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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

3D Construction of Biologically Derived Materials

System for the 3D Construction of Biologically Derived Materials, Structures, and Parts NASA has developed a novel approach for macroscale biomaterial production by combining synthetic biology with 3D printing. Cells are biologically engineered to deposit desired materials, such as proteins or metals, derived from locally available resources. The bioengineered cells build different materials in a specified 3D pattern to produce novel microstructures with precise molecular composition, thickness, print pattern, and shape. Scaffolds and reagents can be used for further control over material product. This innovation provides modern design and fabrication techniques for custom-designed organic or organic-inorganic composite biomaterials produced from limited resources. Benefits Conserves resources. Few raw or bulk starting materials needed Enables custom design of diverse materials Fast, portable, macroscale, on-demand manufacturing High-fidelity microstructures Uses commercially available parts Applications Biomaterials, biotechnology Organic-inorganic composite materials On-demand manufacturing In situ resource utilization Space stations Military Infrastructure materials The Technology Once genes for a desired material type, delivery mode, control method and affinity have been chosen, assembling the genetic components and creating the cell lines can be done with well-established synthetic biology techniques. A 3D microdeposition system is used to make a 3D array of these cells in a precise, microstructure pattern and shape. The engineered cells are suspended in a printable 'ink'. The 3D microdeposition system deposits minute droplets of the cells onto a substrates surface in a designed print pattern. Additional printer passes thicken the material. The cell array is fed nutrients and reagents to activate the engineered genes within the cells to create and deposit the desired molecules. These molecules form the designed new material. If desired, the cells may be removed by flushing. The end product is thus a 3D composite microstructure comprising the novel material. This innovation provides a fast, controlled production of natural, synthetic, and novel biomaterials with minimum resource overhead and reduced pre- and post-processing requirements.

3D↗
NASA NTRS2023

Automated Fluidics Device for Extraction and Quantification of miRNA Biomarkers From Blood

Radiation Assessment DuRing Exposure And long-Duration Spaceflight (RADREADS) demonstrates space-compatible point-of-care technology for quantitative biological monitoring of blood miRNA biomarkers in response to long-term low dose radiation exposure. This individualized monitoring approach will inform targeted treatment strategies to maximize medical resource utilization by accounting for individual susceptibility to radiation-related illnesses. As human spaceflight progresses beyond Earth’s magnetic shielding, radiation exposure poses a significant risk to astronaut health and safety. Extended operation in this environment comes with an increased risk of radiation exposure, leading to higher risks of radiation sickness, cancer, central nervous system effects, and degenerative diseases. While conventional physical dosimetry techniques capture radiation dose, individualistic susceptibility to radiation damage is varied. Multiple characteristics, including age, body weight, sex, genetics, and immune status, have been found to influence radiosensitivity (Liu et al. 2011, and Bouffler 2016). This differential response necessitates individualized monitoring and targeted treatment strategies to maximize medical resource utilization; however, a practical diagnostic platform for quantifying long-term, low dose radiation-induced tissue damage does not currently exist. MicroRNAs (miRNAs) are a class of small, non-coding RNAs that regulate gene expression by mediating the degradation of messenger RNA. The levels of particular miRNAs are influenced by biological processes such as inflammation and serve as biomarkers for a variety of conditions including cancer (Singh et al. 2017). MicroRNAs are found in various bodily fluids and are amenable to collection via liquid biopsies, providing a minimally invasive and easily quantifiable readout for a variety of radiosensitive reporters. A preliminary signature of 15 spaceflight sensitive miRNA has been identified in rodent and human studies, including miR-21-5p, miR-24-3p, miR-92a-3p, miR-17-5p, miR-16a-3p, miR-34a-3p, and miR-223-3p. These targets generally increased expression with radiation dose and linear energy transfer, though variation between individuals is not yet described. Current gaps in the field include a lack of understanding of longitudinal biological responses to long-term, low dose radiation exposure and the absence of space-compatible point-of-care technology for quantitative biological monitoring. In this body of work, we aim to develop an automated bleed-to-read system to process whole blood for the detection of miRNA biomarkers in order to monitor individualistic responses to radiation exposure. This will be achieved via separating serum (or plasma) from whole blood, followed by extraction, amplification, and quantification of the miRNA using a RT-qPCR reaction. Previously, the WetLab-2 hardware enabled execution of a RT-qPCR reaction aboard ISS; however, it is a manual system that requires crew manipulation and bulky components (Parra et al. 2017). To address these issues, automated fluid handling hardware was developed for each stage of sample preparation. Extraction of total RNA is achieved by sequentially pumping reagents through an off-the-shelf nucleic acid binding column (miRNeasy Serum/Plasma Advanced Kit, Qiagen). This approach eliminates several manual pipetting and centrifuging steps and limits the use of toxic chemicals commonly found in other sample processing techniques. The resulting elution will then be automatically dispensed for RT-qPCR analysis using a compact rotary qPCR (Mic qPCR Cycler, Bio Molecular Systems) that will improve spaceflight compatibility by removing bubbles from the detection region, another challenge highlighted by WetLab-2 (Parra et al. 2017). Efforts are also being made to simplify the RT-qPCR reaction to a 1-step air-dryable mix to improve long-term reagent stability at room temperature and reduce system complexity. By automating the RT-qPCR processes via microfluidic manipulation, RADREADS will reduce crewmember hands-on time and enable the personalized detection of radiation-induced tissue damage during long duration missions. Minimally invasive, longitudinal monitoring of individual’s response to radiation exposure will inform how the physiological system responds to long-term low dose space radiation and enables development of targeted countermeasures by the medical team. Ultimately, this portable technology will require minimal technical expertise and can also be used to monitor miRNA biomarkers associated with other diseases.

Tristen Head↗
NASA NTRSDate not supplied

Does Collection Time Bias the Ecology of Cleanroom Air Samples?

Microbial monitoring of astromaterials collections has taken on increased importance with the return of biologically sensitive samples from the asteroids Ryugu and Bennu and the initiation of the Mars Sample Return Program. Terrestrial bacteria and fungi can alter the mineralogy and organic composition of our collections causing irreversible contamination of pristine samples and increasing the risk of false positives for life detection measurements. NASA has conducted routine microbial monitoring of its existing collections since 20181. Initial monitoring focused on surface samples collected with foam swabs. Although, airborne microbiology is often decoupled from surface microbiology in the built environment2 culture-based air sampling techniques like impactors were not compliant with existing contamination control requirements. Bringing organic rich media, gelatin or liquids into curation cleanrooms presents an unacceptable risk to pristine samples. In 2022 NASA purchased a materials complaint air sampler and began collecting air samples from the cleanrooms in addition to surface samples3. The new instrument uses an electret filter to collect samples that are suitable for cultivating organisms or for direct DNA sequencing. Preliminary DNA sequencing results appeared to indicate that longer sampling times biased the microbial community in favor of hearty, spore-forming bacteria3. We present the results of a study comparing overnight sampling (17 hours) to short (1 hour) sampling of unoccupied curation cleanrooms. The results will help us optimize our monitoring protocols and develop a more detailed inventory of the ecology of astromaterials curation cleanrooms. Methods: We analyzed 72 paired air samples from six different cleanrooms including the meteorite processing lab (ISO 7 equivalent, 16 samples), the lunar lab (ISO 6 equivalent, 10 samples), the stardust lab (ISO 5 equivalent 14 samples), the OSIRIS-REx lab (ISO 5 equivalent, 12 samples), the Hayabusa2 lab (ISO 5 equivalent, 14 samples), and the Genesis lab (ISO 4 equivalent, 6 samples). All the samples were collected with an InnovaPrep Bobcat air sampler operating at a sampling rate of 200 L/min. The sampler operates for 5 minutes out of every 20 minute period. Half of the samples were collected by filtering 3,000L (15 min. of active sampling) of air across an electret filter for one hour. The rest of the samples were collected by filtering approximately 51,000 L air across the filter overnight (~17 hours, 255 min. of active sampling). Cells were eluted from the filter using 6-7 ml of pressurized 0.15% tween 20 in PBS (phosphate buffered saline). This liquid was used to cultivate bacteria according to previously published methods1,4,5 and for DNA extraction and next generation sequencing. DNA was extracted with a Qiagen MagAttract PowerMicrobiome kit6. To identify bacteria and archaea, the 16S rRNA gene was amplified using Earth Microbiome primers for the V4 region 7. The amplified DNA was sequenced on an Illumina MiSeq using a V3 reagent kit. The resulting sequences were processed using DADA2 and QIIME2 as implemented on the EDGE bioinformatics platform8–10. Results: Only two of the 72 samples had no amplifiable DNA. Amplified DNA concentrations ranged from 2.67 – 0.272 ng/µl. The median concentration of amplified DNA for the 1 hour samples was 0.770 ± 0.368 ng/µl. The median concentration of amplified DNA for the overnight samples was 0.877 ± 0.434 ng/µl. On average the overnight samples had slightly more sequences (58,960 vs. 59,456) and ASV’s (amplicon sequence variants) (60 vs 64.5) than the one hour samples, but these differences are not statistically significant. The most abundant ASV in every sample mapped to the genus Cupravidus. ASV’s mapping to the genuses Bacillus, Schlegelella, Thermus, and Staphylococcus were also common. Discussion and Future Work: Alpha diversity statistics like Shannon Entropy and Faith Phylogenetic Diversity are used to describe the diversity of organisms in a single sample. If a longer sampling time was biasing the data, we would expect to see a change in these diversity statistics vs. sample time. However, we did not observe this in our data. The median Shannon entropy was slightly higher for the overnight samples (3.773 vs 3.611) as was the Faith Phylogenetic Diversity (4.042 vs 3.596), but both values were within a standard deviation of each other for the two sampling times (Fig. 1). It is unlikely, that the longer sampling time is introducing bias into our data. We do observe a significant decrease in diversity when comparing the air samples by lab. The Genesis lab (ISO 4 equivalent) has a lower median number of ASV’s (45.5) than the other labs (62). Median values for Shannon Entropy (3.717 vs. 3.430) and Faith Phylogenetic Diversity (3.796 vs. 3.548) are also lower for Genesis, but those values are with one standard deviation of each other for the different sampling times. This is consistent with previous culture-based results suggesting that the environment in cleanrooms tends to select for a core group of organisms capable of surviving under dry, low nutrient, conditions. The presence of the ASV’s mapping to Cupravidus and Thermus in our sequencing blanks and controls suggests that several of the most common organisms in our samples represent contaminants from the reagents used to perform the DNA extractions and sequencing. Further work is needed to identify these contaminants, remove them from our data and recalculate the diversity statistics. This is a systematic error. Therefore, we do not expect removing the sequencing contaminants to change our conclusions. Longer air sample collection times appear to result in slightly higher diversity and do not bias the results towards “hardy” bacteria like spore-formers. Based on these preliminary results we conclude that sampling at least 3,000 liters of air is sufficient to capture the microbial diversity of cleanrooms, and that air samples can also be collected overnight without negatively impacting diversity. These results allow us to be flexible when designing microbial monitoring plans so that they do not interfere with routine lab activity. References: 1. Regberg, A. B. et al. 49th Lunar and Planetary Science Conference (2018). 2. The United States Pharmacopeial Convention. USP General Chapter <1116> (2013). 3. Regberg, A. B., et al. 54th Lunar and Planetary Science Conference (2023). 4. Regberg, A. B. et al. 53rd Lunar and Planetary Science Conference ( 2022). 5. Davis, R. E.,et al. 50th Lunar and Planetary Science Conference (2019). 6. Qiagen. MagAttract® PowerMicrobiome® DNA/RNA EP Kit Handbook. (2018). 7. Walters, W. et al. mSystems 1, (2015). 8. Callahan, B. J. et al. Nat. Methods 13, 581–583 (2016). 9. Hall, M. & Beiko, R. G. Microbiome Analysis: Methods and Protocols113–129 (Springer, 2018). 10. Philipson, C. et al. Bio-Protoc. 7, e2622 (2017).

A. B. Regberg↗
DOE OSTI2020

Improved methods for separation of Cobalt, Manganese, Nickel, Lithium from Waste Lithium-ion Battery Scrap

Improved methods for separation of Cobalt, Manganese, Nickel, Lithium from Waste Lithium-ion Battery Scrap Mark L. Strauss1, John Klaehn1 Luis Diaz Aldana1, Tedd Lister1 Idaho National Laboratory1, Biological and Chemical Processing Department, Idaho Falls, Idaho 83415 ABSTRACT The current methods for the separation of Co, Mn, Ni, Li require that the leach solution have a pH between 2-4 in order to use many Cyanex cationic exchange products. Using a unique buffer solution for the reagent combined with the leachate of innovative electrochemical leaching process for lithium batteries demonstrates the separation is possible without a large of pH modification as other commercial hydrometallugical separation process. This research demonstrates a process that is more environmentally sustainable because the reagent consumption may be less. The corresponding McCable-Thiele diagrams and number of theoretical stages were determined to achieve a 80-90% purity of cobalt, manganese, nickel and lithium.

42 ENGINEERING↗
DOE OSTI2021

Aminopolycarboxylates in trivalent f-element separations

Aminopolycarboxylate reagents strongly bind a variety of metal ions. Trivalent f-elements are no exception. The formed complexes are very stable, especially when aminopolycarboxylate structure contains multiple aminoacetate groups. The efficient coordination of trivalent f-elements by these reagents prompted decades of research and development efforts devoted to separation and purification of f-block metal ions. This chapter overviews the fundamental and applied aspects of aminopolycarboxylate use in trivalent f-element separations. First, a brief synopsis on how the chemical properties of 4f and 5f metal ions determine their similar solution behavior is followed by a discussion of aqueous complexation as means to perturb it. The synthetic methodologies for preparation of aminopolycarboxylate complexants are discussed next. Fundamental features of trivalent f-element complexation by aminopolycarboxylates are summarized, focusing on a variety of structure-function relationships demonstrated for this class of chelators and theoretical efforts to accurately describe such coordination environments. Finally, historical accounts of aminopolycarboxylate use in 4f and 5f element separations are supplemented by recent advances in those research fields.

Jansone-Popova, Santa↗
DOE OSTI2021

Radiolytic transformation of AHA under single-cycle conditions

Historically, the radiation robustness of extractant ligands and the impact of their radiolysis products have been used to evaluate the radiolytic feasibility of solvent system formulations for used nuclear fuel (UNF) reprocessing. However, other key additives (e.g., reducing and hold-back reagents) are employed by these solvent systems. These chemical species have typically been overlooked from a radiolytic perspective, and consequently little is known on how they impact process performance. Therefore, to holistically support the development of advanced, simplified, single-cycle flowsheets for UNF reprocessing, the radiation robustness of two key proposed additives – (i) the complexing reductant acetohydroxamic acid (AHA) and (ii) the hold-back reagent 1,2-cyclohexylenedinitrilotetraacetic acid (CDTA) – have been evaluated under envisioned process conditions using a combination of steady-state gamma and time-resolved pulsed electron irradiation techniques.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Revival and Technology Transfer of 90SrTiO3 Production for Heat Source Applications

Demand for radioisotope power systems (RPS) appears to be on the rise, and it is unlikely that this new demand can be met by plutonium-238. As a result, new heat source designs are under development. One such design is Z1. Z1 is a strontium-90 demonstration heat source developed by Zeno Power Systems in collaboration with the University of Dayton Research Institute and the Pacific Northwest National Laboratory. SrTiO3 was chosen as the fuel form for Z1. SrTiO3 was used to produce dozens of terrestrial RPS decades ago. While this indicates the technology is proven, the skill and experience necessary to effectively produce SrTiO3 has been lost. Recapturing SrTiO3 production technology therefore became necessary. Development started with non-radioactive surrogate experiments using natural strontium. This work showed that the old Oak Ridge flowsheets for SrTiO3 production are quite robust, but some critical pieces of the technology are left out of the old documentation. Specifically, particle sizes of the reagents are critical to producing a phase pure SrTiO3. If the reagent particles are not the right size, then a significant Sr3Ti2O7 phase impurity is observed. This phase impurity was proven to be the result of an incomplete reaction between the strontium and titanium precursors. This technology was transferred to Pacific Northwest National Laboratory where the technology was adapted for use in a hot cell. With the adaptations complete, this technology was used to produce the fuel for Z1 late last year. This represents the first new heat source design produced in the U.S. in over 40 years.

90Sr, strontium titanate, SrTi03, RTG, Radioisotop↗
DOE OSTI2025

Extraction and Separation of Rare-Earth Elements from Coal Fly Ash and Leachate using a Recyclable Ionic Liquid

Coal fly ash (CFA) can be a promising source for recovering rare-earth elements (REEs), as it contains a broad range of REEs with average concentrations frequently exceeding those in traditional rare earth mines. Recent research from our group has demonstrated that REEs can be preferentially extracted from CFA solids using a recyclable ionic liquid (IL), betainium bis-(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]). When CFA was heated with the mixture of IL and an aqueous solution above 65°C, most leached REEs partitioned into the IL phase and were separated from the bulk elements. Subsequent acid stripping of the REE-loaded IL removed the REEs and regenerated the IL for reuse in multiple extraction cycles. This IL-based REE-CFA recovery method has been applied to ten CFA samples derived from different coal sources, including ash recovered from disposal ponds. Analysis of 34 elements confirmed the process consistently achieved high REE recovery efficiency, with strong selectivity over bulk and trace elements across diverse CFA types. In addition to the IL-solid extraction, the performance of [Hbet][Tf2N] in extracting REEs from fly-ash leachates have been evaluated by four commonly used leaching reagents, including HCl, HNO3, H2SO4, and citrate. During the IL-leachate extraction, [Hbet][Tf2N] was mixed and heated with a Class C fly ash leachate generated from each leaching reagent, followed by an acid stripping. It was observed that the partitioning and recovery of REEs increased as the leachate pH increased from 3 to 11. Among the investigated leachates, HCl and citrate proved to be the most compatible with IL extraction, exhibiting a slightly higher REE recovery and a lower non-REE co-extraction compared to the IL-solid extraction. Sc, Y, Nd, Sm, Gd, Dy, and Yb consistently showed a high recovery rate from both CFA solids and leachates. Notably, Pr, Tb, and Ho, which were not previously leached from the CFA solids, were partially recovered from the leachates. Overall, our studies revealed the strong potential of [Hbet][Tf2N] for effectively recovering REEs from leachates, highlighting its applicability as a sustainable strategy for other aqueous REE feedstocks. Furthermore, a techno-economic analysis will be performed to quantify the economic viability of the IL-based REE recovery method and guide future process improvement.

42 ENGINEERING↗
DOE OSTI2021

Benzene Ring Knitting Achieved by Ambient-Temperature Dehalogenation via Mechanochemical Ullmann-Type Reductive Coupling

The current approaches capable of affording conjugated porous networks (CPNs) still rely on solution-based coupling reactions promoted by noble metal complexes or Lewis acids, on-surface polymerization conducted in ultrahigh-vacuum environment at very high temperatures (>200 °C), or mechanochemical Scholl-type reactions limited to electron-rich substrates. To develop simple and scalable approaches capable of making CPNs under neat and ambient conditions, herein, a novel and complementary method to the current oxidative Scholl coupling processes is demonstrated to afford CPNs via direct aromatic ring knitting promoted by mechanochemical Ullmann-type reactions. The key to this strategy lies in the dehalogenation of aromatic halides in the presence of Mg involving the formation of Grignard reagent intermediates. Products (Ph-CPN-1) obtained via direct C-C bond formation between 1,2,4,5-tetrabromobenzene (TBB) monomer feature high surface areas together with mesoporous architecture. The versatility of this approach is confirmed by the successful construction of various CPNs via knitting of the corresponding aromatic rings (e.g., pyrene and triphenylene), and even highly crystalline graphite product was obtained. The CPNs exhibit good electrochemical performance as the anode material in lithium-ion batteries (LIBs). Overall, this approach expands the frontiers of CPN synthesis and provides new opportunities to their scalable applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Defining optimal enzyme and matrix combination for replating of human induced pluripotent stem cell-derived cardiomyocytes at different levels of maturity

Human induced pluripotent stem cell-derived cardiomyocytes (hiPSC-CM) create an unlimited cell source for basic and translational research. Depending on the maturity of cardiac cultures and the intended applications, obtaining hiPSC-CMs as a single-cell, monolayer or three-dimensional clusters can be challenging. Here, we defined strategies to replate hiPSC-CMs on early days (D15-30) or later more mature (D60-150) differentiation cultures. After generation of hiPSCs and derivation of cardiomyocytes, four dissociation reagents Collagenase A/B, Collagenase II, TrypLE, EDTA and five different extracellular matrix materials Laminin, iMatrix-511, Fibronectin, Matrigel, and Geltrex were comparatively evaluated by imaging, cell viability, and contraction analysis. For early cardiac differentiation cultures mimicking mostly the embryonic stage, the highest adhesion, cell viability, and beating frequencies were achieved by treatment with the TrypLE enzyme. Video-based contraction analysis demonstrated higher beating rates after replating compared to before treatment. For later differentiation days of more mature cardiac cultures, dissociation with EDTA and replating cells on Geltrex or Laminin-derivatives yielded better recovery. Cardiac clusters at various sizes were detected in several groups treated with collagenases. Collectively, our findings revealed the selection criteria of the dissociation approach and coating matrix for replating iPSC-CMs based on the maturity and the requirements of further downstream applications.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Rapid Quantification of 237 U Specific Activity for Nuclear Forensics

In the event of an unattributed nuclear explosion, rapid assessment of the short-lived uranium isotope activity and mass can provide valuable information for subsequent forensic analysis. Rapid analysis in the field is enabled by using microfluidic chemistry and deployable instrumentation. Here, this work presents a flow chemistry system, controlled in LabVIEW, that integrates three functionalities: (1) selective extraction of uranium from the sample matrix via a 3D-printed supported liquid membrane module; (2) UV–visible absorbance spectrophotometry to measure the total uranium concentration in the strip flow; and (3) a portable CdTe γ-ray spectrometer coupled to a 3D-printed flow cell to measure 237 U activity concentration in the strip solution. The system was calibrated using standard solutions, and its functionality was demonstrated using a solution of depleted uranium spiked with 237 U. Uranium concentrations of 40–5000 μg/mL were directly quantified online using a 100 mm optical flow cell, while concentrations of 0.5–10 μg/mL were quantified online using a colorimetric reagent. The mass concentration measurement takes approximately 60 min while the activity concentration via γ-ray spectrometry varies depending on the activity of 237 U, with 1 kBq/mL requiring about 30 min of acquisition time to obtain <10% uncertainty at 1σ. This platform provides a fieldable approach for quantifying uranium mass and radioactivity relevant to postdetonation nuclear debris.

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

Assessment of TMT Labeling Efficiency in Large-Scale Quantitative Proteomics: The Critical Effect of Sample pH

Isobaric labeling via tandem mass tag (TMT) reagents enables sample multiplexing prior to LC–MS/MS, facilitating high-throughput large-scale quantitative proteomics. Consistent and efficient labeling reactions are essential to achieve robust quantification; therefore, embedded in our clinical proteomic protocol is a quality control (QC) sample that contains a small aliquot from each sample within a TMT set, referred to as “Mixing QC.” This Mixing QC enables the detection of TMT labeling issues by LC–MS/MS before combining the full samples to allow for salvaging of poor TMT labeling reactions. While TMT labeling is a valuable tool, factors leading to poor reactions are not fully studied. We observed that relabeling does not necessarily rescue TMT reactions and that peptide samples sometimes remained acidic after resuspending in 50 mM HEPES buffer (pH 8.5), which coincided with low labeling efficiency (LE) and relatively low median reporter ion intensities (MRIIs). To obtain a more resilient TMT labeling procedure, we investigated LE, reporter ion missingness, the ratio of mean TMT set MRII to individual channel MRII, and the distribution of log 2 reporter ion ratios of Mixing QC samples. We discovered that sample pH is a critical factor in LE, and increasing the buffer concentration in poorly labeled samples before relabeling resulted in the successful rescue of TMT labeling reactions. Moreover, resuspending peptides in 500 mM HEPES buffer for TMT labeling resulted in consistently higher LE and lower missing data. By better controlling the sample pH for labeling and implementing multiple methods for assessing labeling quality before combining samples, we demonstrate that robust TMT labeling for large-scale quantitative studies is achievable.

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

Reaction Discovery Using Spectroscopic Insights from an Enzymatic C–H Amination Intermediate

Engineered hemoproteins can selectively incorporate nitrogen from nitrene precursors like hydroxylamine, O-substituted hydroxylamines, and organic azides into organic molecules. Although iron-nitrenoids are often invoked as the reactive intermediates in these reactions, their innate reactivity and transient nature have made their characterization challenging. Here we characterize an iron-nitrosyl intermediate generated from NH 2 OH within a protoglobin active site that can undergo nitrogen-group transfer catalysis, using UV–vis, electron paramagnetic resonance (EPR) spectroscopy, and high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) techniques. The mechanistic insights gained led to the discovery of aminating reagents—nitrite (NO 2 – ), nitric oxide (NO), and nitroxyl (HNO)—that are new to both nature and synthetic chemistry. Based on the findings, we propose a catalytic cycle for C–H amination inspired by the nitrite reductase pathway. Furthermore, this study highlights the potential of engineered hemoproteins to access natural nitrogen sources for sustainable chemical synthesis and offers a new perspective on the use of biological nitrogen cycle intermediates in biocatalysis.

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

Browne_EtOHCIMS_SGP_2021

Mixing ratios of ammonia and pyridine. These were measured on a chemical ionization time-of-flight mass spectrometer with ethanol reagent ion at the ARM Southern Great Plains site in October 2021.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Potential Advantages to Employing an Onsite Laboratory at FUSRAP Sites Contaminated with Radionuclides and Metals - 20353

Various factors that support an evaluation of the relative costs, advantages and disadvantages of utilizing an onsite laboratory or an offsite laboratory for remediation of Formerly Utilized Sites Remedial Action Program (FUSRAP) sites contaminated with radionuclides and metals are presented. In terms of how much more quickly an onsite laboratory provides results versus an offsite laboratory, the results of this study provide tools for calculating the amount of cost savings per day for excavation of contaminated soils for various scenarios including: - State, municipal or local property remediation where the remediation schedule becomes time-critical due to the extra cost and inconvenience to the town or municipality caused by the need for increased security and safety personnel, possible road closures and detours, and the inconvenience to the public due to modified or decreased services of State or municipal facilities; - Residential property where the remediation schedule becomes time-critical due to the inconvenience to the homeowner as well as the importance of maintaining good community relations; - Commercial property where the remediation schedule becomes time-critical due to the hardship and potential loss of revenue endured by the property owner; - Open area where treatment of excavation water is required, and - Open area where treatment of excavation water is not required. For every scenario, the number of matrices, radionuclide and metal contaminants of concern and the project duration are important factors. The costs for the onsite laboratory included the capital costs associated with setting up the lab such as trailer(s) or building(s), power and water hookup, analytical testing equipment, balances, computers, desks and bookcases; support equipment such as hot plates, filtration assemblies, safety equipment, ovens, etc.; and supplies such as glassware, pipettes, filters, etc. and ongoing costs such as labor, chemicals and reagents, standards, cost of the laboratory obtaining certification and maintenance. Offsite laboratory sample testing costs are generally very competitive and typically substantially lower than onsite laboratory costs if only the sample testing costs are considered. The great disadvantage of using an offsite laboratory is that they often cannot guarantee rapid turnaround times for results which creates project delays associated with the remediation process including delays determining the completeness of the characterization and remediation processes, delays in backfilling a property and additional costs for treating wastewater (excavation water, stormwater or both). These costs will vary greatly depending upon the area of the country in which the project is located due to the wide range of labor costs for the onsite laboratory and field workers, as well as the contaminants of interest, matrices and most importantly the size of the impacted area and the number of properties located in that area. This paper provides guidelines for calculating the cost savings that may be realized if an onsite laboratory can generate results more quickly than an offsite laboratory by estimating the costs associated with the remediation process for the various scenarios noted above such as work crew labor costs, excavator and dump truck equipment rentals, wastewater treatment costs (if applicable) and the additional costs incurred by homeowners, commercial property owners and towns/municipalities that are reimbursed by the potentially responsible parties. Key assumptions involve the typical quickest turnaround time provided by the onsite and offsite laboratories. Costs for the operation of a wastewater treatment system and the remediation of a site area or property were provided by personnel who have been involved in the operation of a large FUSRAP site in New Jersey for many years. This study provides valuable information for determining the most cost-effective approach for analysis of project samples and therefore may be used on upcoming FUSRAP projects. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Mercury Speciation via Diffusive Gradients Thin-Films Technology

Objectives: Develop and test various diffusive gradient in thin films (DGT) samplers for mercury - SRNL is developing reactive DGTS (rDGTs). Test chemistry to differentiate methylmercury from total and/or inorganic mercury in environmental samples. Fabricate and test rDGT samplers for deployment. Deploy the rDGTs in variable settings. Mercury is a persistent-bioaccumulative-toxic environmental pollutant. Mercury exists in different species such as elemental, inorganic, and methyl. Mercury speciation determine mercury behavior and toxicity. For example, methylmercury strongly accumulates in biota such as fish resulting in potential human health impacts. DGTs are innovative samplers to measure water concentration by diffusion and capture. Types of Hg DGTs used: Total Hg, Inorganic Hg, and Methyl Hg. Deployment Sites: Upper Three Runs, Lower Three Runs, Steele Creek, East Fork Poplar Creek (SRNL Sites), Horizons Creek, NOA Creek, Bruners Creek (ORNL Sites). DGT concentration estimates closely matched alternative measurements for soluble mercury at each Oak Ridge site - DGTs did not respond to particulate mercury. DGTs provide a representative measure for biota uptake since they are left out longer which allows for an average exposure concentration. DMA-80 provided an efficient and quick analysis. Variability in site location made a difference in Hg species. DGT preparations and sampling wasn't as quick and simple as microcolumn technology. Copper reagent degraded agarose gel - more work and cleaner data are needed to assess speciation in rDGTs. Future Work: Use cross-linked polyacrylamide for the collection layer for a stronger plastic. Make a copper diffusion layer without agarose. Test copper separation in lab using realistic stream conditions such as high organic carbon.

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

Development of an In-Situ Leaching Technology for Extracting Residual Uranium from Remediated Soil - 20099

Site-specific chemical solutions for extracting uranium were developed and evaluated for treating previously remediated soil at a former thorium mill tailings site, known as the Former Rare Earths Facility (REF), in West Chicago, Illinois. Prior remediation efforts had resulted in residual sand and gravel aggregate that met the soil cleanup standards. The target soil contains residual levels of uranium, which continues to leach into the site groundwater at levels exceeding groundwater protection standards (GWPS). A series of bench-scale tests were conducted to evaluate the efficacy and viability of in-situ leaching (ISL) technology to treat the target soil for the purposes of attaining uranium GWPS at the REF. Specific objectives of the bench-scale tests entailed identification and selection of optimal leaching, quantification of the extent and rate of uranium released as a function of chemical composition, chemical concentrations, chemical residence times, and obtaining critical data to estimate treatment costs. A combination of sodium bicarbonate and sodium carbonate reagent was the most effective leaching solution. In general, leaching solutions containing a higher concentration of sodium carbonate demonstrated superior uranium leaching capabilities. Removal of 50% of the uranium mass from the soil matrix was adequate for achieving compliance with the site-specific GWPS. After six to seven pore volume flushes (PVFs), the uranium leaching effectiveness of all leaching solutions was similar. The amount of initial uranium removed with each subsequent PVF was minimal, suggesting limited solubility of the remaining mass of uranium. The effects of leaching duration were significant and persisted through at least the first five consecutive PVFs. Leaching of uranium also resulted in leaching of several non-uranium constituents, many of which exceeded applicable National Pollutant Discharge Elimination System (NPDES) standards. Given historical operations and waste disposal practices at the site, leaching of non-uranium constituents was expected. Hydrochloric acid was used to stabilize treated soil. Savings of approximately $148 million in direct and indirect remediation costs are expected with an ISL alternative compared to the excavation and landfill disposal remediation option. (authors)

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DOE OSTI2020

The Argonne SuperGel for CBRN Decontamination - 20160

The Argonne SuperGel was developed between 2003 and 2015 to fill a gap in our nation's capability to quickly decontaminate important structures following a radiological or nuclear release event. Specifically, the decontamination technology was developed to minimize damage to monuments, high valued structures, and critical infrastructure while reducing environmental and health impacts. An important criterion during its development, common reagents were employed that could be easily acquired in order to minimize the timeline for its deployment. Its current formulation uses off-the-shelf super-absorbing hydrogels common to the food and agricultural industry and common salts. Over the years, two formulations of the Argonne SuperGel have been developed to specifically target radioactive cesium contaminations and then, more generically, actinide and fission product contaminations. A biodegradable derivative of phosphoric acid is used in small amounts to promote the removal of insoluble actinide species. The original order of unit operations for the SuperGel technology was 1) applying the wash solution to promote mobility of the contaminants on the surface, 2) applying the hydrogel to absorb the wash solution and contaminants, and 3) removing the hydrogel for disposal. During the course of our studies, we tested a new formulation of the gel technology that eliminated the need for a separate step to apply the wash solution without a compromise in decontamination factors. Greater than 70% and >95% of Cs-137 were removed from concrete and tile coupons, respectively, after two decontaminations, with the best results using wash solutions of 1.0 M KCl and 1.0 M NH{sub 4}Cl formulations. We found no statistical difference between results at 30 deg. C and 40 deg. C or at 70% and 90% relative humidity. We tested the gel under strong UV irradiation to simulate extreme environments. While a tropical noontime UV flux did not adversely affect the gel system decontamination of Cs-137 from concrete or tile coupons, the noontime flux resulted in significant dehydration of the gel after two hours of constant exposure. The rehydration of the gel by the humid air (at 90% humidity and 40 deg. C) was slow and may not be sufficient to offset dehydration by the sun. Americium decontamination from concrete was 70% after optimizing the phosphoric acid derivative and carbonate salt concentration in the wash solution. Since its development, we have had the opportunity to test the SuperGel in the removal of legacy contaminations in hot cell facilities and former glovebox facilities at Argonne. This has provided a unique opportunity to evaluate the SuperGel on a range of contaminants outside the original specifications for its use. We will report on the origin of the gel formulation, some highlighted experimental data including independent testing by the US EPA which has never been reported, and its efficacy for removing legacy alpha contaminations and its potential use for removal of chemical and biological hazardous agents. (authors)

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