optical properties for each of the species represented in GOGART. However, single visible wavelength AOD data does not contain sufficient information content to correct errors in either aerosol vertical placement or composition, critical elements for a proper characterization of surface PM2.5. Despite this, we find that the data-assimilation equipped version of GEOS-5 better represents observed PM2.5 between 2003 and 2012 compared to the same version of the model without AOD assimilation. Compared to measurements from the EPA-AQS network, MERRAero shows better PM2.5 agreement with the IMPROVE network measurements, which are composed essentially of rural stations. Regardless the data network, MERRAero PM2.5 are closer to observation values during the summer while larger discrepancies are observed during the winter. Comparing MERRAero to PM2.5 data collected by the Chemical Speciation Network (CSN) offers greater insight on the species MERRAero predicts well and those for which there are biases relative to the EPA observations. Analysis of this speciated data indicates that the lack of nitrate emissions in MERRAero and an underestimation of carbonaceous emissions in the Western US explains much of the reanalysis bias during the winter. To further understand discrepancies between the reanalysis and observations, we use complimentary data to assess two important aspects of MERRAero that are of relevance to the diagnosis of PM2.5, in particular AOD and vertical structure

Air Pollution↗
NASA NTRS2014

Revised (Mixed-Effects) Estimation for Forest Burning Emissions of Gases and Smoke, Fire/Emission Factor Typology, and Potential Remote Sensing Classification of Types for Ozone and Black-Carbon Simulation

We summarize recent progress (a) in correcting biomass burning emissions factors deduced from airborne sampling of forest fire plumes, (b) in understanding the variability in reactivity of the fresh plumes sampled in ARCTAS (2008), DC3 (2012), and SEAC4RS (2013) airborne missions, and (c) in a consequent search for remotely sensed quantities that help classify forest-fire plumes. Particle properties, chemical speciation, and smoke radiative properties are related and mutually informative, as pictures below suggest (slopes of lines of same color are similar). (a) Mixed-effects (random-effects) statistical modeling provides estimates of both emission factors and a reasonable description of carbon-burned simultaneously. Different fire plumes will have very different contributions to volatile organic carbon reactivity; this may help explain differences of free NOx(both gas- and particle-phase), and also of ozone production, that have been noted for forest-fire plumes in California. Our evaluations check or correct emission factors based on sequential measurements (e.g., the Normalized Ratio Enhancement and similar methods). We stress the dangers of methods relying on emission-ratios to CO. (b) This work confirms and extends many reports of great situational variability in emissions factors. VOCs vary in OH reactivity and NOx-binding. Reasons for variability are not only fuel composition, fuel condition, etc., but are confused somewhat by rapid transformation and mixing of emissions. We use "unmixing" (distinct from mixed-effects) statistics and compare briefly to approaches like neural nets. We focus on one particularly intense fire the notorious Yosemite Rim Fire of 2013. In some samples, NOx activity was not so suppressed by binding into nitrates as in other fires. While our fire-typing is evolving and subject to debate, the carbon-burned delta(CO2+CO) estimates that arise from mixed effects models, free of confusion by background-CO2 variation, should provide a solid base for discussion. (c) We report progress using promising links we find between emissions-related "fire types" and promising features deducible from remote observations of plumes, e.g., single scatter albedo, Angstrom exponent of scattering, Angstrom exponent of absorption, (CO column density)/(aerosol optical depth).

Remote sensing↗
NASA NTRS2017

Ground-Based High Spectral Resolution Lidar Observation of Aerosol Vertical Distribution in the Summertime Southeast United States

As part of the Southeast United States-based Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS), and collinear with part of the Southeast Atmosphere Study, the University of Wisconsin High Spectral Resolution Lidar system was deployed to the University of Alabama from 19 June to 4 November 2013. With a collocated Aerosol Robotic Network (AERONET) sun photometer, a nearby Chemical Speciation Network (PM2.5) measurement station, and near daily ozonesonde releases for the August-September SEAC4RS campaign, the site allowed the regions first comprehensive diurnal monitoring of aerosol particle vertical structure. A 532nm lidar ratio of 55 sr provided good closure between aerosol backscatter and AERONET (aerosol optical thickness, AOT). A principle component analysis was performed to identify key modes of variability in aerosol backscatter. ''Fair weather'' days exhibited classic planetary boundary layer structure of a mixed layer accounting for approx. 50% of AOT and an entrainment zone providing another 25%. An additional 5-15% of variance is gained from the lower free troposphere from either convective detrainment or frequent intrusions of western United States biomass burning smoke. Generally, aerosol particles were contained below the 0 C level, a common level of stability in convective regimes. However, occasional strong injections of smoke to the upper troposphere were also observed, accounting for the remaining 10-15% variability in AOT. Examples of these common modes of variability in frontal and convective regimes are presented, demonstrating why AOT often has only a weak relationship to surface PM2.5 concentration.

HSRL↗
NASA NTRSDate not supplied

Particle and Trace Gas Emissions Indices Measured During the 2021 Boeing ecoDemonstrator Emissions Ground Test

We present particle and trace gas emissions indices sampled on the ground at 30 meters behind the CFM LEAP-1B engines of the 2021 Boeing ecoDemonstrator, an Alaska Airlines 737-9 aircraft. Testing was carried out at Boeing Field in Seattle, WA, USA in Fall of 2021. Four different fuels were investigated including a 100% sustainable aviation fuel (SAF), a petroleum-based Jet A fuel, and two SAF blends. Total and non-volatile particle number concentrations were measured with a pair of condensation particle counters with one operating behind a custom-built thermal denuder heated to 350 degrees Celsius. Similarly, total and non-volatile particle number size distributions were measured with a pair of Scanning Mobility Particle Sizers (SMPSs). Non-volatile particle mass was estimated from particle light absorption techniques using an assumed mass absorption coefficient, while particle chemical speciation was measured by an Soot Particle Aerosol Mass Spectrometer (SP-AMS). A detailed list of instruments is given on the project website [1]. Overall, the results are consistent with expectations based on ICAO Emissions Databank certification data for the LEAP-1B with a stark reduction in non-volatile particle number and mass observed for the higher thrust conditions when the combustor was staged. The production of volatile particles under these conditions as well as experimental considerations related to background subtraction methods will be discussed. References: [1] Boeing ecoDemonstrator Science and Engineering Team (2022). 2021 Boeing ecoDemonstrator Emissions Ground Test Dataset

Richard H Moore↗
NASA NTRSDate not supplied

Particle and Trace Gas Emissions Indices Measured During the 2021 Boeing ecoDemonstrator Emissions Ground Test

We present particle and trace gas emissions indices sampled on the ground at 30 meters behind the CFM LEAP-1B engines of the Boeing ecoDemonstrator 737-9 aircraft. Testing was carried out at Boeing Field in Seattle, WA, USA in Fall of 2021. Four different fuels were investigated including a 100% sustainable aviation fuel (SAF), a petroleum-based Jet A fuel, and two SAF blends. Total and non-volatile particle number concentrations were measured with a pair of condensation particle counters with one operating behind a custom-built thermal denuder heated to 350 degrees Celsius. Similarly, total and non-volatile particle number size distributions were measured with a pair of Scanning Mobility Particle Sizers (SMPSs). Non-volatile particle mass was estimated from particle light absorption techniques using an assumed mass absorption coefficient, while particle chemical speciation was measured by an Soot Particle Aerosol Mass Spectrometer (SP-AMS). A detailed list of instruments is given on the project website [1]. Overall, the results are consistent with expectations based on ICAO Emissions Databank certification data for the LEAP-1B with a stark reduction in non-volatile particle number and mass observed for the higher thrust conditions when the combustor was staged. The production of volatile particles under these conditions as well as experimental considerations related to background subtraction methods will be discussed.

Benjamin A. Nault↗
DOE OSTI2024

Probing O 2 -dependence of cyclopentyl reactions via isomer-resolved speciation

Modeling chemical kinetics relevant to low-temperature combustion requires complete description of reactions involving critical species such as hydroperoxyalkyl radicals, Q̇OOH, which undergo competing unimolecular reactions and bimolecular reactions with O 2 . The balance of flux across the two pathways affects rates of chain-branching and depends on temperature, pressure, and oxygen concentration. Accordingly, the influence of [O 2 ] on product formation from alkyl + O 2 reactions and the subsequent fate of Q̇OOH and related products is central to the development of an accurate chemical kinetics mechanism. Furthermore, chemical reactions consuming Q̇OOH-mediated species are often simplified to such a degree that mechanism truncation error (uncertainty derived from incomplete reaction networks) becomes significant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Using PACE Aerosol Optical and Microphysical Properties to Capture Aerosol Composition

Improvements in air quality and Earth’s climate predictions can only be achieved through improvements of the aerosol speciation in chemical transport models, using observational constraints. Aerosol speciation (e.g., organic aerosols, black carbon, sulfate, nitrate, ammonium, dust or sea salt) is typically determined using in situ instrumentation. Continuous, routine surface network aerosol composition measurements are not uniformly widespread over the globe. Satellites, on the other hand, can provide a maximum coverage of the horizontal and vertical atmosphere but observe aerosol optical properties (and not aerosol speciation) based on remote sensing instrumentation. Combinations of satellite-derived aerosol optical properties can inform on air mass aerosol types (e.g., clean marine, dust, polluted continental). We investigate the relative skill of various combinations of aerosol optical properties used as tools to define air mass aerosol types and how much these optical properties can capture dominant aerosol speciation.

Meloe Shenandoah Kacenelenbogen↗
NASA NTRS2022

Identifying Chemical Aerosol Signatures Using Optical Suborbital Observations: How Much Can Optical Properties Tell us about Aerosol Composition?

Improvements in air quality and Earth’s climate predictions require improvements of the aerosol speciation in chemical transport models, using observational constraints. Aerosol speciation (e.g., organic aerosols, black carbon, sulfate, nitrate, ammonium, dust or sea salt) is typically determined using in situ instrumentation. Continuous, routine surface network aerosol composition measurements are not uniformly widespread over the globe. Satellites, on the other hand, can provide a maximum coverage of the horizontal and vertical atmosphere but observe aerosol optical properties (and not aerosol speciation) based on remote sensing instrumentation. Combinations of satellite-derived aerosol optical properties can inform on air mass aerosol types (AMTs e.g., clean marine, dust, polluted continental). However, these AMTs are subjectively defined, might often be misclassified and are hard to relate to the critical parameters that need to be refined in models. In this paper, we derive AMTs that are more directly related to sources and hence to speciation. They are defined, characterized, and derived using simultaneous in situ gas-phase, chemical and optical instruments on the same aircraft during the Study of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS, US, summer of 2013). First, we prescribe well-informed AMTs that display distinct aerosol chemical and optical signatures to act as a training AMT dataset. These in situ observations reduce the errors and ambiguities in the selection of the AMT training dataset. We also investigate the relative skill of various combinations of aerosol optical properties to define AMTs and how much these optical properties can capture dominant aerosol speciation. We find distinct optical signatures for biomass burning (from agricultural or wildfires), biogenic and dust-influence AMTs. Useful aerosol optical properties to characterize these signatures are the extinction angstrom exponent (EAE), the single scattering albedo, the difference of single scattering albedo in two wavelengths, the absorption coefficient, the absorption angstrom exponent (AAE), and the real part of the refractive index (RRI). We find that all four AMTs studied when prescribed using mostly airborne in situ gas measurements, can be successfully extracted from at least three combinations of airborne in situ aerosol optical properties (e.g., EAE, AAE and RRI) over the US during SEAC4RS. However, we find that the optically based classifications for BB from agricultural fires and polluted dust include a large percentage of misclassifications that limit the usefulness of results relating to those classes. The technique and results presented in this study are suitable to develop a representative, robust and diverse source-based AMT database. This database could then be used for widespread retrievals of AMTs using existing and future remote sensing suborbital instruments/networks. Ultimately, it has the potential to provide a much broader observational aerosol data set to evaluate chemical transport and air quality models than is currently available by direct in situ measurements. This study illustrates how essential it is to explore existing airborne datasets to bridge chemical and optical signatures of different AMTs, before the implementation of future spaceborne missions (e.g., the next generation of Earth Observing System (EOS) satellites addressing Aerosol, Cloud, Convection and Precipitation (ACCP) designated observables).

Meloe S F Kacenelenbogen↗
DOE OSTI2020

High-sensitivity nanoscale chemical imaging with hard x-ray nano-XANES

Resolving chemical species at the nanoscale is of paramount importance to many scientific and technological developments across a broad spectrum of disciplines. Hard x-rays with excellent penetration power and high chemical sensitivity are suitable for speciation of heterogeneous (thick) materials. Here, we report nanoscale chemical speciation by combining scanning nanoprobe and fluorescence-yield x-ray absorption near-edge structure (nano-XANES). First, the resolving power of nano-XANES was demonstrated by mapping Fe(0) and Fe(III) states of a reference sample composed of stainless steel and hematite nanoparticles with 50-nm scanning steps. Nano-XANES was then used to study the trace secondary phases in lithium iron phosphate (LFP) particles. We observed individual Fe-phosphide nanoparticles in pristine LFP, whereas partially (de)lithiated particles showed Fe-phosphide nanonetworks. These findings shed light on the contradictory reports on Fe-phosphide morphology in the literature. Nano-XANES bridges the capability gap of spectromicroscopy methods and provides exciting research opportunities across multiple disciplines.

25 ENERGY STORAGE↗
DOE OSTI2025

Solvated Electrons Have Multiple Personalities in Molten Salts

P-Crosscut: Solvated Electrons Have Multiple Personalities in Molten Salts [EFRC – MSEE] Alejandro Ramos-Ballesteros;1 Hung H. Nguyen;2 Kazuhiro Iwamatsu;3 Santanu Roy;4 Vyacheslav Bryantsev;4 Michael E. Woods;1 Ruchi Gakhar;1 Phillip Halstenberg;4 Bobby Layne;5 Jay A. LaVerne;6 Claudio J. Margulis:2* and James F. Wishart5* 1Idaho National Laboratory; 2The University of Iowa; 3Hunter College; 4Oak Ridge National Laboratory; 5Brookhaven National Laboratory; 6University of Notre Dame Abstract: The solvated (eS–) is a powerful reducing agent and one of the primary products of molten salt radiolysis. In these extreme high-temperature environments, the eS– can initiate cascades of redox processes that significantly alter the physical and chemical properties of a molten salt, posing challenges for molten salt reactor (MSR) performance and longevity. Consequently, mastering the fundamental behavior of the eS– could enable the design of specific molten salt mixtures with tailored Lewis acidities for controlling the speciation and chemical reactivity of the eS–, thereby mitigating its overall impact on MSR technologies. Here, we use time-resolved electron pulse radiolysis techniques for determining chemical kinetics and transient absorption spectra, combined with ab initio molecular dynamics simulations to explore the influence of multivalent metal cations on the fundamental speciation and distribution of eS– coordination environments.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2021

Thermochemical Modeling in Molten Fluoride Salts for Radionuclide Speciation

An important aspect of the licensing process for nuclear reactors is providing a reasonable assurance of safety to the general public. This includes modeling potential radionuclide releases from the reactor during normal operations and accident scenarios, which is known as the reactor’s source term. A new class of advanced (non-LWR) reactors are being developed which use molten salts as the coolant fluid. Because the molten salt coolant represents a credited barrier for radionuclide transport between the fuel and the environment, a necessary aspect of mechanistic source term (MST) analysis for the KP-FHR is modeling the thermochemistry of molten salts. Provided here is a review of the theory of the thermodynamic principles governing multicomponent phase equilibria, the background of molten salt thermochemistry research, and a summary of the thermochemical data relevant to the KP-FHR coolant salt, Li 2 BeF 4 , commonly referred to as “FLiBe”. A review of literature is followed by a brief introduction to methods that can be used to model the thermochemical behavior of molten salt mixtures. The methodology outlined is based on the use of a commercial thermodynamic modeling software called FactSage, which is one of only a few available softwares based on the modified quasichemical model(MQM), which is the recommended solution model for molten salts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

An Experimental Kinetics Study of Isopropanol Pyrolysis and Oxidation behind Reflected Shock Waves

Isopropanol has potential as a future bio-derived fuel and is a promising substitute for ethanol in gasoline blends. Even so, little has been done in terms of high-temperature chemical kinetic speciation studies of this molecule. To this end, experiments were conducted in a shock tube using simultaneous CO and H2O laser absorption measurements. Water and CO formation during isopropanol pyrolysis was also examined at temperatures between 1127 and 2162 K at an average pressure of 1.42 atm. Species profiles were collected at temperatures between 1332 and 1728 K and at an average pressure of 1.26 atm for equivalence ratios of 0.5, 1.0, and 2.0 in highly diluted mixtures of 20% helium and 79.5% argon. Species profiles were also compared to four modern C3 alcohol mechanisms, including the impact of recent rate constant measurements. The Li et al. (2019) and Saggese et al. (2021) models both best predict CO and water production under pyrolysis conditions, while the AramcoMech 3.0 and Capriolo and Konnov models better predict the oxidation experimental profiles. Additionally, previous studies have collected ignition delay time (τign) data for isopropanol but are limited to low pressures in highly dilute mixtures. Therefore, real fuel–air experiments were conducted in a heated shock tube with isopropanol for stoichiometric and lean conditions at 10 and 25 atm between 942 and 1428 K. Comparisons to previous experimental results highlight the need for real fuel–air experiments and proper interpretation of shock-tube data. The AramcoMech 3.0 model over predicts τign values, while the Li et al. model severely under predicts τign. The models by Capriolo and Konnov and Saggese et al. show good agreement with experimental τign values. A sensitivity analysis using these two models highlights the underlying chemistry for isopropanol combustion at 25 atm. Additionally, modifying the Li et al. model with a recently measured reaction rate shows improvement in the model’s ability to predict CO and water profiles during dilute oxidation. Finally, a regression analysis was performed to quantify τign results from this study.

09 BIOMASS FUELS↗
DOE OSTI2021

Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging

Dissolved Mn(II) in the hydrothermal plume is known to be microbially oxidized to form Mn(III/IV) oxides, and the Mn oxides scavenge other trace elements in seawater. In the GEOTRACES GP16 cruise, dissolved Mn (dMn) and particulate Mn (pMn) were found to be transported over 4000 km westwards from the Southern Eastern Pacific Rise. Previous studies in this plume showed different removal rates of dMn and pMn as well as pMn size distribution between the near-field (<80 km from the ridge axis) and far-field (>80 km) plumes. In order to understand Mn cycling in these plumes, spatial distribution, oxidation states, and mineral structures of Mn in small size fraction (SSF; 0.8–51 μm) and large size fraction (LSF; >51 μm) particles from the near-field and far-field plumes were examined using micro X-ray fluorescence spectrometry (μ-XRF), X-ray absorption near-edge structure spectroscopy (XANES), chemical species mapping, and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the near-field plume, pMn in the SSF is dominated by oxidized Mn with Mn(III) fractions of ~30%. They are a mixture of δ-MnO 2 and triclinic birnessites that is known to be formed as a result of autocatalytic Mn(II) oxidation at the surface of freshly-formed δ-MnO2, suggesting that both microbial and autocatalytic Mn oxidation occur in the near-field plume. The LSF pMn in the near-field plume is also oxidized and often found in large aggregates several hundreds of μm in size. These aggregates settle out in the near-field and during transport, and are not found in the far-field plume. In the far-field plume where Mn oxides are not newly formed, pMn in the SSF is oxidized, but their Mn(III) fractions are smaller than in the near-field pMn. Unlike the SSF, the far-field plume LSF pMn is dominated by reduced Mn, implying very slow aggregation of pMn in the far-field plume. The different characteristics of pMn between the near-field and far-field plumes affect its scavenging of other trace elements. In the near-field plume, Co, Mo, 231 Pa are associated with pMn, but not in the far-field plume. 231 Pa is adsorbed to pFe rather than pMn in the far-field plume, and Pb is adsorbed to pFe in the entire plume. The result shows that freshly-formed Mn oxides in the near-field plume have higher scavenging capacity than the far-field plume pMn. Our findings suggest that the mineralogical age of Mn oxides may be an important parameter that controls the scavenging of many other trace elements and isotopes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Impact of iodide ions on the speciation of radiolytic transients in molten LiCl–KCl eutectic salt mixtures

The fate of fission-product iodine is critical for the deployment of next generation molten salt reactor technologies, owing to its volatility and biological impacts if it were to be released into the environment. To date, little is known on how ionizing radiation fields influence the redox chemistry, speciation, and transport of iodine in high temperature molten salts. Here we employ picosecond electron pulse irradiation techniques to elucidate for the first time the impact of iodide ions (I – ) on the speciation and chemical kinetics of the primary radiation-induced transient radicals generated in molten chloride salt mixtures (e S – and Cl 2 ˙– ) as a function of temperature (400–700 °C). In the presence of I – ions (≥ 1 wt% KI in LiCl–KCl eutectic), we find that the transient spectrum following the electron pulse is composed of at least three overlapping species: the e S – and the Cl 2 ˙– and ICl ˙– radical anions, for which a deconvoluted spectrum of the latter is reported here for the first time in molten salts. This new transient spectrum was consistent with gas phase density functional theory calculations. The lifetime of the e S – was unaffected by the addition of I – ions. The newly observed interhalogen radical anion, ICl˙ – , exhibited a lifetime on the order of microseconds over the investigated temperature range. The associated chemical kinetics indicate that the predominate mechanism of ICl˙ – decay is via reaction with the Cl 2 ˙– radical anion. The iodine containing product of this reaction is expected to be ICl 2 – , which will have implications for the transport of fission-product iodine in MSR technologies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Mapping the structural trends in zinc aluminosilicate glasses

The structure of zinc aluminosilicate glasses with the composition (ZnO) x (Al 2 O 3 ) y (SiO 2 ) 1-x-y , where 0 ≤ x < 1, 0 ≤ y < 1, and x + y < 1, was investigated over a wide composition range by combining neutron and high-energy x-ray diffraction with 27 Al magic angle spinning nuclear magnetic resonance spectroscopy. The results were interpreted using an analytical model for the composition-dependent structure in which the zinc ions do not act as network formers. Four-coordinated aluminum atoms were found to be in the majority for all the investigated glasses, with five-coordinated aluminum atoms as the main minority species. Mean Al–O bond distances of 1.764(5) and 1.855(5) Å were obtained for the four- and five-coordinated aluminum atoms, respectively. The coordination environment of zinc was not observed to be invariant. Instead, it is dependent on whether zinc plays a predominantly network-modifying or charge-compensating role and, therefore, varies systematically with the glass composition. The Zn–O coordination number and bond distance were found to be 4.36(9) and 2.00(1) Å, respectively, for the network-modifying role vs 5.96(10) and 2.08(1) Å, respectively, for the charge-compensating role. The more open coordination environment of the charge-compensator is related to an enhanced probability of zinc finding bridging oxygen atoms as nearest-neighbors, reflecting a change in the connectivity of the glass network comprising four-coordinated silicon and aluminum atoms as the alumina content is increased.

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

Multiparameter optical fiber sensing for energy infrastructure through nanoscale light–matter interactions: From hardware to software, science to commercial opportunities

Monitoring of energy infrastructure through robust yet economical sensing platforms is becoming an area of increased importance, with ubiquitous applications including the electrical grid, natural gas and oil transportation pipelines, H2 infrastructure (storage and transportation), carbon storage, power generation, and subsurface environments. Plasmonic and functional nanomaterial enabled fiber optic sensors show excellent promise for a wide range of sensing applications due to their versatility to be engineered for specific analytes of interest while retaining inherent advantages of the optical fiber sensor platform. Through the design of novel sensing layers, the optical transduction mechanism and wavelength dependence can also be tailored for ease of integration with low-cost interrogation systems enabling an inexpensive yet highly functional optical fiber sensing platform. In addition, recent advances in artificial intelligence and machine learning theoretical methods have been leveraged to simultaneously extract multiple parameters through multi-wavelength interrogation such that unique wavelengths can also serve as unique sensing elements, analogous to electronic nose sensor technologies. The concept of an optical fiber based “photonic nose” via multiple interrogation wavelengths and/or sensor nodes offers a compelling platform technology to realize multiparameter speciation of chemical analytes within complex gas mixtures. In this Perspective, we further generalize the notion of multiparameter sensing through the novel “photonic nervous system” concept based upon low-cost, functionalized optical fiber sensor probes monitoring a variety of distinct analyte classes (physical, chemical, electromagnetic, etc.) simultaneously to provide broad situational awareness via integrated sensors.

Su, Yang-Duan (ORCID:0000000214820902)↗
DOE OSTI2024

Investigation of Frozen Chemistry for Molten Salt Reactors (MSRs)

Understanding accident progression and the potential/conditions for fission product release from fuel is necessary to evaluate safety for any nuclear reactor system. Molten Salt Reactors (MSRs) under development need such analysis to support safety evaluations. Fission product chemistry specific to MSR concepts is a critical area that introduces distinct considerations relative to the current state-of-knowledge in reactor safety, primarily developed for water-moderated nuclear reactor systems. In Light Water Reactor (LWR) systems, it is necessary to capture the chemical interaction of fission products with the reactor evironment, containment and confinement systems. The overall effects at this point are relatively well understood for the purposes of performing safety evaluations. A key insight from LWR studies is that fission product chemical behavior can be reasonably captured by modeling approaches where the chemistry is "frozen". These modeling approaches assume that radionuclide reaction and speciation can be represented by chemical classes, each with characteristic transport behavior that is invariant under a broad range of thermochemical conditions. However, radionuclides can exhibit a range of behavior in the liquid salt-melt phase of the coolant used in MSRs. Radionuclides, salt, and the metal containment surfaces (i.e. pipes) can co-exist in dynamic equilibrium that could evolve with small system mass changes. A detailed investigation to the degree the equilibrium state can dynamically evolve with changes in the conditions of the molten salt mixture has not been previously conducted. It is currently not well understood where frozen chemistry assumptions are valid. Expanding the state-of-knowledge in this regard is relevant to better assessing the range of chemical effects that should be incorporated as part of MSR safety assessments. This investigation used the Oak Ridge Isotope GENeration (ORIGEN) module of the Standardized Computer-Analysis for Licensing Evaluation (SCALE) code to generate simulated radionuclide inventories for the MSR Experiment (MSRE) and then modeled reactor chemical speciation using the Molten Salt Thermodynamic Database – Thermochemical (MSTDB-TC) coupled with Thermochimica. The effect of composition variation during decay of fission product inventory in a molten salt over a period of 500 days prolonged post- at multiple temperatures was studied. Mass fractions for fluorine and berilium were varied in order to probe the effects of free fluorine control. Finally, speciation of fluoride reactors were showed by comparing MSRE readionuclide inventories with a FLiBe based molten salt breeder reactor (MSBR). The results showed that fission product mass change has little effect on phase mass changes and vapor pressures for fluoride species, but differ with varying carrier and fuel salt compositions. However, iodine species were found to have a vapor pressure not only dependent on temperature, but also the free fluorine potential, releasing iodine when the free fluorine potential is equal to the iodine inventory. This observation, however, arose under free fluorine potentials that are very unlikely to be realized in typical molten salt mixtures. Despite this observation, temperature was found to be the dominant parameter that drove phase change and fission product species vapor pressure. The results indicate that the current frozen chemistry approach is adequate for MSR analysis.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗