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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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NASA NTRS2004

Acquisition of a High-resolution Inductively Coupled Plasma Mass Spectrometer for Cosmochemical and Geochemical Research

The primary goal of our research in this program is to develop new techniques for the analysis of volatile trace elements in very small samples using inductively coupled plasma mass spectrometry (ICP-MS) in preparation for samples returned by the Stardust mission. The instrument that will serve as the basis of our experiments is the ELEMENT2 high-resolution ICP-MS. We have spent the past year designing the laboratory to house this instrument as well as space to store and prepare samples returned by the Stardust mission. Unfortunately, the location that we had initially selected for the instrument turned out to be insufficient for our needs. This was determined almost eight months into the first year of our funding cycle, after extensive work including the production of engineering drawings. However, during this time the Lunar and Planetary Laboratory was selected to lead Phoenix, the first Mars Scout mission. As a result of this award LPL purchased a new, 50,000 square foot building. We have acquired 1400 square feet of laboratory space in this new facility. Four-hundred square feet will be used for a class-100 clean room. This area is designated for storage and preparation of extraterrestrial materials. The additional 1000 square feet will house the ELEMENT2 ICP-MS and peripheral devices. This is an enormous amount of space for this instrument, but it provides plenty of room for expansion in the future. The ICP-MS and the clean room facilities have been purchased. The instrument has been delivered. The startup time for this instrument is relatively short and we expect to be collecting our first data by mid-summer.

Lauretta, D. S.↗
DOE OSTI2025

f-Element complexes with benzyl and cyclohexyl substituted trihydroborates

Actinide complexes containing the simplest borohydrides (BH 4 ) 1- and (MeBH 3 ) 1- can exhibit remarkably highly volatility, which creates unique hazards and handling challenges, especially when making measurements on solid samples under vacuum. Here we describe efforts to prepare new actinide borohydride complexes with attenuated volatility by adding bulkier benzyl (Bn) and cyclohexyl (Cy) substituents to boron. Reactions of ThCl 4 , UI 3 (thf) 4 , and NdI 3 with the mixed alkali metal salt Li/K(BnBH 3 )(thf) n yielded Th(BnBH 3 ) 4 (thf) 2 , U(BnBH 3 ) 4 (thf) 2 , and K[Nd(BnBH 3 ) 4 ], respectively. Notable amongst these, the reaction with UI 3 (thf) 4 proceeds via oxidation of U(III) to U(IV) despite the presence of reducing borohydride ligands. Similarly, reactions of the same metal halides with four equivalents of Li(CyBH 3 )(Et 2 O) n yielded Th(CyBH 3 ) 4 , U(CyBH 3 ) 4 (thf) 2 , and [Li(Et 2 O) 3 ][Nd(CyBH 3 ) 4 ]. Single crystal X-ray diffraction studies of the M(BnBH 3 ) 4 (thf) 2 complexes with M = Th and U confirmed their formulations. Furthermore, the complexes have approximate D 2d point group symmetry and adopt bicapped hexagonal antiprismatic coordination geometries with axial thf ligands and κ 3 -BnBH 3 ligands bound in the equatorial plane. K[Nd(BnBH 3 ) 4 ] and [Li(Et 2 O) 3 ][Nd(CyBH 3 ) 4 ], which were prepared for comparison to U(III) complexes that were unsuccessfully targeted, were also structurally characterized to reveal complex anions with tetrahedral arrangements of trihydroborate ligands bound to Nd(III). Crystals obtained for Th(CyBH 3 ) 4 and U(CyBH 3 ) 4 (thf) 2 were not suitable for XRD studies, but 1 H and 11 B NMR spectra were consistent with their formulations. Collectively, these complexes represent rare examples of structurally characterized f-element trihydroborate complexes with carbon substituents other than methyl.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2023

Launch Complex 34, SWMU CCO542022 DNAPL Source Zone Operations, Maintenance, and Monitoring, Site-Wide Long-Term Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring Report Cape Canaveral Space Force Station, Florida

This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ), Site-Wide Long-Term Monitoring (LTM), and Hot Spot (HS) 6 Air Sparge (AS) System presents the results of Year 13 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, results of the biennial site-wide LTM event, and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. This site has been designated Solid Waste Management Unit (SWMU) CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act (RCRA) Corrective Action Program. For the site-wide biennial LTM event, a total of 55 monitoring wells were sampled for volatile organic compounds (VOCs) in February 2023 and one well was sampled for polychlorinated biphenyls (PCBs) in December 2022. One well planned for VOC sampling was found to be destroyed and could not be sampled (CW0002). The LTM wells are screened in two lithologic zones: Layer 1 (0 to 25 feet below land surface [bls]) and Layer 2 (25 to 30 ft bls), and are located in the outlying areas of LC34 to monitor groundwater conditions within the Low-Concentration Plume (LCP), defined as concentrations exceeding Groundwater Cleanup Target Levels (GCTLs), and the High-Concentration Plume (HCP), defined as concentrations exceeding Natural Attenuation Default Concentrations (NADCs). Results from the biennial sampling event indicated overall plume stability and delineation for the plume, which extends over 300 acres. The operational period for Year 13 of the HCS was from April 1, 2022 to March 31, 2023. Operational runtime for the system was 90 percent during Year 13, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2023, a total of 313,673,241 cumulative gallons of groundwater containing 88,337 pounds of VOCs have been removed by the HCS. Influent concentrations of trichloroethene (TCE) have decreased since startup from approximately 280,000 μg/L (January 2010) to 12,000 μg/L (March 2023). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in December 2022 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2021. Full vertical profile sampling was completed at each DPT from 8 to 98 feet bls, at 5-foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 μg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations and at depths ranging from 8 to 98 feet bls. In addition to DPT sampling, groundwater samples were collected from deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2022 to verify vertical delineation. Layer 7/8 monitoring well results were non-detect in December 2022, with exception of three wells (IW0162, IW043D2, and IW044D2), where TCE, cis-1,2-dichloroethene (cDCE), and/or vinyl chloride (VC) were detected above GCTLs. These wells are screened 105 to 115 feet bls, which is below the existing recovery well capture zone. TCE was first detected in IW0162 in December 2021 and has since been sampled at least monthly to monitor TCE concentrations. The maximum TCE concentration during this operational period was 15,000 μg/L at IW0162 in March 2023. Because of the increased TCE concentrations in this well, a new recovery well (RW21D), screened 86 to 106 feet bls, was installed in January 2023 and incorporated into existing HCS operations. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual in 2020. The HS 6 AS system remained operational during the reporting period covered under this report. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2022 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. A Phase Two Expansion of the HS 6 AS IM was recently completed. As of the date of this report, the expansion became operational in August 2023 and the first quarter of monitoring was conducted in November 2023. Details of the construction, start-up, and performance monitoring will be included in a future Annual PMR. Overall, the tasks associated with Year 13 operation of the HC IM, operation of the HS 6 AS IM, and biennial site-wide sampling were performed in accordance with recommendations included in the previous 2021 LC34 (Year 12) annual report. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives. Results from the site-wide biennial LTM program also show that the overall network of monitoring wells is adequate to continue monitoring plume-wide conditions.

Complex 34↗
DOE OSTI2020

Y-12 Groundwater Protection Program Groundwater and Surface Water Sampling and Analysis Plan (CY 2021)

This plan provides a description of the groundwater and surface water quality monitoring activities planned for calendar year (CY) 2021 at the U.S. Department of Energy Y-12 National Security Complex (Y-12) that will be managed by the Y-12 Groundwater Protection Program (GWPP). Groundwater and surface water monitoring is performed by the GWPP. Groundwater and surface water monitoring will be performed in three hydrogeologic regimes at Y-12: the Bear Creek Hydrogeologic Regime (Bear Creek Regime), the Upper East Fork Poplar Creek Hydrogeologic Regime (East Fork Regime), and the Chestnut Ridge Hydrogeologic Regime (Chestnut Ridge Regime). The Bear Creek and East Fork regimes are located in Bear Creek Valley and the Chestnut Ridge Regime is located south of Y-12. Additional surface water monitoring will be performed north of Pine Ridge along the boundary of the Oak Ridge Reservation. The following sections of this report provide details regarding the CY 2021 groundwater and surface water monitoring activities. Section 2 describes the monitoring locations in each regime and the processes used to select the sampling locations. A description of the field measurements and laboratory analytes is provided in Section 3. Sample collection methods and procedures are described in Section 4, and Section 5 lists the documents cited for more detailed operational and technical information. The narrative sections of the report reference several appendices. Figures (maps and diagrams) and tables (excluding a data summary table presented in Section 4) are in Appendix A and Appendix B, respectively. Groundwater Monitoring Schedules (when issued throughout CY 2021) will be inserted in Appendix C, and addenda to this plan (if issued) will be inserted in Appendix D. Laboratory requirements (bottle lists, holding times, etc.) are provided in Appendix E, and an approved Waste Management Plan is provided in Appendix F. Modifications to the CY 2021 monitoring program may be necessary during implementation. Changes in programmatic requirements may alter the analytes specified for selected monitoring wells or may add or remove wells from the planned monitoring network. Each modification to the monitoring program will be approved by the Y-12 GWPP manager and documented as an addendum to this sampling and analysis plan.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2024

Components Refurbishment and Chemical Analysis Facility, Hot Spot 1 Solid Waste Management Unit #041 Year 4 Annual Performance Monitoring Report Kennedy Space Center, Florida

This Year 4 Annual Performance Monitoring Report (PMR) presents the operations, maintenance, and monitoring activities for the Hydraulic Containment System (HCS) Interim Measure (IM) at the Components Refurbishment and Chemical Analysis (CRCA) facility located at John F. Kennedy Space Center (KSC), Florida. The primary objective of the HCS is to attain hydraulic control of the dissolved-phase chlorinated volatile organic compound (CVOC) plume, with the secondary objective to reduce concentrations of CVOCs in the high-concentration plume to support transition to monitored natural attenuation (MNA). CRCA has been designated Solid Waste Management Unit 041 under the KSC Resource Conservation and Recovery Act Corrective Action Program. The timeframe for activities documented in this Year 4 PMR extends from November 2022 through September 2023. Baseline sampling activities were completed in June 2019, and full-scale startup of the HCS IM was completed in July-August 2019. The operational runtime of the HCS for the Year 4 reporting period was approximately 94%, with the majority of downtime attributed to associated groundwater sampling events, maintenance, and Hurricane Nicole. Almost five million gallons of groundwater were treated during Year 4 of HCS operations, and concentrations of the site’s contaminants of concern (trans-1,2-dichloroethene and vinyl chloride) have been reduced by over 99%. This PMR describes the activities that were performed during Year 4 to operate and monitor the HCS IM, which includes three extraction wells, seven injection wells, and conveyance piping to a modular structure containing the control panel and an air stripper. Influent and effluent sampling results from the air stripper show that the system is operating as designed and is reducing concentrations of contaminants of concern to below detection limits. In addition to HCS operation, this PMR also discusses performance monitoring that has been implemented to assess progress of the HCS IM and overall plume conditions through scheduled groundwater (quarterly and semi-annual) and sub-slab soil gas (quarterly) sampling and analysis. Two ambient air samples were also collected on a quarterly basis in the vicinity of the modular structure and the paved driveway east of the Solvent Reclamation Area during routine operation and maintenance (O&M) activities to ensure safe breathing zone air quality for on-site personnel. All sub-slab soil gas and ambient air sampling conducted during the Year 4 operational period showed results below applicable regulatory air screening limits. Predictions made during the Year 2 groundwater model updates were in close correlation to post Year 4 plume conditions. A supplemental DPT study conducted in 2022 and 2023. This study indicated that low-concentration plume conditions, where concentrations exceed State of Florida Groundwater Cleanup Target Levels, expanded westward to Kennedy Parkway North and northward to the vicinity of the railroad tracks. Based on these results, recommendations were made to install 14 wells to monitor the downgradient and boundary conditions of the expanded LCP. The contents of this Year 4 PMR were presented during the November 2023 KSC Remediation Team meeting, where Team consensus was reached on several items including continued O&M of the HCS, and continued monitoring of groundwater, ambient air, and sub-slab soil gas. Sampling for per- and polyfluoroalkyl substances at CRCA is ongoing and will be submitted under separate cover.

K. Alex Murphy↗
NASA NTRSDate not supplied

Noble Gases in Samples Returned From Asteroids Ryugu and Bennu

Introduction: The asteroid sample return missions, JAXA’s Hayabusa2 [1] and NASA’s OSIRIS-REx [2], fromC-rich asteroids Ryugu and Bennu offer unique opportunities to sample pristine early solar system material, unaffected by terrestrial weathering and contamination, and with a known geological context. The comparison with most primi-tive members of carbonaceous –and inner solar system ordinary and enstatite– chondrite classes allows us to (i) assess the variation (or the lack of thereof) of the distribution of the most volatile elements throughout the entire early solar system, (ii) determine the effects of parent body thermal and aqueous alteration, and (iii) learn about the dynamic evolution and history of the various parent bodies, as sampled by both return missions and meteorite delivery. Here we will present noble gas data obtained from newly received particles from Ryugu and Bennu. Samples & Analysis: We received nine particles allocated by JAXA, with masses of 0.5-1.7 mg mass: four col-lected during Hayabusa2’s first touchdown (chamber A) and five from a small artificial crater (chamber C). We received three particles from Bennu of 0.07, 0.89 and 0.94 mg mass (OREX-800032-102/3/4). All particles were processed, allocated, weighed, and transferred into our UHV sample chamber within pure N2, to prevent any contact with air. We examined all He-Xe isotopes with our custom-built mass spectrometer “Albatros” ([3,4]). Gases were extracted individually from each particle by melting induced by a 1064 μm Nd:YAG IR laser in 2–4 heating steps. Large amounts of water and other reactive volatiles were released, consistent with the presence of abundant volatiles from both Ryugu and Bennu. Residues of Ryugu particles remaining after lasering, subsequently exposed to air, were additionally extracted in a crucible to verify complete gas extraction. Only the particle that still showed a “crystalline” structure after lasering contained detectable Ryugu noble gases, whereas all other particles turned immediately into glassy spheres by laser heating and lacked any gas. Results & Discussion: Ryugu and Bennu matter contains noble gases similar to the most pristine, unheated aqueously altered meteorites, e.g., CM or CI chondrites [5,6]. Remarkably, all four chamber A samples that originated from Ryugu’s surface show solar wind (SW) Ne (trapped (20Ne/22Ne)tr ~12–13), whereas all five chamber C samples do not ((20Ne/22Ne)tr ~9.0–10.7 consistent with the presence of non-solar trapped Ne components such as Q and HL). This demonstrates that JAXA’s sampling strategy succeeded: Chamber C samples analyzed in this work originated from areas shielded from SW, slightly below the surface, that was sampled after the impactor excavated material. The three Bennu particles populate the same range as the Ryugu particles in Ne isotope space with one particle containing SW suggesting that it was part of the uppermost surface layer of Bennu during sampling, while Ne in the smallest sample can be explained best by mixing Ne from presolar diamonds and SiC or graphite, and that in the third one by mixing of, e.g., Q and HL. Using cosmic ray production rates given by [7] yields preliminary exposure ages for Ryugu particles in the same range as determined in [7]. There is, as expected, also no systematic difference between samples from chambers A and C because both sample sets were likely collected within the uppermost layer of Ryugu, which were not shielded from cosmic rays. The concentration of cosmogenic (cos) Ne in the Bennu particle, where Necos was resolvable, is in the same range as found for Ryugu, suggesting roughly similar exposure time to cosmic rays for 5–8 Ma for all particles examined here. The Xe isotopic compositions of all particles are consistent with those of phase Q, with small additions of Xe-HL from presolar diamonds and excess 129Xe* from short-lived 129I decay. The comparably high 129Xe*/129XeQ ratio is similar in all samples, suggesting similar initial I concentrations and closure to Xe loss –or the incorporation of a well-mixed Xe reservoir. The Bennu material was in brief contact with air in the capsule, after atmospheric entry and before storage in pure N2 in a clean room. Both, the –most diagnostic– Xe isotopes and the Ar/Xe vs. Kr/Xe systematics prove that the noble gases are not affected by terrestrial contamination, in contrast to many CI, CY, and CM chondrites found on Earth [5,6], illustrating the importance of sample return. He-Xe concentrations in all particles unaffected bySW are comparable to but at the upper end of ranges reported [5-7]. In accordance with the strong aqueous alteration experienced on the parent bodies of Ryugu and Bennu [1,2], all samples lack the Ar-rich and water-susceptible noble gas components found in less aqueously altered CMs or CRs [e.g., 5,8] and all COs.

Henner Busemann↗
NASA NTRS2008

Final Report on Portable Laser Coating Removal Systems Field Demonstrations and Testing

Processes currently used throughout the National Aeronautics and Space Administration (NASA) to remove corrosion and coatings from structures, ground service equipment and small components results in waste streams consisting of toxic chemicals, spent media blast materials, and waste water. When chemicals are used in these processes they are typically high in volatile organic compounds (VOC) and are considered hazardous air pollutants (HAP). When blast media is used, the volume of hazardous waste generated is increased significantly. Many of the coatings historically used within NASA contain toxic metals such as hexavalent chromium, and lead. These materials are highly regulated and restrictions on worker exposure continue to increase. Most recently the EPA reduced the permissible exposure limit (PEL) for hexavalent chromium. The new standard lowers OSHA's PEL for hexavalent chromium from 52 to 5 micrograms of Cr(V1) per cubic meter of air as an 8-hour time-weighted average. Hexavalent chromium is found in the pretreatment and primer coatings used within the Shuttle Program. In response to the need to continue to protect assets within the agency and the growing concern over these new regulations, NASA is researching different ways to continue the required maintenance of both facility and flight equipment in a safe, efficient and environmentally preferable manner. The use of laser energy to remove prepare surfaces for a variety of processes, such as corrosion and coating removal, weld preparation and non destructive evaluation is a relatively new technology that has shown itself to be environmentally preferable and in many cases less labor intensive than currently used removal methods. The development of a Portable Laser Coating Removal System (PLCRS) started as the goal of a Joint Group on Pollution Prevention (JG-PP) project, led by the Air Force, where several types of lasers in several configurations were thoroughly evaluated. Following this project, NASA decided to evaluate the best performers on processes and coatings specific to the agency. Laser systems used during this project were all of a similar design, most of which had integrated vacuum systems in order to collect materials removed from substrate surfaces during operation. Due to the fact that the technology lends itself to a bide variety of processes, several site demonstrations were organized in order to allow for greater evaluation of the laser systems across NASA. The project consisted of an introductory demonstration and a more in-depth evaluation at Wright-Patterson Air Force Base. Additionally, field demonstrations occurred at Glenn Research Center and Kennedy Space Center. During these demonstrations several NASA specific applications were evaluated, including the removal of coatings within Orbiter tile cavities and Teflon from Space Shuttle Main Engine gaskets, removal of heavy grease from Solid Rocket Booster components and the removal of coatings on weld lines for Shuttle and general ground service equipment for non destructive evaluation (NDE). In addition, several general industry applications such as corrosion removal, structural coating removal, weld-line preparation and surface cleaning were evaluated. This included removal of coatings and corrosion from surfaces containing lead-based coatings and applications similar to launch-structure maintenance and Crawler maintenance. During the project lifecycle, an attempt was made to answer process specific concerns and questions as they arose. Some of these initially unexpected questions concerned the effects lasers might have on substrates used on flight equipment including strength, surface re-melting, substrate temperature and corrosion resistance effects. Additionally a concern was PPE required for operating such a system including eye, breathing and hearing protection. Most of these questions although not initially planned, were fully explored as a part of this project. Generally the results from tesng were very positive. Corrosion was effectively removed from steel, but less successfully from aluminum alloys. Coatings were able to be removed, with varying results, generally dark, matte and thin coatings were easier to remove. Steel and aluminum panels were able to be cleaned for welding, with no known deleterious effects and weld-lines were able to have coatings removed in critical areas for NDE while saving time as compared to other methods.

Rothgeb, Matthew J.↗
NASA NTRS2022

A Detailed Analysis of the Gl 486 Planetary System

Context . The Gl 486 system consists of a very nearby, relatively bright, weakly active M3.5V star at just 8 pc with a warm transiting rocky planet of about 1.3 R ⨁ and 3.0 M ⨁ . It is ideal for both transmission and emission spectroscopy and for testing interior models of telluric planets. Aims . To prepare for future studies, we aim to thoroughly characterise the planetary system with new accurate and precise data collected with state-of-the-art photometers from space and spectrometers and interferometers from the ground. Methods . We collected light curves of seven new transits observed with the CHEOPS space mission and new radial velocities obtained with MAROON-X at the 8.1m Gemini North telescope and CARMENES at the 3.5m Calar Alto telescope, together with previously published spectroscopic and photometric data from the two spectrographs and TESS. We also performed near-infrared interferometric observations with the CHARA Array and new photometric monitoring with a suite of smaller telescopes (AstroLAB, LCOGT, OSN, TJO). This extraordinary and rich data set was the input for our comprehensive analysis. Results . From interferometry, we measure a limb-darkened disc angular size of the star Gl 486 at θ LDD = 0.390 ± 0.018 mas. Together with a corrected Gaia EDR3 parallax, we obtain a stellar radius R * = 0.339 ± 0.015 R ⨀ . We also measure a stellar rotation period at P rot = 49.9 ± 5.5 days, an upper limit to its XUV (5–920 Å) flux informed by new Hubble/STIS data, and, for the first time, a variety of element abundances (Fe, Mg, Si, V, Sr, Zr, Rb) and C/O ratio. Moreover, we imposed restrictive constraints on the presence of additional components, either stellar or sub-stellar, in the system. With the input stellar parameters and the radial-velocity and transit data, we determine the radius and mass of the planet Gl 486 b at R p = 1.343 +0.063 -0.062 R ⨀ and M p = 3.00 +0.13 -0.13 M ⨁ , with relative uncertainties of the planet radius and mass of 4.7% and 4.2%, respectively. From the planet parameters and the stellar element abundances, we infer the most probable models of planet internal structure and composition, which are consistent with a relatively small metallic core with respect to the Earth, a deep silicate mantle, and a thin volatile upper layer. With all these ingredients, we outline prospects for Gl 486 b atmospheric studies, especially with forthcoming James Webb Space Telescope (Webb) observations.

Planetary systems↗
DOE OSTI2021

VFA Biorefinery Design for Informed Production of Ground and Aviation Fuels

The rising demand for low-carbon intensity fuel options requires evaluation of a system which can support their production economically and sustainably. Volatile fatty acids (VFAs) ranging from C2 to C8 can be derived in high yield from arrested anaerobic digestion of biomass. This talk provides an overview of our work in which we upgrade wet waste-derived VFAs using ketonization to elongate their carbon backbone to reach a range relevant to jet or diesel fuels. Kinetic models were used to predict ketone profiles from varying VFA profiles, thereby informing potential carbon flow to either (a) mixed paraffins for use in diesel or aviation fuel, or (b) ethers for use in diesel fuel. To do this, the anticipated products were screened for critical fuel characteristics using predictive tools. The criteria for neat and blended bioblendstocks were chosen based on conventional petrofuel requirements, and they were applied to inform fuel targets, identify limiting characteristics, and guide conversion development. While paraffins can serve as either diesel or aviation fuels, the latter has stringent criteria which include a precise distillation curve range tied to carbon distribution. Fuels which fall outside this range typically fail to meet other property metrics, and as such flashpoint and viscosity were identified as potentially limiting properties of this VFA aviation fuel. However, paraffin fractions which fall outside aviation criteria may meet diesel fuel requirements, which are looser except for the flashpoint minimum. Flashpoint was also a concern for smaller VFA diesel ethers, which posed an additional oxygenate risk of high water solubility. This fuel-informed conversion design process was demonstrated through production of paraffins with reduced sooting as compared to petrodiesel (~34%), and increased renewable aviation fuel blend levels (>70%). VFA-derived ethers improved petrodiesel by increasing fuel autoignition quality by 56% and reducing sooting by 86%. These VFA aviation and diesel fuels could enable greenhouse gas (GHG) reductions of over 165% and 50%, respectively, relative to their purely fossil-derived counterparts. Collectively, this work provides (i) an overview of how we leveraged the flexibility of VFAs for fuel production; and (ii) insight into the potential of a VFA biorefinery to accommodate varied feed and fuel applications, while also considering the merit of tailored fuel production pathways and GHG reduction potential.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2020

Predicting secondary organic aerosol phase state and viscosity and its effect on multiphase chemistry in a regional-scale air quality model

Atmospheric aerosols are a significant public health hazard and have substantial impacts on the climate. Secondary organic aerosols (SOAs) have been shown to phase separate into a highly viscous organic outer layer surrounding an aqueous core. This phase separation can decrease the partitioning of semi-volatile and low-volatile species to the organic phase and alter the extent of acid-catalyzed reactions in the aqueous core. A new algorithm that can determine SOA phase separation based on their glass transition temperature (T g ), oxygen to carbon (O:C) ratio and organic mass to sulfate ratio, and meteorological conditions was implemented into the Community Multiscale Air Quality Modeling (CMAQ) system version 5.2.1 and was used to simulate the conditions in the continental United States for the summer of 2013. SOA formed at the ground/surface level was predicted to be phase separated with core–shell morphology, i.e., aqueous inorganic core surrounded by organic coating 65.4 % of the time during the 2013 Southern Oxidant and Aerosol Study (SOAS) on average in the isoprene-rich southeastern United States. Our estimate is in proximity to the previously reported ~70 % in literature. The phase states of organic coatings switched between semi-solid and liquid states, depending on the environmental conditions. The semi-solid shell occurring with lower aerosol liquid water content (western United States and at higher altitudes) has a viscosity that was predicted to be 10 2 –10 12 Pa s, which resulted in organic mass being decreased due to diffusion limitation. Organic aerosol was primarily liquid where aerosol liquid water was dominant (eastern United States and at the surface), with a viscosity <10 2 Pa s. Phase separation while in a liquid phase state, i.e., liquid–liquid phase separation (LLPS), also reduces reactive uptake rates relative to homogeneous internally mixed liquid morphology but was lower than aerosols with a thick viscous organic shell. The sensitivity cases performed with different phase-separation parameterization and dissolution rate of isoprene epoxydiol (IEPOX) into the particle phase in CMAQ can have varying impact on fine particulate matter (PM 2.5 ) organic mass, in terms of bias and error compared to field data collected during the 2013 SOAS. This highlights the need to better constrain the parameters that govern phase state and morphology of SOA, as well as expand mechanistic representation of multiphase chemistry for non-IEPOX SOA formation in models aided by novel experimental insights.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2023

Components Refurbishment and Chemical Analysis Facility, Hot Spot 1 SWMU #041 Year 3 Annual Performance Monitoring Report Kennedy Space Center, Florida

This Year 3 Annual Performance Monitoring Report (PMR) presents the operations, maintenance, and monitoring activities for the Hydraulic Containment System (HCS) Interim Measure (IM) at the Components Refurbishment and Chemical Analysis (CRCA) facility located at John F. Kennedy Space Center (KSC), Florida. The primary objective of the HCS is to attain hydraulic control of the dissolved-phase chlorinated volatile organic compound (CVOC) plume, with the secondary objective to reduce concentrations of CVOCs in the high-concentration plume to support transition to monitored natural attenuation (MNA). CRCA has been designated Solid Waste Management Unit 041 under the KSC Resource Conservation and Recovery Act Corrective Action Program. The timeframe for activities documented in this Year 3 PMR extends from September 2021 through October 2022. Baseline sampling activities were completed in June 2019, and full-scale startup of the HCS IM was completed in July-August 2019. The operational runtime of the HCS for the Year 3 reporting period was approximately 91%, with the majority of downtime attributed to system maintenance and repair. This is generally consistent with Year 1 and Year 2 runtimes of 85% and 92%, respectively. To help reduce downtime, an anti-scaling amendment, Redux 390, has been used to reduce scaling and help maintain system design parameters. Over nine million gallons of groundwater were treated during Year 3 of HCS operations, and concentrations of the site’s contaminants of concern (trans-1,2-dichloroethene and vinyl chloride) have been reduced by over 97%. This PMR describes the activities that were performed during Year 3 to operate and monitor the HCS IM, which includes three extraction wells, seven injection wells, and conveyance piping to a modular structure containing the control panel and an air stripper. Influent and effluent sampling results from the air stripper show that the system is operating as designed and is reducing concentrations of contaminants of concern to below detection limits. In addition to HCS operation, this PMR also discusses performance monitoring that has been implemented to assess progress of the HCS IM and overall plume conditions through scheduled groundwater (quarterly and semi-annual) and sub-slab soil gas (quarterly) sampling and analysis. Two ambient air samples were also collected on a quarterly basis in the vicinity of the modular structure and the paved driveway east of the Solvent Reclamation Area during routine operation and maintenance (O&M) activities to ensure safe breathing zone air quality for on-site personnel. All sub-slab soil gas and ambient air sampling conducted during the Year 3 operational period showed results below applicable regulatory air screening limits. Predictions made during the Year 2 groundwater model updates were in close correlation to post Year 3 plume conditions. Therefore, it can be assumed that the projected path remains valid for transition to MNA in one to two years of continuous HCS operation. The contents of this Year 3 PMR were presented during the February 2023 KSC Remediation Team meeting, where Team consensus was reached on several items including continued O&M of the HCS, and continued monitoring of groundwater, ambient air, and sub-slab soil gas. Replacement of MW0019 and VMP04 was also recommended, as well as additional direct-push technology sampling to further delineate the downgradient plume and confirm overall site-wide low-concentration plume boundaries. Sampling for per- and polyfluoroalkyl substances at CRCA is ongoing and will be submitted under separate cover.

K. Alex Murphy↗
NASA NTRS2022

Measurement report: Closure Analysis of Aerosol–cloud Composition in Tropical Maritime Warm Convection

Cloud droplet chemical composition is a key observable property that can aid understanding of how aerosols and clouds interact. As part of the Clouds, Aerosols and Monsoon Processes – Philippines Experiment (CAMP2Ex), three case studies were analyzed involving collocated airborne sampling of relevant clear and cloudy air masses associated with maritime warm convection. Two of the cases represented a polluted marine background, with signatures of transported East Asian regional pollution, aged over water for several days, while the third case comprised a major smoke transport event from Kalimantan fires. Sea salt was a dominant component of cloud droplet composition, in spite of fine particulate enhancement from regional anthropogenic sources. Furthermore, the proportion of sea salt was enhanced relative to sulfate in rainwater and may indicate both a propensity for sea salt to aid warm rain production and an increased collection efficiency of large sea salt particles by rain in subsaturated environments. Amongst cases, as precipitation became more significant, so too did the variability in the sea salt to (non-sea salt) sulfate ratio. Across cases, nitrate and ammonium were fractionally greater in cloud water than fine-mode aerosol particles; however, a strong covariability in cloud water nitrate and sea salt was suggestive of prior uptake of nitrate on large salt particles. A mass-based closure analysis of non-sea salt sulfate compared the cloud water air-equivalent mass concentration to the concentration of aerosol particles serving as cloud condensation nuclei for droplet activation. While sulfate found in cloud was generally constrained by the sub-cloud aerosol concentration, there was significant intra-cloud variability that was attributed to entrainment – causing evaporation of sulfate-containing droplets –and losses due to precipitation. In addition, precipitation tended to promote mesoscale variability in the sub-cloud aerosol through a combination of removal, convective downdrafts, and dynamically driven convergence. Physical mechanisms exerted such strong control over the cloud water compositional budget that it was not possible to isolate any signature of chemical production/loss using in-cloud observations. The cloud-free environment surrounding the non-precipitating smoke case indicated sulfate enhancement compared to convective mixing quantified by a stable gas tracer; however, this was not observed in the cloud water (either through use of ratios or the mass closure), perhaps implying that the warm convective cloud timescale was too short for chemical production to be a leading-order budgetary term and because precursors had already been predominantly exhausted. Closure of other species was truncated by incomplete characterization of coarse aerosol (e.g., it was found that only 10 %–50% of sea salt mass found in cloud was captured during clear-air sampling) and unmeasured gasphase abundances affecting closure of semi-volatile aerosol species (e.g., ammonium, nitrate and organic) and soluble volatile organic compound contributions to total organic carbon in cloud water.

Ewan Crosbie↗
DOE OSTI2021

Initial Assessment of TeF 6 Adsorption

Research and development that supports the management of off-gases from nuclear fuel reprocessing has historically been focused on the off-gas streams that arise from aqueous reprocessing technology. However, as Gen-IV reactor development pathways move toward deployment, alternative spent nuclear fuel (SNF) processing and disposition pathways have been considered more actively. This work is focused upon aspects of fluoride volatility (FV) processing. The versatility of this method for deployment against multiple types of spent fuel encourages the continued advancement of both the primary separations processes and the secondary processes, including waste treatment, material control and accountability, and engineering designs. Recent work noted that TeF 6 , the most highly volatile fluorinated compound produced during FV processing, did not have a clear abatement technology recommended in the literature. Thus, this work performed scoping tests on activated alumina and copper shot to assess whether they could be used to remove TeF 6 from gas streams that bear F 2 . Previous work on this topic was not well described in the literature and was not performed with excess F 2 in the stream as would be typical of spent fuel processing via FV. To support an understanding of the concentration of TeF 6 contacting the adsorbent beds, a series of preliminary testing identified the TeF 6 production rate and the equilibrium concentration of TeF 6 in the gas stream contacting the adsorbent. Excess F 2 was determined to not affect the ability of activated alumina to remove TeF 6 from the gas stream quickly and completely. A determination of whether excess F 2 affected the distribution depth of Te in the sorbent bed is still pending analysis of the used sorbent. Literature suggests that when activated alumina is near saturation, TeF 6 could migrate from the sorbent bed. Future testing should investigate this possibility. Copper metal did not adsorb TeF 6 in the presence of F 2 across the sorbent temperature range of 50 to 335°C. F 2 was fully removed by the copper bed. Although preliminary thermodynamics would indicate adsorption to be energetically favorable, other factors that impact adsorption (e.g., slow kinetics, excess fluorine on the copper surface, an unfavorable transition state) are likely preventing the adsorption of TeF 6 at an easily measurable rate. The work also investigated TeF 6 production from multiple forms of Te in the temperature range of 100 to 250°C. No previous study had assessed the initial reaction rates for this process. A carefully designed study allowed determination of the activation energy for the production of TeF 6 from Te metal. The substantial amount of data collected during this study merits analysis beyond what is described here. A more in-depth kinetic analysis will be pursued. Additional analytical results will provide the ability to benchmark adsorption coefficients for TeF 6 , understand the distribution of TeF 6 within the alumina bed, and better understand the effect of F 2 partial pressure on Te fluorination. The data from this report, as supplemented by these additional analyses, will be submitted to a peer-reviewed journal.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Apollo Next Generation Sample Analysis (ANGSA): an Apollo Participating Scientist Program to Prepare the Lunar Sample Community for Artemis

As a first step in preparing for the return of samples from the Moon by the Artemis Program, NASA initiated the Apollo Next Generation Sample Analysis Program (ANGSA). ANGSA was designed to function as a low-cost sample return mission and involved the curation and analysis of samples previously returned by the Apollo 17 mission that remained unopened or stored under unique conditions for 50 years. These samples include the lower portion of a double drive tube previously sealed on the lunar surface, the upper portion of that drive tube that had remained unopened, and a variety of Apollo 17 samples that had remained stored at -27 °C for approximately 50 years. ANGSA constitutes the first preliminary examination phase of a lunar “sample return mission” in over 50 years. It also mimics that same phase of an Artemis surface exploration mission, its design included placing samples within the context of local and regional geology through new orbital observations collected since Apollo and additional new “boots-on-the-ground” observations, data synthesis, and interpretations provided by Apollo 17 astronaut Harrison Schmitt. ANGSA used new curation techniques to prepare, document, and allocate these new lunar samples, developed new tools to open and extract gases from their containers, and applied new analytical instrumentation previously unavailable during the Apollo Program to reveal new information about these samples. Most of the 90 scientists, engineers, and curators involved in this mission were not alive during the Apollo Program, and it had been 30 years since the last Apollo core sample was processed in the Apollo curation facility at NASA JSC. There are many firsts associated with ANGSA that have direct relevance to Artemis. ANGSA is the first to open a core sample previously sealed on the surface of the Moon, the first to extract and analyze lunar gases collected in situ, the first to examine a core that penetrated a lunar landslide deposit, and the first to process pristine Apollo samples in a glovebox at -20 °C. All the ANGSA activities have helped to prepare the Artemis generation for what is to come. The timing of this program, the composition of the team, and the preservation of unopened Apollo samples facilitated this generational handoff from Apollo to Artemis that sets up Artemis and the lunar sample science community for additional successes.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2008

Final Report on NASA Portable Laser Coating Removal Systems Field Demonstrations and Testing

Processes currently used throughout the National Aeronautics and Space Administration (NASA) to remove corrosion and coatings from structures, ground service equipment, small parts and flight components result in waste streams consisting of toxic chemicals, spent media blast materials, and waste water. When chemicals are used in these processes they are typically high in volatile organic compounds (VOC) and are considered hazardous air pollutants (HAP). When blast media is used, the volume of hazardous waste generated is increased significantly. Many of the coatings historically used within NASA contain toxic metals such as hexavalent chromium, and lead. These materials are highly regulated and restrictions on worker exposure continue to increase. Most recently the Occupational Safety and Health Administration (OSHA) reduced the permissible exposure limit (PEL) for hexavalent chromium (CrVI) from 52 to 5 micrograms per cubic meter of air as an 8-hour time-weighted average. Hexavalent chromium is found in numerous pretreatment and primer coatings used within the Space Shuttle Program. In response to the need to continue to protect assets within the agency and the growing concern over these new regulations, NASA is researching different ways to continue the required maintenance of both facility and flight equipment in a safe, efficient, and environmentally preferable manner. The use of laser energy to prepare surfaces for a variety of processes, such as corrosion and coating removal, weld preparation, and non destructive evaluation (NDE) is a relatively new application of the technology that has been proven to be environmentally preferable and in many cases less labor intensive than currently used removal methods. The novel process eliminates VOCs and blast media and captures the removed coatings with an integrated vacuum system. This means that the only waste generated are the coatings that are removed, resulting in an overall cleaner process. The development of a Portable Laser Coating Removal System (PLCRS) started as the goal of a Joint Group on Pollution Prevention (JG-PP) project, led by the Air Force, where several types of lasers in several configurations were thoroughly evaluated. Following this project, NASA decided to evaluate the best performers on processes and coatings specific to the agency. Laser systems used during this project were all of a similar design, between 40 and 500 Watts, most of which had integrated vacuum systems in order to collect materials removed from substrate surfaces during operation.

Rothgeb, Matthew J↗
NASA NTRSDate not supplied

Leveraging VIPER Geotechnical and Mobility Insights for Endurance Rover and Traverse Development

A new generation of lunar surface rover exploration is rapidly approaching. This is evidenced by the rise of commercially developed rovers from private companies (e.g., Lunar Outpost’s MAPP) and government agencies, like NASA’s Volatiles Investigating Polar Exploration Rover (VIPER), the Lunar Terrain Vehicle (LTV), and the Endurance/Intrepid rover concepts, and the INSPIRE mission concept. The drive distance requirements for off-world vehicles are also rapidly increasing. For example, LTV driving requirements dictate a 20 km range on a single battery charge, with an overall lifetime requirement of 13,000 km over a minimum 10-year service life. Similarly, NASA's Endurance-A mission concept requires a 2000 km vehicle traverse distance, which is nearly 50 times further than the USSR's Lunokhod 2, the longest lunar rover mission to date. Previous planetary surface missions on the Moon and Mars have revealed harsh mobility conditions: aggressive rocky terrains on Mars severely damaged the Curiosity rover’s wheels, soft lunar regolith caused the Lunokhod 2 rover to sink and NASA’s Apollo 15 LRV (Lunar Roving Vehicle) spun out due to poor traction, which required manual correction. This demonstrates that mobility challenges like wheel degradation and soft soil driving performance must be accounted for in a mission’s design phase to meet increasingly aggressive mission durations and mobility goals. The success of these long duration missions requires highly reliable and durable mobility platforms in conjunction with a more developed understanding of the geotechnical properties of the lunar surface. The VIPER mission is uniquely posed to inform future missions about mobility performance, wheel durability, and lunar surface soil mechanics of sunlit and shadowed regions through use of data streams that already exist for other mission purposes. VIPER’s mission to the lunar south pole will provide a new perspective into off-world mobility challenges including traversal into permanently shadowed regions. Mobility data from VIPER’s mission will represent a first glimpse into the surface mobility challenges of the lunar South Pole. Utilization of VIPER’s existing capabilities including cameras, inertial measurement unit (IMU) data, motor currents/torque, drill data, and the rover’s suspension state and kinematics provide the opportunity to determine potentially useful information for future rover and traverse designs, as well as on-Earth testing practices. Data products collected during VIPER’s mission could inform design considerations for the Endurance rover much earlier than NASA’s standard “lessons learned” approach as VIPER has a highly tactical mission operations structure. This work outlines the specific links between possible data products from the VIPER mission and their potential impact on the Endurance/Intrepid mission concepts in their early design phases. From VIPER, we will also gain insights for future development of onboard mobility software as VIPER is a way-point driven rover which requires more constant human operation on Earth than some other rover missions (non-lunar surface). Primary VIPER data products and insights of interest include wheel sinkage, wheel slip, wheel degradation, surface soil shear strength, and terrain slope estimation. VIPER data products will be made available via the Planetary Data System’s Geosciences and Cartography and Imaging Sciences nodes, conforming to the PDS4 standard.

mobility↗
NASA NTRS2020

Reconstructing Magma Storage Depths for the 2018 Kilauean Eruption from melt inclusion CO2 Contents: The importance of Vapor Bubbles

The 2018 Lower East Rift Zone (LERZ) eruption of Kīlauea Volcano and the accompanying collapse of the summit caldera marked the most destructive phase of activity on Hawai’i in the last 200 years. The integration of petrological data extracted from lava samples collected throughout the eruption with geodetic data examining the caldera collapse event, and estimates of the co-erupted flux of SO2 from the main eruptive fissure (Fissure 8), provides an exceptional opportunity to determine the reservoir geometry and magma transport paths supplying Kīlauea’s LERZ. The forsterite contents of erupted olivines and the degree of disequilibrium with their carrier melts indicate that two distinct olivine populations were erupted from Fissure 8. Melt inclusion entrapment pressures reveal that more evolved olivines (Fo<81.5) crystallized at ~2 km depth within the shallower Halema’uma’u reservoir, while more primitive olivines (Fo>81.5)crystallized within the deeper South Caldera reservoir at ~3–5 km depth. Crucially, primitive olivines experienced extensive post-entrapment crystallization, driving the growth of a vapor bubble. Raman spectroscopy reveals that this bubble contains up to 99% of the total inclusionCO2 budget (median=93%). Measurements of CO2 in only the glass phase would have underestimated entrapment depths by up to 60× (median=11×), and the importance of the SC reservoir as a source of magma to Fissure 8 would have been overlooked. Overall, we demonstrate that Raman measurements of bubbles, along with careful choice of suitably-calibrated H2O-CO2 solubility model, is vital to place accurate constraints on the depths of magma storage regions supplying volcanic eruptions.

SIMS↗
NASA NTRS2021

Wilson Corners SWMU 001 2019-2020 Annual Long-Term Monitoring Report Kennedy Space Center, Florida

This report presents a summary of the long-term monitoring (LTM) activities that occurred in 2019 and 2020 at Wilson Corners, Solid Waste Management Unit 001, at the John F. Kennedy Space Center (KSC), Florida. The site is monitored under KSC’s Resource Conservation and Recovery Act Corrective Action Program. Adaptive site management is being utilized through ongoing assessment, design, and interim measures. This approach also meets the requirements of Chapter 62-780, Florida Administrative Code. The goal of LTM at this site is threefold: to determine groundwater flow characteristics, monitor the downgradient concentration trends, and monitor select locations internal to the groundwater plume. Every 5 years, upgradient and side-gradient monitoring wells are sampled to verify delineation. The last time this was performed was in 2015. Sampling of these wells in 2020 was replaced with the direct push technology investigations in October 2020 and April 2021. The activities presented in this report include three field events: (1) December 2019 -groundwater gauging of 38 monitoring wells and sampling of 36 monitoring wells; (2) May 2020 - groundwater sampling of 7 monitoring wells; and (3) December 2020 - groundwater gauging of 49 monitoring wells and sampling of 43 monitoring wells. During the December 2019 and May 2020 events, monitoring wells were sampled using passive diffusion bags and were analyzed for a “full list” of volatile organic compounds (VOCs), including Freon 113. During the December 2020 event, the low flow sampling method was used, and samples were analyzed for a “select list” of VOCs, including Freon 113. The following conclusions can be made based on the 2019 and 2020 LTM results: •In December 2019 and December 2020, groundwater flow for the site was generally to the west with the individual zones only varying by occasional northerly and southerly components. This is generally consistent with historical observations at the site. •The GCTL plume continues to extend both horizontally and vertically beyond our current monitoring well network. •The vertical extent of VOCs was historically generally delineated by monitoring wells screened greater than 48 feet bls. The results from the two vertical extent monitoring wells WILC-MW0078 and WILC-MW0130 that were sampled during the 2019 and 2020 LTM indicate that groundwater VOC concentrations in both wells were greater than the GCTL. •Freon 113 was not detected above GCTLs during the 2019 and 2020 LTM events. Based on groundwater sampling activities performed during this reporting period, including recent DPT groundwater sampling conducted for the implementation of an air sparge system, the following recommendations are provided: •Install 10 new monitoring wells, which will be sampled along with 49 existing monitoring wells, to assist with delineation of the low concentration plume. The wells are listed inTable 4-1, and the proposed locations are presented on Figures4 -1 through 4-5. (Figures 4-1, 4-2, 4-3, and 4-5 also show updated plumes and proposed performance monitoring well locations. This information will be discussed and presented under a separate cover.) •Modify the annual LTM sampling plan as presented inTable 4-1. •Sampling for future events at the site will be conducted using low flow pumping methods. The next annual LTM sampling event is currently planned for December 2021. Please note the 10 new monitoring wells will not be installed before this event but will be installed as part of the upcoming IM construction and will be sampled during baseline sampling, along with the 49 existing monitoring wells. Following this sampling event, it is recommended that the Annual LTM be combined with the performance monitoring under the IM implementation, and LTM be temporarily discontinued. Objectives of the 2021 LTM are to: (i) evaluate groundwater gradient and flow direction by collecting depth to water measurements from LTM wells; (ii) continue monitoring the peripheral VOC trends in the northern, southern, and western portions of the site by monitoring existing wells and installing and monitoring new wells as recommended; and (iii) monitor select internal plume wells.

Jennifer Lynn Joyal↗