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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Pathogenesis of Chapare Virus in Cynomolgus Macaques

Chapare virus (CHAPV) is an emerging New World arenavirus that is the causative agent of Chapare hemorrhagic fever (CHHF) responsible for recent outbreaks with alarmingly high case fatality rates in Bolivia near the Brazilian border. Here, we describe a nonhuman primate (NHP) model of CHHF infection which represents an essential tool to understand this emerging biological threat agent. Cynomolgus macaques challenged intravenously with CHAPV develop clinical disease, which recapitulates several key features of human CHHF. All subjects lost weight and had clinical scores following CHAPV challenge. Notably, one of four NHPs developed lethal disease with viral hepatitis and hemorrhagic features. Clinical chemistry and hematology revealed leukopenia, anemia, thrombocytopenia, and increased transaminase levels. In all four subjects, viremia was detectable for the first week following challenge and viral RNA was detectable in serum and many tissues persisting 35 days-post challenge. Several medical countermeasures (MCM) have efficacy against CHAPV infection in vitro, but the current model for MCM testing and approval of new drugs is reliant on the availability of animal models. This work lays the foundation for future CHHF MCM development.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Structural, magnetic, and electronic evolution of the spin-ladder system BaFe 2 S 3-x Se x with isoelectronic substitution

We reWe report experimental studies of a series of BaF e 2 S 3 - x Se x ( 0 ≤ $x$ ≤ 3 ) single crystals and powder specimens using x-ray diffraction, neutron-diffraction, muon-spin-relaxation, and electrical transport measurements. A structural transformation from $C$ $mcm$ ( BaFe 2 Se 3 ) to $P$ $nma$ ( BaFe 2 Se 3 ) was identified around $x$ = 0.7 - 1 . Neutron-diffraction measurements on the samples with $x$ = 0.2, 0.4, and 0.7 reveal that the Néel temperature of the stripe antiferromagnetic order is gradually suppressed from ~120 to 85 K, while the magnitude of the ordered Fe 2+ moments shows very little variation. Similarly, the block antiferromagnetic order in BaFe 2 Se 3 remains robust for 1.5 ≤ $x$ ≤ 3 with negligible variation in the ordered moment and a slight decrease of the Néel temperature from 250 K ( $x$ = 3 ) to 225 K ( $x$ = 1.5 ). The sample with $x$ = 1 near the $C$ $mcm$ and $P$ $nma$ border shows coexisting, two-dimensional, short-range stripe- and block-type antiferromagnetic correlations. The system remains insulating for all $x$ , but the thermal activation gap shows an abrupt increase when traversing the boundary from the $C$ $mcm$ stripe phase to the $P$ $nma$ block phase. The results demonstrate that the crystal structure, magnetic order, and electronic properties are strongly coupled in the BaFe 2 S 3-x Se x system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Benefit FOA FY2015 - Solid State Magnetocaloric Air Conditioner (Final Report)

The active magnetic refrigeration (AMR) cycle holds great promise to reduce energy consumption of space cooling and heating. It is estimated that it could achieve up to 25% improvement in energy efficiency over conventional vapor compression systems. Prototypes have been built and demonstrated the working principles and energy benefits of the technology. These prototypes however were of low specific cooling power, defined as cooling power obtainable from unit mass of magnetocaloric materials (MCM). Specific cooling power is inversely proportional to the cost of the system. Therefore, for the magnetocaloric technology to be commercially viable, the specific cooling power must be increased. To increase the specific cooling power, for any MCM, the frequency of operation must increase. However, the maximum frequency that an AMR can operate at is limited by the residence time that is required to transfer heat in and out of the regenerator during the cold and got blows. This time length is dependent on the thermal conductivity of the heat transfer medium. The higher the thermal conductivity of the heat transfer medium, the faster heat can be transferred between the medium and the MCM.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Using numerical methods to screen magnetocaloric materials in an active magnetic regenerative cycle

A 2-dimensional numerical model of a room temperature operating Active Magnetic Regenerator (AMR) that comprises of a regenerator, hot and cold heat exchangers, heat transfer fluid is developed. The regenerator is made of a magnetocaloric material (MCM) which heats up upon applying a magnetic field, H, and cools down when the field is removed; thus, making it the most essential part of an AMR. The model takes experimentally measured ΔT ad (H,T) and the C p (H,T) data as input and provides quantitative performance metrics of the magnetic cooling system, such as ΔT span and the cooling load, as output. With this model, it is possible to assess a wide range of MCMs in an AMR. 4 different MCMs were investigated using this model in terms of their ΔT span and the cooling loads—LaFe 10.96 Co 0.97 Si 1.07 , MnFeP (1-x) As (x) and AlFe 2 B 2 and Gd. During the screening of MCMs, all the important operating conditions of the device were fixed such as the fluid flow rate, ambient temperature, cycle duration, magnetic field strength. Our results indicate that Gd exhibits the maximum ΔT span with respectable cooling load, while AlFe 2 B 2 generates the lowest ΔT span . Even though LaFeCoSi compound did not perform as well as Gd, it could be the MCM choice for the realization of magnetic refrigeration on a global scale due to its much lower cost.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Probing the Core–Shell Organization of Nanoconfined Methane in Cylindrical Silica Pores Using In Situ Small-Angle Neutron Scattering and Molecular Dynamics Simulations

Determining the structure of nanoconfined fluids is essential for predicting the fate of these fluids in subsurface geologic formations with nanoporous features and for engineering novel nanoporous materials for storing compressed gases. In this study, we probe the structure of nanoconfined methane at pressures in the range of 15–100 bar using in situ small-angle neutron scattering (SANS) measurements and molecular dynamics (MD) simulations. The structure of methane is probed in MCM-41 and SBA-15 with cylindrical pores and diameters of 3.3 and 6.8 nm, respectively. In situ SANS measurements and MD simulations showed that the confined methane molecules are organized in a core–shell structure, with the shell arising from the adsorption of methane molecules on the silica surface. The shell thicknesses of the adsorbed deuterated methane (CD4) molecules in MCM-41 obtained by SANS measurements are 1.4 ± 0.5, 2.1 ± 0.1, 3.2 ± 0.8, 4.0 ± 0.3, and 6.0 ± 0.7 Å at equilibrated pressures of 15.6, 35.6, 55.5, 73.3, and 95.7 bar, respectively. The shell thicknesses of the adsorbed CD4 layer in SBA-15 pores are 2.7 ± 0.5, 4.3 ± 0.7, 6.6 ± 0.7, 10.2 ± 0.3, and 14.6 ± 0.8 Å at equilibrated pressures of 15.5, 32.7, 52.4, 70, and 99.5 bar, respectively. These experimental results are in close agreement with the results predicted from MD simulations. Adsorption of methane molecules on the silica surfaces is primarily driven by van der Waals interactions between the methane molecules and the hydroxyl groups on the silica surface, while electrostatic interactions play a minor role. In conclusion, the experimental and simulation approaches described in this study provide fundamental insights into the organization of confined gases using methane as a specific example in the context of compressed fluid storage in natural and engineered materials for adaptive energy use.

03 NATURAL GAS↗
DOE OSTI2020

Factors Determining Selectivity of Acid- and Base-Catalyzed Self- and Cross-Condensation of Acetone and Cyclopentanone

In a combined kinetics and density functional theory (DFT) study, we have explored several factors that affect the selectivity of acid- and base-catalyzed self- and cross-aldol condensation of acetone (ACE) and cyclopentanone (CPO). These factors include competitive adsorption, molecular structure, and electron polarization of the two ketones on the catalyst surface. Here, kinetic analysis shows that on MgO, self-condensation of both ACE and CPO is limited by the initial unimolecular enolization step. Accordingly, CPO exhibits a higher self-condensation rate than ACE due to the more favorable α-C–H abstraction by the basic O site. The thermodynamic parameters derived from the kinetic analysis indicate that under cross-condensation reaction conditions, the MgO surface fraction covered by CPO is significantly higher than that covered by ACE. Therefore, the product distribution is dominated by [CPO]-activated products ([CPO]CPO + [CPO]ACE). Also, for a given enolate (indicated as [CPO] or [ACE]), the higher surface coverage of CPO leads to enhanced C–C coupling with CPO as the electrophile ([CPO]CPO > [CPO]ACE; [ACE]CPO > [ACE]ACE). By contrast, for both acid catalysts investigated, the rate-limiting step is the bimolecular C–C coupling, with aspects of this step depending on the density of acid sites. That is, on the high-acid-density MCM-41-SO 3 H catalyst, condensation follows a bimolecular dual-site mechanism (Langmuir–Hinshelwood model). On this catalyst surface, the ACE coverage is higher than that of CPO, which causes a higher selectivity for those products in which ACE is the electrophile ([CPO]ACE > [CPO]CPO; [ACE]ACE > [ACE]CPO). Steric hindrance is another factor that affects selectivity in the same way, favoring products in which the electrophile is ACE since it presents a lower steric hindrance to C–C coupling than CPO. Therefore, the same sequence of products is obtained for the low-acid-density MCM-41-SO 3 H catalyst, which proceeds on a single-acid site with the other molecule in the liquid phase (Eley–Rideal model). In this case, the electrophile coverage is not relevant, but the steric hindrance is, yielding the same trend as above ([CPO]ACE > [CPO]CPO; [ACE]ACE > [ACE]CPO).

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

Evaluation of Subetadex-α-methyl, a Polyanionic Cyclodextrin Scaffold, as a Medical Countermeasure against Fentanyl and Related Opioids

Subetadex-α-methyl (SBX-Me), a modified, polyanionic cyclodextrin scaffold, has been evaluated for its utilization as a medical countermeasure (MCM) to neutralize the effects of fentanyl and related opioids. Initial in vitro toxicity assays demonstrate that SBX-Me has a nontoxic profile, comparable to the FDA-approved cyclodextrin-based drug Sugammadex. Pharmacokinetic analysis showed rapid clearance of SBX-Me with an elimination half-life of ~7.4 h and little accumulation in major organs. SBX-Me was also evaluated for its ability to counteract the effects of fentanyl, carfentanil, and remifentanil in rats. Recovery times in rats exposed to sublethal fentanyl doses were found to be shorter when treated with SBX-Me after opioid exposure. The recovery times were reduced from ~35 to ~17 min for fentanyl, ~172 to ~59 min for carfentanil, and ~18 to ~12 min for remifentanil. SBX-Me increased the elimination half-life for fentanyl and remifentanil from 5.37 to 6.42 h and 8.24 to 9.74 h, respectively. These data support SBX-Me as a solid platform from which further research can be launched for the development of a MCM against the effects of fentanyl and its analogs. Furthermore, the data suggests that SBX-Me and other analogs are attractive candidates as broad spectrum opioids targeting MCMs.

Chemistry↗
DOE OSTI2026

ML–Enabled FPGA Framework for Fast Quantum State Discrimination in Mid-Circuit Measurement Regimes

Accurate and low-latency quantum state discrimination is essential for protocols involving mid-circuit measurement (MCM) and conditional feed-forward. In superconducting quantum systems, conventional readout pipelines transfer measurement data to host processors for post-processing, introducing millisecond-scale delays that far exceed qubit coherence times. To overcome this bottleneck, we present an in-situ machine learning (ML) inference engine implemented on an FPGA for real-time quantum state discrimination. Our design performs inference directly on digitized readout signals with 40 ns latency, supports both qubit and qutrit readout, and enables conditional operations without host-side intervention. This capability is critical for MCM and for feedback-driven protocols such as quantum error correction. We validate the system on superconducting transmon hardware, demonstrating robust discrimination fidelity across multiple qubit and qutrit channels. We further demonstrate conditional qutrit logic driven by FPGA-resident classification, highlighting the potential of low-latency ML-on-FPGA control for NISQ applications and scalable fault-tolerant quantum computing.

Vora, Neel [Lawrence Berkeley National Laboratory ↗
DOE OSTI2023

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL Radiological Response Training Range

This assessment uses screening-level models to calculate potential environmental impacts from proposed tests at the Idaho National Laboratory (INL) Radiological Response Training Range (RRTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K2O, LaBr3, KBr, Cu, Zr, F, Ga, Ga2O3, NaNO2, Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface-soil impacts were calculated with the computer program mixing-cell model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated assuming 12 tests are conducted annually using all 11 material types for a period of 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer-code input, output, executable files, batch files, scripts, and spreadsheet files are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS). It is highly unlikely the test scenarios evaluated in this ECAR will adversely impact human health based on comparisons of calculated dose and concentration against regulatory standards and risk-based screening levels. Conservative estimates of dose to workers and the public from atmospheric transport of possible radionuclide releases are far below federal radiation protection standards. Conservative estimates of potential contaminant concentrations in groundwater are less than federal drinking water standards or screening levels. Predicted radionuclide concentrations in surface soils are below risk-based screening levels, except for Ge-68 (material Ga-68) for the worker. The Ge-68 soil concentration can be made less than the worker PRG, if the number of annual tests using Ga-68 is reduced from 12 to 6. However, the sum of ratios still exceeds one because of the high K-40 ratio. If the EF of the worker (number of days the worker is in the contaminated testing area) is reduced from 225 days/yr (default value for full time worker) to 112 days/yr, the Ge-68 ratio is less than one and the sum of ratios is less than one. Actual radiation doses and groundwater and surface-soil concentrations are likely to be much less than those calculated because of the conservative assumptions and parameters employed in the modeling. For example, atmospheric-transport calculations assume the entire inventory of each material type is readily released to the atmosphere and no plume deposition, depletion, or radioactive decay occurs during transport. The calculations also assume the same meteorological conditions (e.g., wind velocity, wind direction, stability class) that produce the maximum 95th percentile concentration (i.e., concentration representing the 95th percentile of a distribution of concentrations derived from 3 years of hourly meteorological data) at each receptor location are the same for all 12 tests during the year, and each receptor is assumed to be present during all 12 tests. The surface-soil assessment assumes the entire inventory of each test is deposited in the top 5 cm of soil. No atmospheric dispersal is assumed, and the radionuclides are subject only to leaching and radioactive decay. The groundwater-pathway modeling is conservative in that it is one-dimensional in the unsaturated zone (no lateral spreading/dilution) and assumes the entire inventory of contaminants infiltrates into the ground at the same location for every test. This is especially conservative for particulate radionuclides because they would have to dissolve or corrode first and some would be dispersed into the atmosphere. The groundwater receptor is also assumed to consume water directly from a hypothetical well positioned in the location of maximum concentration. In addition, conservative degradation rates were used, and volatilization was not considered for the nonradioactive chemical

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL National Security Test Range

This assessment uses screening-level models to calculate potential environmental impacts from proposed tests at two locations at the Idaho National Laboratory (INL) National Security Test Range (NSTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K 2 O, LaBr 3 , KBr, Cu, Zr, F, Ga, Ga 2 O 3 , NaNO 2 , Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface-soil impacts were calculated with the computer program mixing-cell model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated based on the assumption that 12 tests are conducted annually using all 11 material types for 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer-code input, output, executable files, batch files, scripts, and spreadsheet files, are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS). It is highly unlikely the test scenarios evaluated in this ECAR will adversely impact human health based on comparisons of calculated dose and concentration against regulatory standards and risk-based screening levels. Conservative estimates of dose to workers and the public from atmospheric transport of possible radionuclide releases are far below federal radiation protection standards. Conservative estimates of potential contaminant concentrations in groundwater are less than federal drinking water standards or screening levels. Predicted radionuclide concentrations in surface soils are below risk-based screening levels, except for Ge-68 (material Ga-68) for the worker. The Ge-68 soil concentration can be made less than the worker PRG, if the number of annual tests using Ga-68 is reduced from 12 to 6. However, the sum of ratios still exceeds one because of the high K-40 ratio. If the EF of the worker (number of days the worker is in the contaminated testing area) is reduced from 225 days/yr (default value for full time worker) to 112 days/yr, the Ge-68 ratio is less than one and the sum of ratios is less than one. Actual radiation doses and groundwater and surface-soil concentrations are likely to be much less than those calculated because of the conservative assumptions and parameters employed in the modeling. For example, atmospheric-transport calculations assume the entire inventory of each material type is readily released to the atmosphere and no plume deposition, depletion, or radioactive decay occurs during transport. The calculations also assume the same meteorological conditions (e.g., wind velocity, wind direction, stability class) that produce the maximum 95th percentile concentration (i.e., concentration representing the 95th percentile of a distribution of concentrations derived from 3 years of hourly meteorological data) at each receptor location are the same for all 12 tests during the year, and each receptor is assumed to be present during all 12 tests. The surface-soil assessment assumes the entire inventory of each test is deposited in the top 5 cm of soil. No atmospheric dispersal is assumed, and the radionuclides are subject only to leaching and radioactive decay. The groundwater-pathway modeling is conservative in that it is one-dimensional in the unsaturated zone (no lateral spreading/dilution) and assumes the entire inventory of contaminants infiltrates into the ground at the same location for every test. This is especially conservative for particulate radionuclides because they would have to dissolve or corrode first and some would be dispersed into the atmosphere. The groundwater receptor is also assumed to consume water directly from a hypothetical well positioned in the location of maximum concentration. In addition, conservative degradation rates were used, and volatilization was not considered for the nonradradioactive chemicals modeled. And finally, the calculations assume all 12 tests will be performed at the same place at both locations, and all 11 radioactive material types will be used for each test. This is conservative because it is anticipated that no more than two material types will be used per test.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2024

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL Radiological Response Training Range

This assessment uses screening level models to calculate potential environmental impacts from proposed tests at the Idaho National Laboratory (INL) Radiological Response Training Range (RRTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K 2 O, LaBr 3 , KBr, Cu, Zr, F, Ga, Ga 2 O 3 , NaNO 2 , Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface-soil impacts were calculated with the computer program Mixing-Cell Model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated based on the assumption that 12 tests are conducted annually using all 11 material types for a period of 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer code input, output, executable files, batch files, scripts, and spreadsheet files are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS).

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2024

Assessment of Potential Dose and Environmental Impacts from Proposed Testing at the INL National Security Test Range

This assessment uses screening level models to calculate potential environmental impacts from proposed tests at two locations at the Idaho National Laboratory (INL) National Security Test Range (NSTR) site. Proposed tests could be conducted using 11 different radioactive material types that include K 2 O, LaBr 3 , KBr, Cu, Zr, F, Ga, Ga 2 O 3 , NaNO 2 , Ga-68, and Tc-99m. The tests could potentially release radioactive material to the atmosphere and radionuclides and other contaminants to the soil, which could leach into the unsaturated zone and migrate to the aquifer. Atmospheric transport of radionuclides to potential human receptors and time-integrated air concentrations were calculated with a Gaussian plume model and three years of hourly meteorological data. Potential surface soil impacts were calculated with the computer program Mixing-Cell Model (MCM). Groundwater impacts were calculated with the computer programs MCM and GWSCREEN. Radiological doses from potential atmospheric releases were calculated for public receptors off the INL Site and for workers at nearby INL facilities. Results were compared to regulatory dose limits. Maximum potential groundwater concentrations were estimated in the aquifer below the NSTR site and compared to drinking water standards or risk-based screening levels for resident tap water. Soil concentrations were calculated and compared to risk-based screening levels for workers and potential future residents. All impacts were estimated based on the assumption that 12 tests are conducted annually using all 11 material types for 15 years. This document provides the resources to enable a subject matter expert in the field of environmental assessments to replicate the modeling and calculations. The methodology and parameters are presented in the text. All electronic files, including computer code input, output, executable files, batch files, scripts, and spreadsheet files, are contained in a zip file that can be accessed by selecting “Additional Information” (select Native File) in the INL Electronic Document Management System (EDMS).

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2024

Mid-circuit Measurement & Branching in QSCOUT: A Ping-Pong Teleportation Exemplar Program

This document is intended to help users program the new mid-circuit measurement (MCM) and classical branching capabilities of the Quantum Scientific Computing Open User Testbed (QSCOUT). Here, we present and explain an exemplar “ping-pong teleportation” program that makes repeated MCM and branching calls. The program is written in Jaqal, the quantum assembly language used by QSCOUT. This document is intended to accompany a companion Jupyter notebook Exemplar_one_bit_teleportation_pingpong.ipynb.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Sentinel protist taxa of the McMurdo Dry Valley lakes, Antarctica: a review

High-latitude meromictic lakes such as those in the Antarctic McMurdo Dry Valleys (MDV) harbor aquatic ecosystems dominated by the microbial loop. Within this habitat, which is limited year-round by light and nutrients, protists, or single celled eukaryotes, play outsized roles in the food web as the dominant primary producers and the apex predators. Thus, the MDV lake ecosystem represents an ideal system to study the role of sentinel protist taxa in carbon and nutrient cycling. The perennially ice-covered lakes are part of the McMurdo Long Term Ecological Research (McM LTER; mcmlter.org) established in 1993. In this review we will highlight the diversity and trophic roles of the MDV lake protist community and compare environmental factors driving spatiotemporal patterns in key protist taxa in two lakes within the McM LTER, Lakes Bonney and Fryxell. We will then discuss lessons learned from manipulated experiments on the impact of current and future climate-driven environmental change on sensitive protist taxa. Last, we will integrate knowledge gained from 25 years of lab-controlled experiments on key photosynthetic protists to extend our understanding of the function of these extremophiles within the MDV aquatic food webs. Our research group has studied the distribution and function of the MDV microbial community for nearly two decades, training the next generation of scientists to tackle future problems of these globally significant microbes. This review article will also highlight early career scientists who have contributed to this body of work and represent the future of scientific understanding in the Anthropocene.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Size Dependence of the Tetragonal to Orthorhombic Phase Transition of Ammonia Borane in Nanoconfinement

We have investigated the thermodynamic property modification of ammonia borane via nanoconfinement. Two different mesoporous silica scaffolds, SBA-15 and MCM-41, were used to confine ammonia borane. Using in situ Raman spectroscopy, we examined how pore size influences the phase transition temperature from tetragonal (I4mm) to orthorhombic (Pmn21) for ammonia borane. In bulk ammonia borane, the phase transition occurs at around 217 K; however, confinement in SBA-15 (with ~8 nm pore sizes) reduces this temperature to approximately 195 K, while confinement in MCM-41 (with pore sizes of 2.1–2.7 nm) further lowers it to below 90 K. This suppression of the phase transition as a function of pore size has not been previously studied using Raman spectroscopy. The stability of the I4mm phase at a much lower temperature can be interpreted by incorporating the surface energy terms to the overall free energy of the system in a simple thermodynamic model, which leads to a significant increase in the surface energy when transitioning from the tetragonal phase to the orthorhombic phase.

Najiba, Shah↗
DOE OSTI2021

Structure and reactive properties of Nb-impregnated two-dimensional pillared MWW zeolites for total oxidation of volatile organic compounds

In this work, the structure and reactive properties of niobium (Nb)-impregnated MWW-type materials were evaluated for gas-phase total oxidation of volatile organic compounds, including BTX (benzene, toluene and o -xylene). The role of the type of structure (two or three-dimensional) and the loading of Nb were considered. The results indicated most Nb species with a tetrahedral coordination on the external surfaces of both two- and three-dimensional zeolites, together with a minimal contribution of octahedral extra-framework Nb 2 O 5 species. The texture and Nb content played a key role in the gas-phase total oxidation of BTX. With the same Nb content (5 wt%), the pillared zeolite exhibited a higher specific surface, larger pore volume and mesopores between the MWW nanosheets when compared to the MCM-22 zeolites, which resulted in high accessibility of the reactant molecules to the active sites, reflected in higher BTX conversion at lower and higher temperatures (50–300 °C). The best performance was achieved with the pillared zeolite (10 wt% Nb), reaching a BTX conversion at 300 °C of 92%, 69% and 58%, respectively. Here, the catalyst was stable for up to 30 h of reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Kinetics of 2-Methylfuran Acylation with Fatty Acid Anhydrides for Biorenewable Surfactants

Friedel–Crafts acylation using long-chain fatty acid derivatives and biomass-derived furans is the key reaction to produce “alkyl furan ketones”, an important precursor for biorenewable oleo-furan surfactants. In this work, the steady-state acylation kinetics and reaction mechanism were investigated using a model system of 2-methylfuran and n-octanoic anhydride in a fixed-bed tubular reactor using Al-MCM-41, a mesoporous aluminosilicate. An apparent activation energy (15.5 ± 1.4 kcal mol –1 ) was obtained for the formation of the acylated product, 2-octanoyl-5-methylfuran (2O5MF), for a temperature range of 348–408 K. Furthermore, the apparent reaction rate orders were ~0.6 and ~0.5 in the 2-methylfuran and anhydride concentrations, respectively, while near-zero apparent rate orders were measured in the product concentrations, indicating negligible product inhibition. An Eley–Rideal catalytic acylation mechanism was proposed to explain the experimentally observed apparent rate orders.

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

B‐MWW Zeolite: The Case Against Single‐Site Catalysis

Abstract Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron‐containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B 2 (OH) x O (3− x /2) ( x= 0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM‐22 isomorphously substituted with boron (B‐MWW). Using 11 B solid‐state NMR spectroscopy, we show that the majority of boron species in B‐MWW exist as isolated BO 3 units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B‐MWW for ODH of propane falsifies the hypothesis that site‐isolated BO 3 units are the active site in boron‐based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium‐based catalysts and provides an important piece of the mechanistic puzzle.

Altvater, Natalie R.↗