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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Scanning Electrochemical Microscopy: An Evolving Toolbox for Revealing the Chemistry within Electrochemical Processes

The parallel development of ultramicroelectrodes (UMEs) and groundbreaking scanning probe microscopy techniques in the late 1980s led to the development of the scanning electrochemical microscope. Scanning electrochemical microscopy (SECM) was born from the idea of using a tiny electrode to measure the local electrochemical behavior at operating electrodes. From its foundations, the technique displayed an inherent versatility in measuring sample properties beyond topography. It allowed experimenters to measure and map chemical reactions occurring at diverse interfaces, from inspecting the reversibility of redox mediators at metal electrodes, to detecting the hallmarks of cellular respiration on living plant leaves. Related but distinct electrochemical scanning probe techniques, such as electrochemical atomic force microscopy (EC-AFM), scanning ion conductance microscopy (SICM), and scanning electrochemical cell microscopy (SECCM) have developed in parallel. These techniques have demonstrated exquisite spatial resolution down to the nanoscale regime. However, it is the proposition of this review that SECM remains unmatched at revealing the chemical aspects of electrochemistry. Furthermore, it is our intention to review and demonstrate that the versatile architecture of SECM continues to evolve and address fundamental and emerging challenges in the fields of energy storage and conversion, chemical biology, materials science, and environmental chemistry, among others.

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

Detection of the keto-enol tautomerization in acetaldehyde, acetone, cyclohexanone, and methyl vinyl ketone with a novel VUV light source

The discovery of enols in combustion environments and our atmosphere has garnered increasing attention to the many unanswered questions surrounding enol chemistry. The scarcity of experimental data concerning these enols renders combustion and atmospheric models with a lack of constraining parameters, leading to varying computational predictions. Experimental detection is difficult because mass spectrometry, a powerful tool for probing a wide variety of species, cannot distinguish between enols and their thermodynamically favorable ketone isomers. A solution to this ambiguity is to use tunable vacuum ultraviolet (VUV) light from a synchrotron to identify the presence of the enol by its lower ionization energy compared to the isomer. We present a tabletop-scale VUV light source that implements highly cascaded harmonic generation, a new regime of cascaded nonlinear optics, to provide a set of spectral lines spaced by 1.2 eV. We demonstrate that the variety of photon energies available allows us to detect the keto-enol tautomerization of four aldehydes and ketones. By combining this novel VUV light source with an established microreactor, we first revisit the formation of vinyl alcohol from acetaldehyde and confirm that the observed isomerization is indeed unimolecular. Secondly, we observe the thermal tautomerization of acetone to propen-2-ol for the first time. Finally, we observe the thermal tautomerization of cyclohexanone to 1-cyclohexenol and methyl vinyl ketone to 2-hydroxybutadiene, where the results are in good agreement with those reported at a synchrotron. Furthermore, our measurements can be used to constrain models, inform future experimental studies of enol reactivity, and potentially enhance current understanding of combustion and environmental chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Iron (IV) Formation and the pH Dependent Kinetics of the Fenton Reaction

Despite its widespread importance for biological and environmental chemistry and decades of study, the mechanism underlying the Fenton reaction is still a matter of some controversy. Here, to elucidate the pH dependence of this complex reaction, a new kinetic model is developed to explain the increase in rate and mechanistic shift that occurs from acidic to neutral conditions. This mechanism originated from a re-analysis of a previously proposed model, which neglected explicit iron speciation, leading to unrealistic rate constants. Accounting for speciation suggests a much faster formation rate of Fe(IV), which is estimated to be on the order of 10 6 M −1 s −1 . Expanding on prior kinetic studies that include speciation under acidic conditions, we propose a unified kinetic model that captures the pH-dependent rate acceleration in Fe(II) oxidation by H 2 O 2 , which is a significant step toward resolving the long-standing mechanistic ambiguity of Fenton chemistry.

Cohen, Liron [Lawrence Berkeley National Laborator↗
DOE OSTI2023

Novel gas exposure system for the controlled exposure of plants to gaseous hydrogen fluoride

Abstract Plants can serve as sensitive bioindicators of the presence of contaminant vapors in the atmosphere. This work describes a novel laboratory-based gas exposure system capable of calibrating plants as bioindicators for the detection and delineation of the atmospheric contaminant hydrogen fluoride (HF) as a preparatory step for monitoring release emissions. To evaluate changes in plant phenotype and stress-induced physiological effects attributed to HF alone, the gas exposure chamber must have additional controls to simulate otherwise optimal plant growth conditions including variables such as light intensity, photoperiod, temperature, and irrigation. The exposure system was designed to maintain constant growth conditions during a series of independent experiments that varied between optimal (control) and stressful (HF exposure) conditions. The system was also designed to ensure the safe handling and application of HF. An initial system calibration introduced HF gas into the exposure chamber and monitored HF concentrations by cavity ring-down spectroscopy for a 48-h period. Stable concentrations inside the exposure chamber were observed after approximately 15 h, and losses of HF to the system ranged from 88 to 91%. A model plant species ( Festuca arundinacea ) was then exposed to HF for 48 h. Visual phenotype stress-induced responses aligned with symptoms reported in the literature for fluoride exposure (tip dieback and discoloration along the dieback transition margin). Fluoride concentrations in exposed tissues compared to control tissues confirmed enhanced fluoride uptake due to HF exposure. The system described herein can be applied to other reactive atmospheric pollutants of interest in support of bioindicator research.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Time-resolved electrical potential pump – X-ray photoelectron spectroscopy probe developments for investigating dynamic processes occurring at electrochemical interfaces

Electrode–electrolyte interfaces are of critical importance in several fields, including renewable energy, corrosion, and environmental chemistry. However, investigating these interfaces under operational conditions poses considerable challenges due to the limitations of the instrumentation employed. While recent advancements in in situ and operando techniques have enhanced our comprehension of the steady-state properties of solid-liquid interfaces, the dynamic behaviors of these systems remain inadequately explored. This study introduces a time-resolved X-ray photoelectron spectroscopy (XPS) technique designed to capture transient reaction intermediates and charging dynamics at electrified interfaces. The presented proof-of-principle study demonstrates that electrochemical processes, represented by an equivalent electrical circuit (EEC) model, can be probed and understood using square wave voltage pulses of a potentiostat synchronized to the modified data acquisition of an XPS setup. This method offers a valuable alternative to traditional pump–probe techniques, facilitating the investigation of a broader range of electrochemical systems. A dedicated software package for analyzing time- and energy-resolved XPS with a focus on extracting parameters of the EEC is geared towards benchmarking different EECs in future real-world electrochemical experiments.

Electrochemistry↗
DOE OSTI2022

Near-Quantitative Predictions of the First-Shell Coordination Structure of Hydrated First-Row Transition Metal Ions Using K-Edge X-ray Absorption Near-Edge Spectroscopy

Understanding the solvation structure of transition metal ions is important due to its broad impact on the kinetics, stability, and reactivity in a variety of applications in geochemistry, biochemistry, energy storage, and environmental chemistry. Using water as the common ligand, we study the X-ray absorption pre-edge and near-edge spectra at the K-edge of a near-complete series of hydrated first-row transition metal ions with d-orbital occupancy ranging from d 2 to d 10 . Starting with optimized structures that were derived from an explicit solvation treatment at the density functional theory (DFT) level, we then compute the pre-edge X-ray absorption spectra at the metal ion K-edge at the time dependent density functional theory (TDDFT) and restricted active-space second-order perturbation theory (RASPT2) levels of theory. TDDFT calculations provide accurate results for spectra that are dominated by single excitations, while significant improvements were obtained with RASPT2 calculations that correctly distinguish between singly and doubly excited states, where relevant, with quantitative accuracy compared with experiment. We analyze and assign the dierent pre-edge features for each metal ion in order to reveal the impact of the variations in the d orbital occupancy on the rst-shell coordination environment. For completeness, we also report the lowest energy ligand-field d-d transitions for all the transition metal aqua ions considered in this study using complete active space second order perturbation theory (CASPT2).

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

Unraveling pH-Dependent Changes in Adsorption Structure of Uranyl on Alumina (012)

Mitigating uranium transport in groundwater is imperative for ensuring access to clean water across the globe. Here, in situ resonant anomalous X-ray reflectivity is used to investigate the adsorption of uranyl on alumina (012) in acidic aqueous solutions, representing typical U VI concentrations of contaminated water near mining sites. The analyses reveal that U VI adsorbs at two distinct heights of 2.4-3.2 and 5-5.3 angstrom from the surface terminal oxygens. The former is interpreted as the mixture of inner-sphere and outer-sphere complexes that adsorb closest to the surface. The latter is interpreted as an outer-sphere complex that shares one equatorial H 2 O with the terminal surface oxygen. With increasing pH, we observe an increasing prevalence of these outer-sphere complexes, indicating the enhanced role of the hydrogen bond that stabilizes adsorbed uranyl species. Finally, the presented work provides a molecular-scale understanding of sorption of uranyl on Al-based-oxide surfaces that has implications for environmental chemistry and materials science.

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

Light-driven C–H activation mediated by 2D transition metal dichalcogenides

C–H bond activation enables the facile synthesis of new chemicals. While C–H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C–H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C–C coupling mediated by 2D TMDCs to promote C–H activation and carbon dots synthesis. Our results shed light on 2D materials for C–H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Soil gas probes for monitoring trace gas messengers of microbial activity

Abstract Soil microbes vigorously produce and consume gases that reflect active soil biogeochemical processes. Soil gas measurements are therefore a powerful tool to monitor microbial activity. Yet, the majority of soil gases lack non-disruptive subsurface measurement methods at spatiotemporal scales relevant to microbial processes and soil structure. To address this need, we developed a soil gas sampling system that uses novel diffusive soil probes and sample transfer approaches for high-resolution sampling from discrete subsurface regions. Probe sampling requires transferring soil gas samples to above-ground gas analyzers where concentrations and isotopologues are measured. Obtaining representative soil gas samples has historically required balancing disruption to soil gas composition with measurement frequency and analyzer volume demand. These considerations have limited attempts to quantify trace gas spatial concentration gradients and heterogeneity at scales relevant to the soil microbiome. Here, we describe our new flexible diffusive probe sampling system integrated with a modified, reduced volume trace gas analyzer and demonstrate its application for subsurface monitoring of biogeochemical cycling of nitrous oxide (N 2 O) and its site-specific isotopologues, methane, carbon dioxide, and nitric oxide in controlled soil columns. The sampling system observed reproducible responses of soil gas concentrations to manipulations of soil nutrients and redox state, providing a new window into the microbial response to these key environmental forcings. Using site-specific N 2 O isotopologues as indicators of microbial processes, we constrain the dynamics of in situ microbial activity. Unlocking trace gas messengers of microbial activity will complement -omics approaches, challenge subsurface models, and improve understanding of soil heterogeneity to disentangle interactive processes in the subsurface biome.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2024

The influence of exploration activities of a potential lithium mine to the environment in Western Serbia

The proposed exploitation of the Jadar Valley lithium/borate deposit in Serbia, by the Rio Tinto Corporation, indicates that it would become large-scale processing of boron- and lithium-containing ore. It would be one of the world’s very first lithium mines in populated and agricultural area. The company claims that the envisioned mining will be in accordance with environmental protection requirements. The Jadar Valley deposits have been claimed to cover 90% of Europe’s current lithium needs. Yet, local opposition to the mining has arisen due to potential devastating impacts on groundwater, soil, water usage, biodiversity loss, and waste accumulation. Research drilling by the mining company has already produced environmental damage, with mine water containing high levels of boron leaking from exploratory wells and causing crops to dry out. Furthermore, our investigations reveal substantially elevated downstream concentrations of boron, arsenic, and lithium in nearby rivers as compared to upstream regions. Additionally, here we show that soil samples exhibit repeated breaches of remediation limit values with environmental consequences on both surface and underground waters. With the opening of the mine, problems will be multiplied by the tailings pond, mine wastewater, noise, air pollution, and light pollution, endangering the lives of numerous local communities and destroying their freshwater sources, agricultural land, livestock, and assets.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Landuse and land cover shape organic contaminants distribution in the Oconee River watershed in Georgia

Amid growing concerns over the persistence of organic contaminants, this study examines the influence of land-use patterns on their distribution in the Oconee River watershed, Georgia. Surface water samples from five sites across urban, recreational, and forested areas of Georgia’sOconee River watershed were analyzed for 22 organic contaminants, including pesticides and polycyclic aromatic hydrocarbons. Contaminant concentrations varied, with Acenaphthene (max: 19,462.04 ng/L), Chrysene (max: 984.10 ng/L), and Naphthalene (max: 2428.06 ng/L) being predominant. Atrazine (max: 171.04 ng/L) and Malathion (max: 114.99 ng/L)were the most detected pesticides. Land use and land cover significantly influence organic contaminant distribution, with higher levels in forested and urban areas. Risk Quotient (RQ) analysis confirmed no contaminants surpassed the critical threshold, though cumulative exposure may pose long-term risks. The study emphasizes the need for targeted monitoring and regulatory efforts to safeguard water quality in river systems influenced by diverse land-use practices.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Comprehensive Chemical Fingerprinting by Multidimensional GC and Supervised Machine Learning

This project leverages advances in machine learning based data analysis techniques and untargeted omic analytical methods to progress nuclear nonproliferation technologies beyond current capabilities. The developed approaches can be used to identify and detect complex chemical fingerprints of facilities of interest. These techniques have been developed for fields such as metabolomics and genomics but have not been applied to nuclear nonproliferation applications. Adaptation of these techniques for volatile organic compound analysis has far reaching application within the scientific community including environmental chemistry, atmospheric physics, and climate sciences.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Comprehensive Chemical Fingerprinting by Multidimensional GC and Supervised Machine Learning

This project leveraged advances in machine learning based data analysis techniques and untargeted analytical methods for organic analysis to progress nuclear nonproliferation technologies beyond current capabilities. The developed approaches can be used to detect and identify complex chemical fingerprints of facilities of interest. These techniques have been developed for fields such as metabolomics and genomics but have not been applied to nuclear nonproliferation applications. Adaptation of these techniques for volatile organic compound analysis has far reaching application within the scientific community including environmental chemistry, atmospheric physics, and climate sciences.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
NASA NTRS1985

Training managers for high productivity: Guidelines and a case history

Hughes Aircrafts 13-year productivity study clearly identifies management as the key link in the entire productivity chain. This fact led to the establishment of a long-term series of seminars on personal, managerial, organizational, and operational productivity for all levels and sectors of line and staff management. To inspire the work force to higher levels of productivity and creativity management, itself, must first be inspired. In turn they have to clearly understand the productive and creative processes, fashion an effective productivity improvement plan with sound strategy and implementation, create an optimal environmental chemistry, and provide the outstanding leadership necessary to propel their organizations to achieve full potential. The primary goals of the seminars are to (1) ignite that spark of inspiration, enabling productive action to follow, (2) provide participants a credible roadmap and effective tools for implementation, and (3) develop a dedicated commitment to leadership and productivity throughout the management team.

Ranftl, R. M.↗
NASA NTRS2015

2014 ISS Potable Water Characterization and Continuation of the DMSD Chronicle

During 2014 the crews from Expeditions 38-41 were resident on the International Space Station (ISS). In addition to the U.S. potable water reclaimed from humidity condensate and urine, the other water supplies available for their use were Russian potable water reclaimed from condensate and Russian ground-supplied potable water. Beginning in June of 2014, and for the fourth time since 2010, the product water from the U.S. Water Processor Assembly (WPA) experienced a rise in the total organic carbon (TOC) level due to organic contaminants breaking through the water treatment process. Results from ground analyses of ISS archival water samples returned on Soyuz 38 confirmed that dimethylsilanediol (DMSD) was once again the contaminant responsible for the rise. With this confirmation in hand and based upon the low toxicity of DMSD, a waiver was approved to allow the crew to continue to consume the water after the TOC level exceeded the U.S. Segment limit of 3 mg/L. Several weeks after the WPA multifiltration beds were replaced, as anticipated based upon experience from previous rises, the TOC levels returned to below the method detection limit of the onboard TOC analyzer (TOCA). This paper presents and discusses the chemical analysis results for the ISS archival potable water samples returned in 2014 and analyzed by the Johnson Space Center's Toxicology and Environmental Chemistry laboratory. These results showed compliance with ISS potable water quality standards and indicated that the potable water supplies were acceptable for crew consumption. Although DMSD levels were at times elevated they remained well below the 35 mg/L health limit, so continued consumption of the U.S potable water was considered a low risk to crew health and safety. Excellent agreement between inflight and archival sample TOC data confirmed that the TOCA performed optimally and it continued to serve as a vital tool for monitoring organic breakthrough and planning remediation action.

Straub, John E., II↗
NASA NTRS2015

2014 ISS Potable Water Characterization and Continuation of the Dimethylsilanediol Chronicle

During 2014 the crews from Expeditions 38-41 were in residence on the International Space Station (ISS). In addition to the U.S. potable water reclaimed from humidity condensate and urine, the other water supplies available for their use were Russian potable water reclaimed from condensate and Russian ground-supplied potable water. Beginning in June of 2014 and for the fourth time since 2010, the product water from the U.S. water processor assembly (WPA) experienced a rise in the total organic carbon (TOC) level due to organic contaminants breaking through the water treatment process. Results from ground analyses of ISS archival water samples returned on Soyuz 38 confirmed that dimethylsilanediol was once again the contaminant responsible for the rise. With this confirmation in hand and based upon the low toxicity of dimethylsilanediol, a waiver was approved to allow the crew to continue to consume the water after the TOC level exceeded the U.S. Segment limit of 3 mg/L. Several weeks after the WPA multifiltration beds were replaced, the TOC levels returned to below the method detection limit of the onboard TOC analyzer (TOCA) as anticipated based upon experience from previous rises. This paper presents and discusses the chemical analysis results for the ISS archival potable-water samples returned in 2014 and analyzed by the Johnson Space Center's Toxicology and Environmental Chemistry laboratory. These results showed compliance with ISS potable water quality standards and indicated that the potable-water supplies were acceptable for crew consumption. Although dimethylsilanediol levels were at times elevated, they remained well below the 35 mg/L health limit so the continued consumption of the U.S. potable water was considered a low risk to crew health and safety. Excellent agreement between in-flight and archival sample TOC data confirmed that the TOCA performed optimally and continued to serve as a vital tool for monitoring organic breakthrough and planning remediation action.

Straub, John E., II↗
NASA NTRSDate not supplied

Chemical Challenge Tests on ISS Fire Cartridges

Following a confirmed combustion event onboard the International Space Station (ISS), crewmembers will don Emergency Masks, each fitted with 2 ISS fire cartridge filters. As the crewmember breathes through the filters, combustion products in the cabin air are either filtered or catalyzed by the fire cartridge media to minimize crew exposure to harmful levels of contaminants. Rigorous certification, acceptance, and surveillance programs for the fire cartridges ensure that each lot meets stringent performance requirements during the beginning of and throughout the service life of the cartridges. In accordance with the Quality/Acceptance Test Plan, multiple fire cartridges from each lot undergo chemical challenge tests, with each test lasting 2.5 hours and involving one or more chemicals at specified concentrations. These tests are conducted at specific temperatures, humidity levels, and gas flow rates intended to mimic the worst-case conditions for fire cartridge performance. These challenge tests are conducted by the Environmental Chemistry Laboratory at the NASA Lyndon B. Johnson Space Center. The majority of the challenge tests focus on carbon monoxide (CO), but other gases include hydrogen cyanide (HCN), hydrogen chloride (HCl), cyclohexane, acrolein, and acetaldehyde. A fire cartridge is exposed to the test gas in a test chamber at the specified conditions and the outlet is monitored for breakthrough during the 2.5-hour test. This paper will briefly introduce fire cartridges and how they work, then discuss details of the challenge gas delivery and exposure system, breakthrough monitoring methods, and discussion of issues that have arisen during the course of the test program. Although the focus of this paper will be on the conduction of the challenge tests, a general summary of the performance of the fire cartridges will be provided.

Fire Cartridge↗
NASA NTRSDate not supplied

Chemical Challenge Tests on ISS Fire Cartridges

Following a confirmed combustion event onboard the International Space Station (ISS), crew members will don Emergency Masks, each fitted with 2 ISS fire cartridge filters. As the crew member breathes through the filters, combustion products in the cabin air are either filtered or catalyzed by the fire cartridge media to minimize crew exposure to harmful levels of contaminants. Rigorous certification, acceptance, and surveillance programs for the fire cartridges ensure that each lot meets stringent performance requirements throughout the service life of the cartridges. In accordance with the Quality/Acceptance Test Plan, multiple fire cartridges from each lot undergo chemical challenge tests involving one or more chemicals at specified concentrations. These tests are conducted at specific temperatures, humidity levels, and gas flow rates intended to mimic the worst-case conditions for fire cartridge performance. These challenge tests are conducted by the Environmental Chemistry- Laboratory at the NASA Lyndon B. Johnson Space Center. Many of the challenge tests focus on carbon monoxide (CO), but other gases include hydrogen cyanide (HCN), hydrogen chloride (HCl), cyclohexane, acrolein, ammonia (NH3), and acetaldehyde. A fire cartridge is exposed to the test gas in a chamber at the specified conditions, and the outlet is monitored for breakthrough during the 2.5-hour test. This paper will briefly introduce fire cartridges and how they work and will then discuss details of the challenge gas delivery and exposure system, breakthrough monitoring methods, and discussion of issues that have arisen during the course of the test program. Although the focus of this paper will be on the challenge tests, a general summary of the performance of the fire cartridges will also be provided.

Cristina M. Muko↗