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All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Alternative Perspectives on Risk

The goal of the commercial air transport system is to provide air transportation to the flying public at an acceptable cost with minimal risk. in an ideal situation these three goals would support each other. In fact, it is sometimes the case that the goals conflict: getting passengers to their destinations on time may conflict with fixing a minor mechanical malfunction that may or may not impact safety; flying a route that will avoid turbulence, thereby providing passengers with a more comfortable ride, may consume more fuel; managing traffic density may mean aircraft are delayed or must use an approach that will result in a long taxi to their gates, costing time and fuel. Various players in the system--pilots, dispatchers, controllers, as well as managers in the airline carriers and traffic management system--make decisions every day that involve trade-offs of benefits and costs. The prospect of revisions in the air traffic management system, with shifts in responsibilities from controllers to users, including airline operations center personnel and pilots, means that individuals may be performing either new jobs or old jobs under new guidance. It will be essential to know how the various players (a) perceive the risks and benefits associated with the decisions they will make under the old and new control structures, and (b) how much risk they are willing to accept in making decisions. Risk is here defined as the probability and magnitude of negative events (after Slovic, 1987). Of primary interest are risks associated with traffic, weather, and operational factors such as schedule, fuel consumption, and passenger service. Previous research has documented differences between groups in perceptions of risks associated with both everyday and aviation related situations. Risk perception varies as a function of familiarity with the situation, degree to which one is potentially affected by the risk, the level of control one has over the situation, and one's level of experience and responsibility in the situation. In our presentation we will consider several factors that may influence differences in risk perception, risk tolerance and risk management among the three major categories of participants in the aviation system (pilots, dispatchers, and controllers). Primary factors that may affect risk attitudes (the collective term we will use for the three components of risk) include: expertise or job-specific knowledge or training, personal involvement or vulnerability to consequences, goals, time horizon (imminence of consequences), span of control and type of control, and information or technology support. These will be considered in the context of five different types of risk (physical threat, economic, social, legal, and ethical). A study designed to study differences between pilots and controllers in their perceptions and responses to traffic risks under the present and a user-preferred control situation will be described. Future studies involving dispatchers' risk perceptions regarding various types of risk will be discussed.

Davison, Jeannie↗
NASA NTRS2012

Nano Sponges for Drug Delivery and Medicinal Applications

This invention is a means of delivering a drug, or payload, to cells using non-covalent associations of the payload with nano-engineered scaffolds; specifically, functionalized single-walled carbon nanotubes (SWNTs) and their derivatives where the payload is effectively sequestered by the nanotube's addends and then delivered to the site (often interior of a cell) of interest. Polyethylene glycol (PEG) and other water-soluble organic molecules have been shown to greatly enhance the solubility of SWNTs in water. PEG groups and other water-solubilizing addends can act to sequester (sponge) molecules and deliver them into cells. Using PEG that, when attached to the SWNTs, the SWNT/PEG matrix will enter cells has been demonstrated. This was visualized by the addition of fluorescein isothiocyanate (FITC) to the SWNT/PEG matrix. Control studies showed that both FITC alone and FITC/PEG did not enter the cells. These observations suggest that the FITC is highly associated with the SWNT/PEG matrix that brings the FITC into the cells, allowing visualization of SWNTs in cells. The FITC is not covalently attached, because extended dialysis in hot DMF will remove all fluorescence quickly (one week). However, prolonged dialysis in water (1-2 months) will only slowly diminish the fluorescence. This demonstrates that the SWNT/PEG matrix solubilizes the FITC by sequestering it from the surrounding water and into the more solubilizing organic environment of the SWNT/PEG matrix of this type. This can be extended for the sequestering of other molecules such as drugs with PEG and other surfactants.

Tour, James M.↗
NASA NTRS2016

Flash Spectroscopy: Emission Lines From the Ionized Circumstellar Material Around 10-Day-Old Type II Supernovae

Supernovae (SNe) embedded in dense circumstellar material (CSM) may show prominent emission lines in their early-time spectra (< or =10 days after the explosion), owing to recombination of the CSM ionized by the shock-breakout flash. From such spectra ("flash spectroscopy"), we can measure various physical properties of the CSM, as well as the mass-loss rate of the progenitor during the year prior to its explosion. Searching through the Palomar Transient Factory (PTF and iPTF) SN spectroscopy databases from 2009 through 2014, we found 12 SNe II showing flash-ionized (FI) signatures in their first spectra. All are younger than 10 days. These events constitute 14% of all 84 SNe in our sample having a spectrum within 10 days from explosion, and 18% of SNe II observed at ages <5 days, thereby setting lower limits on the fraction of FI events. We classified as "blue/featureless" (BF) those events having a first spectrum that is similar to that of a blackbody, without any emission or absorption signatures. It is possible that some BF events had FI signatures at an earlier phase than observed, or that they lack dense CSM around the progenitor. Within 2 days after explosion, 8 out of 11 SNe in our sample are either BF events or show FI signatures. Interestingly, we found that 19 out of 21 SNe brighter than an absolute magnitude M(sub R) = −18.2 belong to the FI or BF groups, and that all FI events peaked above M(sub R) = −17.6 mag, significantly brighter than average SNe II.

supernovae: general↗
NASA NTRSDate not supplied

NASA MUREP-DEAP Institutes - Year 1 Updates on Capacity Building, Community Building and Research Initiatives

Through the Minority University Research and Education Project (MUREP), NASA engages underrepresented populations via various initiatives, including by means of three year competitive awards for Data Science Equity, Access, and Priority in Research and Education (DEAP) Institutes led by Historically Black Colleges and Universities (HBCUs). MUREP DEAP Institutes, multi-institutional consortia, conduct data science research and capacity building initiatives that aim to enhance the research, academic, and technological capabilities of the participating HBCUs while providing NASA-specific knowledge, skills and opportunities for students and faculty who have historically been underrepresented and underserved in the STEM workforce. Three MUREP DEAP Institutes, led by Bethune-Cookman University, North Carolina A&T University, and North Carolina Central University, are conducting data science and natural hazard related research utilizing remote sensing and earth observations, with mentorship for the Institutes provided by scientists from NASA’s Marshall Space Flight Center. Each Institute has unique capabilities, needs, and goals, but overlap in their common interest to conduct cutting edge data science and natural hazard related research and to build capacity, broaden participation, and increase retention of a diverse group of participating students and faculty​. Here, successes and challenges from the first year of activities at each MUREP DEAP institute are discussed, where activities focused primarily on the recruitment of a diverse group of students and the upskilling of students and faculty in data science and remote sensing concepts. The planned activities and goals of each DEAP Institute for the upcoming two years of activities will also be discussed, both from research and community-building perspectives.

Ronan Lucey↗
DOE OSTI2012

Weapons Experiments Division Explosives Operations Overview

Presentation covers WX Division programmatic operations with a focus on JOWOG-9 interests. A brief look at DARHT is followed by a high level overview of explosives research activities currently being conducted within in the experimental groups of WX-Division. Presentation covers more emphasis of activities and facilities at TA-9 as these efforts have been more traditionally aligned with ongoing collaborative explosive exchanges covered under JOWOG-9.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2016

A New Group Crystallization Approach in Used Nuclear Fuel Recycling: A Look at Fission Product Behaviors

Nuclear energy has the potential to play a large role in meeting future needs of the U.S. sustainable energy strategy, as a clean, carbon-free power source. However, to take advantage of the inherent benefits, many hurdles must be overcome in order for nuclear power to achieve these expectations. One of the largest challenges faced, is the management of used nuclear fuel (UNF). Currently, no strategy has been identified to deal with the growing UNF problem, and so the UNF remains stored on site at nuclear power plants either in cooling pools or in dry cast storage. The amount of stored UNF continues to grow, and with it, so does the concern surrounding its long-term radiotoxicity. This material could be reprocessed to recover the actinides, maximizing the energy potential of the UNF and minimizing the waste generation. Not only do U and Pu, the major energy producing actinides, need to be recovered, but recovering Np and Am would make waste generated from reprocessing significantly safer for long-term storage in a geological repository. There are a number of methods currently in use to reprocess UNF; throughout Europe, the Purex process is widely implemented, while the Japanese have developed the Next process. The Next process removes a bulk of the U by crystallization prior to a Purex-like separation scheme. In the Next process, it is undesirable to have any other species removed from solution in the crystallization step, but rather the goal is to obtain a pure uranyl nitrate hexahydrate (UNH) product. Alternatively, a group separation of U-Am by a crystallization process would provide an elegant solution. Such a process has become attainable with the renewed interest in accessing Am(VI) in nitric acid solutions. In order to synthesize and stabilize Am(VI), a highly oxidizing system is required, which has only been demonstrated on a limited basis. By oxidizing Np, Pu, and Am to their hexavalent state, they can be co-crystallized with UNH, and thereby removed from solution. Recent results have demonstrated that all the hexavalent actinide (An) species are removed from solution in near proportion, by a simple reduction of temperature in 6-8 M HNO{sub 3}. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

A New Group Crystallization Approach in Used Nuclear Fuel Recycling: A Look at Fission Product Behaviors

Nuclear energy has the potential to play a large role in meeting future needs of the U.S. sustainable energy strategy, as a clean, carbon-free power source. However, to take advantage of the inherent benefits, many hurdles must be overcome in order for nuclear power to achieve these expectations. One of the largest challenges faced, is the management of used nuclear fuel (UNF). Currently, no strategy has been identified to deal with the growing UNF problem, and so the UNF remains stored on site at nuclear power plants either in cooling pools or in dry cask storage. The amount of stored UNF continues to grow, and with it, so does the concern surrounding its long-term radiotoxicity. This material could be reprocessed to recover the actinides, maximizing the energy potential of the UNF and minimizing the waste generation. Not only do U and Pu, the major energy producing actinides, need to be recovered, but recovering Np and Am would make waste generated from reprocessing significantly safer for long-term storage in a geological repository. There are a number of methods currently in use to reprocess UNF; throughout Europe, the Purex process is widely implemented, while the Japanese have developed the Next process. The Next process removes a bulk of the U by crystallization prior to a Purex-like separation scheme. In the Next process, it is undesirable to have any other species removed from solution in the crystallization step, but rather, the goal is to obtain a pure uranyl nitrate hexahydrate (UNH) product. Alternatively, a group separation of U-Am by a crystallization process would provide an elegant solution. Such a process has become attainable with the renewed interest in accessing Am(VI) in nitric acid solutions. In order to synthesize and stabilize Am(VI) which has only been demonstrated on a limited basis, a highly oxidizing system is required. By oxidizing Np, Pu, and Am to their hexavalent state, they can be co-crystallized with UNH, and thereby removed from solution. Recent results have demonstrated that all the hexavalent actinide (An) species are removed from solution in near proportion, by a simple reduction of temperature in 6-8 M HNO{sub 3}.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Electrical Tuning of Tin-Vacancy Centers in Diamond

Group-IV color centers in diamond have attracted significant attention as solid-state spin qubits because of their excellent optical and spin properties. Among these color centers, the tin-vacancy (Sn-V - ) center is of particular interest because its large ground-state splitting enables long spin coherence times at temperatures above 1 K. However, color centers typically suffer from inhomogeneous broadening, which can be exacerbated by nanofabrication-induced strain, hindering the implementation of quantum nodes emitting indistinguishable photons. Although strain and Raman tuning have been investigated as promising tuning techniques to overcome the spectral mismatch between distinct group-IV color centers, other approaches need to be explored to find methods that can offer more localized control without sacrificing emission intensity. Here, we study the electrical tuning of Sn-V - centers in diamond via the direct-current Stark effect. We demonstrate a tuning range beyond 1.7 GHz. We observe both quadratic and linear dependence on the applied electric field. Further, we also confirm that the tuning effect we observe is a result of the applied electric field and is distinct from thermal tuning due to Joule heating. Stark tuning is a promising avenue toward overcoming detunings between emitters and enabling the realization of multiple identical quantum nodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2012

Absolute Position of Targets Measured Through a Chamber Window Using Lidar Metrology Systems

Lidar is a useful tool for taking metrology measurements without the need for physical contact with the parts under test. Lidar instruments are aimed at a target using azimuth and elevation stages, then focus a beam of coherent, frequency modulated laser energy onto the target, such as the surface of a mechanical structure. Energy from the reflected beam is mixed with an optical reference signal that travels in a fiber path internal to the instrument, and the range to the target is calculated based on the difference in the frequency of the returned and reference signals. In cases when the parts are in extreme environments, additional steps need to be taken to separate the operator and lidar from that environment. A model has been developed that accurately reduces the lidar data to an absolute position and accounts for the three media in the testbed air, fused silica, and vacuum but the approach can be adapted for any environment or material. The accuracy of laser metrology measurements depends upon knowing the parameters of the media through which the measurement beam travels. Under normal conditions, this means knowledge of the temperature, pressure, and humidity of the air in the measurement volume. In the past, chamber windows have been used to separate the measuring device from the extreme environment within the chamber and still permit optical measurement, but, so far, only relative changes have been diagnosed. The ability to make accurate measurements through a window presents a challenge as there are a number of factors to consider. In the case of the lidar, the window will increase the time-of-flight of the laser beam causing a ranging error, and refract the direction of the beam causing angular positioning errors. In addition, differences in pressure, temperature, and humidity on each side of the window will cause slight atmospheric index changes and induce deformation and a refractive index gradient within the window. Also, since the window is a dispersive media, the effect of both phase and group indices have to be considered. Taking all these factors into account, a method was developed to measure targets through multiple regions of different materials and produce results that are absolute measurements of target position in three-dimensional space, rather than simply relative position. The environment in which the lidar measurements are taken must be broken down into separate regions of interest and each region solved for separately. In this case, there were three regions of interest: air, fused silica, and vacuum. The angular position of the target inside the chamber is solved using only phase index and phase velocity, while the ranging effects due to travel from air to glass to vacuum/air are solved with group index and group velocity. When all parameters are solved simultaneously, an absolute knowledge of the position of each target within an environmental chamber can be derived. Novel features of this innovation include measuring absolute position of targets through multiple dispersive and non-dispersive media, deconstruction of lidar raw data from a commercial off-the-shelf unit into reworkable parameters, and use of group velocities to reduce range data. Measurement of structures within a vacuum chamber or other harsh environment, such as a furnace, may now be measured as easily as if they were in an ambient laboratory. This analysis permits transformation of the raw data into absolute spatial units (e.g., mm). This technique has also been extended to laser tracker, theodolite, and cathetometer measurements through refractive media.

Kubalak, David↗
DOE OSTI2017

Preclinical evaluation of 18 F-ML-10 to determine timing of apoptotic response to chemotherapy in solid tumors

Here, we investigated 2-(5-fluoro-pentyl)-2-methyl-malonic acid ( 18 F-ML-10) positron emission tomography (PET) imaging of apoptosis posttherapy to determine optimal timing for predicting chemotherapy response in a mouse head/neck xenograft cancer model. BALB/c nude mice (4-8 weeks old) were implanted with UM-SCC-22B tumors. The treatment group received 2 doses of doxorubicin (10 mg/kg, days 0, 2). Small animal 18 F-ML-10 PET/computed tomography was performed before and on days 1, 3, and 7 postchemotherapy. Using regions of interest around tumors, 18 F-ML-10 uptake change was measured as %ID/g and uptake relative to liver. Terminal Uridine Nick-End Labeling (TUNEL) immunohistochemistry assay was performed using tumor samples of baseline and on days 1, 3, and 7 posttreatment. As a result, treated mice demonstrated increased 18 F-ML-10 uptake compared to baseline and controls, and 10 of 13 mice showed tumor volume decreases. All control mice showed tumor volume increases. Tumor-to-liver (T/L) ratios from the control group mice did not show significant change from baseline ( P > .05); however, T/L ratios of the treatment group showed significant 18 F-ML-10 uptake differences from baseline compared to days 3 and 7 posttreatment ( P < .05), but no significant difference at 1 day posttreatment. In conclusion, 2-(5-Fluoro-pentyl)-2-methyl-malonic acid PET imaging has the potential for early assessment of treatment-induced apoptosis. Timing and image analysis strategies may require optimization, depending on the type of tumor and cancer treatment.

18F-ML-10↗
DOE OSTI2018

Reduced adiposity by compensatory WAT browning upon iBAT removal in mice

Highlights: • Prolonged time course for cold exposure was utilized to elucidate dynamic changes in BAT and in WAT browning in mice. • Loss of classic iBAT enhanced WAT browning due to compensatorily increased sympathetic WAT input in mice. • Significantly reduced adiposity in the iBAT removal group compared with the control group in mice. The strong effects of classic brown adipose tissue (BAT) and recruited beige adipocytes in treatment of obesity and metabolic syndrome have been attracting increasing research interest. Cold treatment is an effective, convenient approach to stimulate BAT activity and induce white adipose tissue (WAT) browning. Here, we utilized prolonged cold exposure (from 2 h to 2 weeks in a 4° cold chamber) to elucidate dynamic changes in BAT and in WAT browning during acute and chronic cold exposure in mice. BAT mass decreased quickly, with reduced lipid droplet sizes within 8 h of cold exposure owing to the utilization of BAT pre-storage triglycerides, and subsequently increased during prolonged cold exposure. These dynamic morphological changes in BAT were confirmed by gene expression changes in ADRB3 and PGC1α, while UCP1 and ELOVL3 expression was continuously up-regulated throughout the entire cold exposure period. Additionally, cold treatment increased BAT secretion of FGF21, which has been reported to activate beige adipocyte formation. Thus, to illustrate potential crosstalk between secreted BAT proteins (so-called BATokines) and beige adipogenesis during cold stress, we performed an interscapular BAT (iBAT) removal experiment in mice. Surprisingly, loss of classic iBAT enhanced WAT browning due to compensatorily increased sympathetic WAT input. Unexpectedly, we observed significantly reduced adiposity in the iBAT removal group compared with the control group. These results further suggest that WAT browning plays an important role in whole-body energy metabolism during cold acclimation, even without iBAT. Furthermore, our data imply that enhanced WAT browning may be an efficient therapeutic tool to combat obesity and related syndromes.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Integrating regulatory, programmatic and technical needs for modeling tools to support decision-making - 15219

The U.S. Department of Energy (US DOE) Office of Environmental Management (EM), Office of Soil and Groundwater Remediation, is supporting development of the Advanced Simulation Capability for Environmental Management (ASCEM). ASCEM provides a modeling work-flow to support decision-making for site restoration, tank closure and waste management activities. Potential users involved in regulatory applications (e.g., performance and risk assessments and other activities supporting regulatory decisions) are a key target group for the tool-set. Decision-making in these applications often requires consideration of multiple perspectives, including: regulators and the public, oversight and project management personnel, as well as practitioners involved in conducting the calculations, each with different interests. From its inception, a key objective of the ASCEM project has been to actively seek input from these different user perspectives to help guide development. ASCEM formed a User Steering Committee (USC) with membership representing interests from management/staff at DOE Site Contractors, DOE-HQ and Field offices and Regulators (State and Federal). The project also provides opportunities for input from the broader user community through participation in meetings of the Performance and Risk Assessment (P and RA) Community of Practice (CoP), routine briefings and participation in meetings of the Low-Level Waste Disposal Facility Federal Review Group, and direct interactions with users involved in regulatory applications. Interactions with users involved in regulatory applications have influenced the requirements for the tool-sets and are reflected in capabilities that have been and are being implemented. (authors)

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

Randomized Trial of Radiation Therapy With Weekly Cisplatin or Cetuximab in Low-Risk HPV-Associated Oropharyngeal Cancer (TROG 12.01) – A Trans-Tasman Radiation Oncology Group Study

The excellent prognosis of patients with low-risk human papillomavirus (HPV)- associated oropharyngeal squamous cell carcinoma has led to concerns about overtreatment and excessive toxicity with radiation therapy and cisplatin, leading to interest in de-intensification trials. We investigated whether cetuximab, an epidermal growth factor receptor targeting antibody, when combined with radiation therapy would result in a decrease in symptom burden and toxicity with similar efficacy compared with weekly cisplatin.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2015

Ligand- and oxygen-isotope-exchange pathways of geochemical interest

It is through ligand-exchange kinetics that environmental geochemists establish an understanding of molecular processes, particularly for insulating oxides where there are not explicit electron exchanges. The substitution of ligands for terminal functional groups is relatively insensitive to small changes in structure but are sensitive to bond strengths and acid–base chemistry. Ligand exchanges involving chelating organic molecules are separable into two classes: (i) ligand substitutions that are enhanced by the presence of the chelating ligand, called a ‘spectator’ ligand and (ii) chelation reactions themselves, which are controlled by the Lewis basicity of the attacking functional group and the rates of ring closure. In contrast to this relatively simple chemistry at terminal functional groups, substitutions at bridging oxygens are exquisitely sensitive to details of structure. Included in this class are oxygen-isotope exchange and mineral-dissolution reactions. In large nanometer-sized ions, metastable structures form as intermediates by detachment of a surface metal atom, often from a underlying, highly coordinated oxygen, such as μ4-oxo, by solvation forces. A metastable equilibrium is then established by concerted motion of many atoms in the structure. The newly undercoordinated metal in the intermediate adds a water or ligand from solution, and protons transfer to other oxygens in the metastable structure, giving rise to a characteristic broad amphoteric chemistry. These metastable structures have an appreciable lifetime and require charge separation, which is why counterions affect the rates. As a result, the number and character of these intermediate structures reflect the symmetry of the starting structure.

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

Collaborative Research: Natural Organic Matter and Microbial Controls on Mobilization/Immobilization of I and Pu in Soils and Waters Affected by Radionuclide Releases in USA and Japan

In this project, the relationship between natural organic matter (NOM) and two radioactive elements that are relevant to nuclear waste disposal were studied: Plutonium (Pu) and Iodine. The human and environmental risks associated with Pu stem mainly from the very long half-lives of several of its isotopes ( 238 Pu, 88 yr; 239 Pu, 24,100 yr; 240 Pu, 6560 yr) and its radiotoxicity. Understanding Pu biogeochemical behavior in both near-field (>10-11M) and far-field scales (<10-11M) is imperative to the development of approaches for reprocessing Pu, remediation of Pu contamination and accurate assessment of risks posed by disposal practices for Pu-bearing wastes. The environmental mobility of Pu can be affected by redox potential, pH, adsorption, precipitation, complexation, colloid formation, and microbial activity, of which the first characteristic has the most profound influence. Numerous studies have shown high affinity of Pu towards NOM, as well as to mineral phases. NOM is ubiquitous in the environment, e.g., both fulvic and humic acids are able to reduce Pu(V,VI) to Pu(IV) and the redox potential of NOM is positively related to the abundance of phenolic/acidic OH groups. NOM can either facilitate or limit actinide migration, depending on specific biogeochemical conditions including pH, mineral and organic matter characteristics, etc. The other radionuclide of interest is radioiodine ( 129 I). 129I is a major by-product of nuclear fission and of serious concern to the Department of Energy (DOE) as it is among the top risk drivers at existing and potential radiowaste-contaminated sites. The risk of 129 I stems largely from its high bioconcentration factor (90% of the body’s iodine is accumulated in the thyroid), a high inventory at source terms, a very long-half life (16M years), and rapid mobility in the subsurface environment. As a consequence, 129 I has the lowest drinking water standard (1 pCi/L) among all radionuclides in the Federal Register. With a novel and sensitive gas chromatography-mass spectrometry (GC-MS) method developed in our lab, it is possible to quickly and simultaneously determine the distribution of 129 I and stable 127 I forms in environments, as low as 2 pCi/L for 129 I. This method was subsequently validated using accelerator mass spectroscopy, AMS. IO 3 - and organo-I were determined as major species in the groundwater of SRS and the Hanford Site, contrary to thermodynamic predictions that I- should be the dominant species at these sites. Mobility of 129 I was also demonstrated to depend greatly on the I species and its concentration, sediment pH, and redox state, with times to achieve equilibrium taking up to 12 weeks. Along the groundwater pathway in the F-Area of SRS, 129 I- supplied from the seepage basins was transformed to 129 IO 3 - and organo- 129 I with increasing iodine sediment sorption, causing the lower total 127 I and 129 I concentrations along the gradient transect of the waste plume. By contrast, groundwater 129 I concentrations in the wetlands (as high as 1617.3 pCi/L) were greatly elevated with respect to the source term (159.3 pCi/L). While the NOM promoted the uptake of 129 I to the wetland sediment, it also promoted the formation of soluble organic fraction. A small fraction of NOM that is bound to iodine can behave as a mobile organo-I source. Iodide was enzymatically incorporated into NOM, whereas both iodide and iodate were abiotically bound to NOM, under certain conditions. Iodate removal from the mobile aqueous phase can also occur through incorporation into carbonate (e.g., at the Hanford Site, USA). Thus immobilization and re-mobilization of iodine species were influenced by pH, Eh and the presence of NOM and metal oxides, which adds to the complexity of site remediation action. A ground-breaking result was to elucidate the products (i.e. organo-iodine moieties formed via enzymatic and non-enzymatic processes) at the molecular level by nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). We found that iodine-NOM interactions may be influenced by NOM hydrophobic aliphatic moieties. From the perspective of ESI-FTICRMS, organo-iodine formulas were ascribed to the groups of unsaturated hydrocarbons, lignins and proteins. Iodate is likely abiotically reduced to reactive iodine species by lignin- and tannin-like compounds or carboxylic-rich alicyclic molecules (CRAM). We also investigated microbial mechanisms in iodine incorporation into NOM. We established that soil bacteria isolated from F-Area of SRS did not accumulate significant amounts of I- (0.2-2%). Intracellular uptake of I- decreases with increasing pH when pH ranged from 4 to 6. In contrast, 44 out of 84 strains isolated from the F-Area of SRS can transform I- to IO 3 - and organo-iodine. In some cases, oxidation was facilitated in the presence of H 2 O 2 . Microbes can also excrete organic acids that enhance I- oxidation by lowering the ambient pH and reacting with H 2 O 2 to form peroxy carboxylic acids. At lower pH values (≤5), H 2 O 2 hydrolysis was the driving force for iodide-oxidation; whereas, at pH ≥ 6, spontaneous decomposition of peroxy carboxylic acids, originating from H 2 O 2 and organic acids were the primary cause of iodide oxidation. Lastly, it was determined that microbial processes involved in Mn (II) are capable of directly oxidizing I- via enzymatic catalysis (i.e., multicopper oxidases), or indirectly through the formation of reactive oxygen species (ROS) and/or biogenic manganese oxides. ROS-mediated oxidation of I- was found to predominate at pH >5, whereas the enzymatic and Mn oxide pathways were more active at pH < 5. Together, this project has resulted in 9 publications in high-impact journals, and the training of 1 Ph.D and 4 undergraduate students.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Stimuli‐Responsive Emission from Hybrid Metal Halides

Abstract Stimuli‐responsive photoluminescent (PL) materials have attracted considerable attention in recent years owing to their potential applications in anti‐counterfeiting, information encryption, and sensing. Further investigations of the transformation mechanism and potential applications of stimulus‐responsive PL materials are considerably important. In the current study, an organic–inorganic metal halide, C 9 H 15 N 3 SbCl 5 ([C 9 H 13 N 3 ] 2+ is a 1‐(2‐pyridyl) piperazine cation) is obtained, which exhibits a 0D structure withP‐1 space group. At room temperature, when excited by UV light, the C 9 H 15 N 3 SbCl 5 single crystals exhibit unimodal blue light emission at 405 nm, and grinding or hydrostatic pressure induces double‐peak emissions at 405 and 650 nm. Interestingly, double‐emission samples can be restored to single‐emission samples by short annealing or storage in air for 2 weeks, and this process is reversible. Luminescence response to mechanical stimuli can also be achieved in the presence of hydrochloric acid and water. Spectral analysis and the analysis of the microstructural changes revealed that the structural modifications of the inorganic group play a pivotal role in the response to the stimulus. Finally, a composite film device based on C 9 H 15 N 3 SbCl 5 is prepared to demonstrate the potential of these smart materials in anti‐counterfeiting and sensing applications.

Chemistry↗
NASA NTRS1999

Return to the Moon: A New Strategic Evaluation

This paper reviews the value of a new lunar program, initially robotic and eventually manned, in the light of developments since the 1991 Synthesis Group study of the Space Exploration Initiative. The objective is to evaluate a return to the Moon in comparison to proposed Mars programs as a focus for American space exploration with humans in the next century. The Moon is demonstrably accessible, hospitable, useful, and interesting. Lunar programs are inherently faster and less risky from a programmatic viewpoint than comparable Mars programs such as Mars Direct. The dominant reason for a resumption of manned lunar missions, focussed on a single site such as Grimaldi, is to rebuild the infrastructure for missions beyond earth orbit, the last of which was in 1972. A transitional program, corresponding to the 10 Gemini missions that bridged the gap between Mercury and Apollo, was considered absolutely essential by the Synthesis Group. Further justification for a return to the Moon is the demonstrated feasibility of a robotic lunar observatory, concentrating on optical and infrared interferometry. Many unsolved scientific questions about the Moon itself remain, and could be investigated using telerobotic lunar rovers even before the return of humans. Mars is unquestionably more interesting scientifically and far more hospitable for long-term colonization. A new lunar program would be the most effective possible preparation for the human exploration, settlement, and eventually the terraforming of Mars. Lunar and Mars programs are complementary, not competitive. Both can be justified in the most fundamental terms as beginning the dispersal of the human species against uncontrollable natural disasters, cometary or asteroidal impacts in particular, to which mankind is vulnerable while confined to a single planet. Three specific programs are recommended for the 2001-2010 period: Ice Prospectors, to evaluate polar ice or hydrogen deposits; a robotic lunar observatory; and a manned lunar base and observatory.

Lowman, Paul D., Jr.↗
NASA NTRS1999

Return to the Moon: A New Strategic Evaluation

This paper reviews the value of a new lunar program, initially robotic and eventually manned, in the light of developments since the 1991 Synthes Group study of the Space Exploration Initiative. The objective is to evaluate a return to the Moon in comparison to proposed Mars programs as a focus for American space exploration with humans in the next century. The Moon is demonstrably accessible, hospitable, useful, and interesting. Lunar programs are inherently faster and less risky from a programmatic viewpoint than comparable Mars programs such as Mars Direct. The dominant reason for a resumption of manned lunar missions, focused on a single site such as Grimaldi, is to rebuild the infrastructure for missions beyond Earth orbit, the last of which was in 1972. A transitional program, corresponding to the 10 Gemini missions that bridged the gap between Mercury and Apollo, was considered absolutely essential by the Synthesis Group. Further justification for a return to the Moon is the demonstrated feasibility of a robotic lunar observatory, concentrating on optical and infrared interferometry. Many unsolved scientific questions about the Moon itself remain, and could be investigated using telerobotic lunar rovers even before the return of humans. Mars is unquestionably more interesting scientifically and far more hospitable for long-term colonization. A new lunar program would be the most effective possible preparation for the human exploration, settlement and eventually the terraforming of Mars. Lunar and Mars programs are complementary, not competitive. Both can be justified in the most fundamental terms as beginning the dispersal of the human species against uncontrollable natural disasters, cometary or asteroidal impacts in particular, to which mankind is vulnerable while confined to a single planet. Three specific programs are recommended for the 2001-2010 period: Ice Prospectors, to evaluate polar ice or hydrogen deposits; a robotic lunar observatory; and a manned lunar base and observatory.

Lowman, Paul D., Jr.↗