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Pushing the limits of pulse shape discrimination in a large liquid xenon detector

Abstract The LUX-ZEPLIN (LZ) experiment is a direct-detection dark matter experiment, optimized to search for weakly interacting massive particles (WIMPs) through WIMP-nucleon interactions. The main challenge in dark matter detection is differentiating between WIMP signals and background events. In LZ, the ratio of ionization to scintillation signals (charge-to-light) is the primary method for rejecting electronic recoil (ER) background. Pulse shape discrimination (PSD) offers a method for additional ER backgrounds rejection in liquid xenon detectors. In this paper, the discrimination power of PSD with the LZ experiment is discussed. To precisely characterize the scintillation pulse shape, an analysis framework is developed to reconstruct the detection time of individual photons. Using LZ calibration data, the photon-timing tail fraction discriminator is optimized and achieves ER leakage as low as $$15\%$$ 15 % . For specific background processes such as $$^{124}$$ 124 Xe double electron capture, the leakage is reduced further to about $$5\%$$ 5 % . PSD is combined with charge-to-light to form two-factor discrimination (TFD). The optimized TFD performance is compared with the performance of the charge-to-light method, with the corresponding false positive rate reduced by up to a factor of two for large scintillation pulses. Finally, PSD and TFD are applied to data from LZ’s WS2024 run and their performance is summarized.

Akerib, D. S. [SLAC National Accelerator Laborator↗

Design of an Excavation Robot: Regolith Advanced Surface Systems Operations Robot (RASSOR) 2.0

To continue on a sustainable and flexible path, NASA needs to address the challenge of collecting and moving large amounts of regolith at the destination. Acquiring the water resources on Mars will require mining significant quantities of regolith and this is not possible with the state-of-the-art low mass excavation systems. Low gravity environments (Mars = 3/8 G) and launch mass restrictions limit the traction and the resulting reaction force of the vehicle, making current terrestrial techniques impractical. This project addressed this challenge by developing a completely new technology that can mine large quantities of regolith on Mars. Recent measurements by the “Curiosity” rover on Mars have found that the regolith contains ~ 2% water by weight globally, ~4% in Jezero Crater (Human Architecture Team’s reference landing site), and much more at the poles(Leshin et al, 2013). RASSOR 2.0 is a planetary excavator, which has a mass of 66 kg, with a 0.38 kg vehicle mass per kilogram, per hour of excavation rate and power usage of 4 W per kg of regolith excavation rate. A single RASSOR 2.0 can excavate a minimum of 2.7 metric tons of regolith per day.This is accomplished by using counteracting excavation forces on two opposing digging implements called bucket drums and an autonomous mining control system. This work has addressed several major research areas outlined in the NASA Technology Area (TA) 04 Robotics & Autonomous Systems and TA 07 Human Destination Systems roadmaps. This project started at Technology Readiness Level (TRL) 4 as a low fidelity “proof of concept” prototype which has successfully demonstrated basic regolith simulant excavation functionality in a lab-scale gravity off load test. The foundational technology described here was awarded US patent number: US 9027265 for a “Zero horizontal reaction force excavator” on May 12, 2015.

RASSOR↗

Innovations in Sustainable Passive Wastewater Treatment - 20236

Sustainable water treatment systems, engineered to mimic natural processes and utilize natural materials, yield economic and environmental benefits through reductions in long term operational inputs, including: power, chemicals, and labor. Golder is an industry leader in the development and implementation of sustainable technologies at operating and closed mines. We continue to innovate these technologies and customize solutions to meet client needs by applying past experience and focused research. Sustainable (or passive) water treatment systems include ponds, wetlands, flow-through natural media beds, and limestone drains. These systems can blend in with a natural environment, are highly cost-effective for long-term water treatment, and can outcompete traditional active treatment technologies. Application of sustainable technologies relative to active technologies can be influenced by the influent water matrix, effluent limitations, flow rate of water requiring treatment, and available land area. In this presentation, four Golder-developed systems are reviewed as case studies, demonstrating our continued progressive approach to advancing sustainable water treatment technologies to meet industry needs. These case studies focus on design innovations and operational performance from data collected from the operational systems. Resources (power, chemicals, labor) required for the operation of each case study are compared with those that would be required for operation of their active treatment technology alternatives. - Case Study 1 presents an anaerobic biochemical reactor (BCR), a technology typically implemented for metals treatment and acid neutralization, for the treatment of sulfate to low concentrations (<250 mg/L). Active treatment via reverse osmosis (RO) membrane filtration is typically required for treatment of sulfate to similar concentrations, this innovation provides potential for sustainable treatment to replace the need for energy, chemical, labor, and waste (brine) intensive RO treatment for specific applications. Magnetite waste rock materials from the site were upcycled for use in this system to provide sequestration of the sulfide generated in the BCR. - Case Study 2 examines another novel application of the conventional BCR, modified for the removal of radionuclides and metals (uranium, radium, and selenium) at a closed uranium mine. - Case Study 3 presents implementation of sustainable treatment for mine drain water from a historic mine site, now a state park with around 100,000 visitors per year. The system includes a pond, wetland, and manganese removal bed surrounded by public trails designed to maintain the character of the park. The system treats for arsenic, iron, and manganese at relatively high flows (up to 1,200 gpm), with large seasonal fluctuations in flow and quality. - Case Study 4 is a unique project for which Golder is currently designing a sustainable treatment system, with no energy input, to treat nitrate in mine water post-closure at a site near the arctic circle. In this unprecedented application, climate, management of freshet, and space availability presented substantial technical challenges. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mining and beneficiation: A review of possible lunar applications

Successful exploration of Mars and outer space may require base stations strategically located on the Moon. Such bases must develop a certain self-sufficiency, particularly in the critical life support materials, fuel components, and construction materials. Technology is reviewed for the first steps in lunar resource recovery-mining and beneficiation. The topic is covered in three main categories: site selection; mining; and beneficiation. It will also include (in less detail) in-situ processes. The text described mining technology ranging from simple diggings and hauling vehicles (the strawman) to more specialized technology including underground excavation methods. The section of beneficiation emphasizes dry separation techniques and methods of sorting the ore by particle size. In-situ processes, chemical and thermal, are identified to stimulate further thinking by future researchers.

Chamberlain, Peter G.↗

Microbial ecology of acidic, biogenic gypsum: community structure and distribution of extremophiles on freshly formed and relict sulfate deposits in a hydrogen sulfide-rich cave

Sulfate minerals are abundant on the Martian surface, and many of these evaporite deposits are thought to have precipitated from acidic fluids. On Earth, gypsum (CaSO 4 •2H 2 O) and other sulfates sometimes form under acidic conditions, so exploring the extremophilic life that occurs in these mineral environments can help evaluate the astrobiological potential of acid sulfate depositional settings. Here, we characterized the microbial communities associated with acidic gypsum deposits in a sulfuric acid cave, where sulfate precipitation is driven by sulfide-oxidizing bacteria and archaea. We used 16S rRNA gene sequencing and cell counts to characterize gypsum-associated microorganisms in freshly formed and relict deposits throughout the cave, to test how microbial community composition and abundance would vary with distance from the sulfidic water table and with the concentration of H 2 S(g) and other gases in the cave atmosphere. We found that actively forming gypsum in the lower cave levels was colonized by low-diversity communities that have few cells compared to other environments in the cave. The most abundant taxa were Acidithiobacillus, Metallibacterium, Mycobacteria, and three different Thermoplasmatales-group archaea, which occupied distinct niches based on proximity to sulfidic streams and the concentration of gases in the cave air. By contrast, deposits in older cave levels had more diverse communities that were distinct from those associated with freshly formed gypsum and likely represent a community reliant on different energy resources. These findings show that acidic sulfate deposits serve as habitats for extremophilic microorganisms and broaden our knowledge of the life associated with terrestrial sulfates.

58 GEOSCIENCES↗

Estimating the Electric Fields Driving Lightning Dart Leader Development With BIMAP‐3D Observations

Abstract In this paper, a numerical dart leader model has been implemented to understand the leader's development and the corresponding electric field changes observed by the 3D broadband mapping and polarization (BIMAP‐3D) system. The model assumes the extending leader channel is equipotential and has a linear charge distribution induced by an ambient electric field. The charge distribution induced by the ambient field can be used to model the electric field change at the ground. We then find the ambient electric field which best fits the field change measurements at the two BIMAP stations. The estimated ambient electric field decreases in the direction of dart leader propagation. Our observations and modeling results are consistent with our earlier hypothesis that dart leader speed is proportional to the electric field at the leader tip. The model also supports our earlier analysis that leader speed variations near branch junctions were due to previous charge deposits near the junctions. The modeled tip electric field is generally lower than the breakdown field unless the pre‐dart‐leader channel has a significant temperature of 3,000 K. This is consistent with the fact that dart leaders typically do not form new branches into the virgin air. Furthermore, the tip field is generally close to the negative streamer stability field at ambient temperatures, explaining the nature of the narrow and well‐defined channel structure. In addition to the charge distribution and the ambient and tip electric field, the development of the channel potential and current distribution are also presented.

3D lightning mapping↗

A critical review of the state of foreign space technology

Scientific and technical capabilities of foreign nations, i.e., USSR, Japan, West Germany, UK, France, and other ESA nations, are reviewed. Attention is given to areas in which these nations are concentrating their efforts, as well as to areas in which achievements have already been realized. Among them: space industry and processing (including nonterrestrial mining), communications satellite technology, life support systems and space colonies, earth observation, space-borne astronomy and unmanned planetary probes, materials and propulsion, and exobiology (CETI/SETI).

Grey, J.↗

Hydrothermal solubility of Dy hydroxide as a function of pH and stability of Dy hydroxyl aqueous complexes from 25 to 250 °C

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.

58 GEOSCIENCES↗

The economics of mining the Martian moons

The costs for extracting and shipping volatiles such as water, carbon, and nitrogen that might be found on Phobos and Deimos are estimated. The costs are compared to the cost of shipping the same volatiles from earth, assuming the use of nuclear powered mining facilities and freighters. Mineral resources and possible products from the Martian moons, possible markets for these products, and the costs of transporting these resources to LEO or GEO or to transportation nodal points are examined. Most of the technology needed to mine the moons has already been developed. The need for extraterrestrial sources of propellants for ion propulsion systems and ways in which the mining of the moons would reduce the cost of space operations near earth are discussed. It is concluded that it would be commercially viable to mine the Martian moons, making a profit of at least a 10 percent return on capital.

Leonard, Raymond S.↗

Evidence for a Single Holocene Paleoseismic Event on the Pajarito Fault, Northern New Mexico

Low-slip rate fault systems tend to be less studied than their high-slip rate counterparts, and paleoseismic techniques used to study them may pose challenges in interpretation that differ from high-slip rate systems. A good example of this is the Pajarito fault system (PFS), a normal fault complex within the Rio Grande rift. Despite numerous previous paleoseismic trenching studies conducted on the PFS between 1990 and 2003, considerable uncertainty remains regarding its Holocene paleoseismic history, particularly for the primary Pajarito fault (PF). To further clarify the PF paleoseismic history, we present data from paleoseismic investigations of 6 trenches at 3 distinct locations along the PF. Though the totality of the age and structural data obtained in this study is complex and not entirely consistent with any one interpretation, a single Holocene paleoearthquake occurring younger than ∼1,600 to 2,300 kcal yr BP is the simplest interpretation. It is possible that the PF records two Holocene events, with a penultimate event 6.9–2.4 kcal yr BP event and the aforementioned most recent event (MRE) between 2.3 and 1.6 kcal yr BP. However, only a single wall of one trench, out of a total of 12 walls in our 6 trenches, provides evidence supporting that interpretation. This study finds evidence of a single late Holocene paleoseismic event on the PF and sparse evidence for 2 Holocene paleoseismic events on the PF and highlights the benefits of logging multiple trench walls to better understand the complexity that results from this low-slip rate, low-deposition-rate fault system.

58 GEOSCIENCES↗

Evaluation of Cease Fire CFP 640 for Use in Gloveboxes (Final Report)

A Los Alamos National Laboratory (LANL) task group was established to discuss and evaluate a candidate fire suppression system (FSS) for gloveboxes (GB) and dropboxes (DB, for brevity, this report will simply refer to gloveboxes). Suitability criteria include compliance, compatibility, and capability. LANL contracted with New Mexico Tech (NMT) to quantitatively evaluate the perfor mance of one of those systems including its ability to extinguish GB fires, limit over-pressurization of the GB, etc. Additionally, the results of these experiments provide data points that could be used when fire hazard evaluations (FHEs) are conducted for determining when to require a fire suppres sion system installation within a GB (as required by NFPA 801, Standard for Facilities Handling Radioactive Materials, DOE Standard 1066-2012 Fire Protection, and AGS-G010-2011 Standard of Practice for Glovebox Fire Protection).

42 ENGINEERING↗

Improve Data Mining and Knowledge Discovery Through the Use of MatLab

Data mining is widely used to mine business, engineering, and scientific data. Data mining uses pattern based queries, searches, or other analyses of one or more electronic databases/datasets in order to discover or locate a predictive pattern or anomaly indicative of system failure, criminal or terrorist activity, etc. There are various algorithms, techniques and methods used to mine data; including neural networks, genetic algorithms, decision trees, nearest neighbor method, rule induction association analysis, slice and dice, segmentation, and clustering. These algorithms, techniques and methods used to detect patterns in a dataset, have been used in the development of numerous open source and commercially available products and technology for data mining. Data mining is best realized when latent information in a large quantity of data stored is discovered. No one technique solves all data mining problems; challenges are to select algorithms or methods appropriate to strengthen data/text mining and trending within given datasets. In recent years, throughout industry, academia and government agencies, thousands of data systems have been designed and tailored to serve specific engineering and business needs. Many of these systems use databases with relational algebra and structured query language to categorize and retrieve data. In these systems, data analyses are limited and require prior explicit knowledge of metadata and database relations; lacking exploratory data mining and discoveries of latent information. This presentation introduces MatLab(R) (MATrix LABoratory), an engineering and scientific data analyses tool to perform data mining. MatLab was originally intended to perform purely numerical calculations (a glorified calculator). Now, in addition to having hundreds of mathematical functions, it is a programming language with hundreds built in standard functions and numerous available toolboxes. MatLab's ease of data processing, visualization and its enormous availability of built in functionalities and toolboxes make it suitable to perform numerical computations and simulations as well as a data mining tool. Engineers and scientists can take advantage of the readily available functions/toolboxes to gain wider insight in their perspective data mining experiments.

Shaykhian, Gholam Ali↗

Improve Data Mining and Knowledge Discovery through the use of MatLab

Data mining is widely used to mine business, engineering, and scientific data. Data mining uses pattern based queries, searches, or other analyses of one or more electronic databases/datasets in order to discover or locate a predictive pattern or anomaly indicative of system failure, criminal or terrorist activity, etc. There are various algorithms, techniques and methods used to mine data; including neural networks, genetic algorithms, decision trees, nearest neighbor method, rule induction association analysis, slice and dice, segmentation, and clustering. These algorithms, techniques and methods used to detect patterns in a dataset, have been used in the development of numerous open source and commercially available products and technology for data mining. Data mining is best realized when latent information in a large quantity of data stored is discovered. No one technique solves all data mining problems; challenges are to select algorithms or methods appropriate to strengthen data/text mining and trending within given datasets. In recent years, throughout industry, academia and government agencies, thousands of data systems have been designed and tailored to serve specific engineering and business needs. Many of these systems use databases with relational algebra and structured query language to categorize and retrieve data. In these systems, data analyses are limited and require prior explicit knowledge of metadata and database relations; lacking exploratory data mining and discoveries of latent information. This presentation introduces MatLab(TradeMark)(MATrix LABoratory), an engineering and scientific data analyses tool to perform data mining. MatLab was originally intended to perform purely numerical calculations (a glorified calculator). Now, in addition to having hundreds of mathematical functions, it is a programming language with hundreds built in standard functions and numerous available toolboxes. MatLab's ease of data processing, visualization and its enormous availability of built in functionalities and toolboxes make it suitable to perform numerical computations and simulations as well as a data mining tool. Engineers and scientists can take advantage of the readily available functions/toolboxes to gain wider insight in their perspective data mining experiments.

Shaykahian, Gholan Ali↗

Overview of NASA ISRU Plans, Priorites, and Activities

Introduction:The National Aeronautics andSpace Administration (NASA) of the United States ofAmerica (US) has initiated the Artemis Moon to Marsprogram to send astronauts (the first woman andperson of color) back to the lunar surface, create asustainable human lunar exploration program, andlead the first human exploration mission to the Marssurface in the 2030’s [1]. A major objective of thisprogram is to characterize the resources that exist onthe Moon and Mars, and learn how to utilize them forsustained and affordable exploration. Commonlyknown as In Situ Resource Utilization (ISRU), thesearch for, acquisition, and processing of resources inspace has the potential to greatly reduce thedependency on transporting mission consumables andinfrastructure from Earth, thereby reducing missioncosts, risks, and dependency on Earth.ISRU is Enabling: Through the extraction andprocessing of resources into mission commoditiessuch as rocket propellants, life support consumables,and fuel cell reactants, ISRU enhances and evolvesthe cis-lunar, lander, and surface transportationsystems required for human exploration; expandingand enhancing HOW humans can explore and returnfrom the Moon. Through the extraction andprocessing of resources into metals, silicon, and othermanufacturing and construction feedstock, ISRUenhances and allows for the expansion of criticalinfrastructure using in situ manufacturing andconstruction capabilities that influence WHAT humanscan do on the Moon and in cis-lunar space. Becauseof this, ISRU supports and enables commercialinvolvement beyond NASA and governmentalagencies by both lowering the cost of sustainedtransportation to/from/on the Moon as well assupporting the market required for needing thesetransportation systems. Strategic Framework:To achieve this vision,NASA’s Space Technology Mission Directorate(STMD) ensures the coordinated development ofISRU and other critical space and surfaceinfrastructure elements such as propulsion, power,manufacturing, construction, and robotics through theStrategic Technology Architecture Roundtable(STAR) process. Through STAR, an integratedframework and process has been created allowing forcapabilities and technologies to be linked andassessed, gaps to be identified, specifications andmetrics to be established, and provide a means toprioritize and implement technology development andmissions. A critical part of the STAR effort has beenthe establishment of the Strategic Framework thatorganizes all work under four major Thrusts (Go,Land, Live, and Explore) and identifies the drivingOutcomes for each of these Thrusts. From the Thrustsand Outcomes, all work can be categorized and linkedbetween Capability Areas, and Technology Gaps canbe identified and addressed (Figure 1.)Figure 1. Strategic Framework and STAR FrameworkISRU Envisioned Future: To drive thedevelopment of technologies and capabilities, theSTAR process starts with establishing a ‘grand vision’of where each Outcome and Capability is aiming tobe considered complete. For ISRU, the EnvisionedFuture is “Scalable ISRU production/utilizationcapabilities including sustainable commodities on thelunar and Mars Surface”. This involves starting with10’s of metric tons of products, but evolves into 100’sto 1000’s of metric tons of water, oxygen, propellants,construction and manufacturing feedstock, andcommodities for habitat and food production andoperations. For ISRU, the ‘Prospect to Product’philosophy starts with Destination Reconnaissance &Resource Assessment, followed by ResourceAcquisition, Isolation, and Preparation, leading intoResource Processing (which is further subdivided intomission consumables and feedstocks for constructionand manufacturing). The ISRU Envisioned Futurealso considers what resources are available andattempts to address what and when these resourceswill be evaluated and harnessed, as well asconsidering which products/commodities can beobtained for early use and which ones require moretime and/or users of refined products.It Takes an Architecture: ISRU does not existon its own. By definition, it requires customers/users SHORT TITLE HERE: A. B. Author and C. D. Authorto use the products/commodities produced by ISRUsystems. Also, for an ISRU capability to exist, itmust obtain products and services from other systemsand infrastructure. An important aspect of the STARprocess and the ISRU Envisioned Futures Prioritiesstrategy is to identify and link all of these systems andcapabilities to achieve the desired end state (Figure2).Figure 2. ISRU as Part of a Larger ArchitectureISRU Capability Drivers: The guidingprinciples for NASA’s Space TechnologyDevelopment for Artemis are to develop criticaltechnologies and capabilities that enable (i) asustainable Lunar surface presence, (ii) the future goalof sending humans to Mars, and (iii) promotingcritical technologies to enable future science andcommercial missions. It is a major goal of theArtemis campaign to establish some sort of base campat the lunar South Pole by approximately the end ofthe decade. The ISRU Envisioned Futures Prioritiesstrategy is aligned with the Artemis campaign todevelop and demonstrate ISRU capabilities in thistimeframe that could lead to sustained surfaceoperations, infrastructure growth, and commercialoperations in the next decade (Figure 3).Figure 3. ISRU Dual Path to Full Implementation and CommercializationState of the Art and Gaps: To achieve theenvisioned future, an extensive effort was performedto understand the State of the Art (SOA) for ISRUgoing back decades, and to assess the SOA against thenear and long-term goals and objectives of the ISRUStrategic Outcome objectives. While the releasedISRU Envisioned Futures Priorities only includes atop-level definition of both the SOA and Gaps, furtherinformation on these for ISRU can be found in theISRU Gap Assessment Study performed for theInternational Space Exploration Coordination Group(ISECG) [2]. To provide further guidance to industryand academia, a top level assessment was performedand provide that divides critical areas of ISRUcapabilities and technologies into 3 categories:Significant Funding, Partially Covered/MoreRequired, and Limited/No Funded Activities.Envisioned Future Priorities- Next Steps forISRU: While a significant amount of work over abroad range of technology areas has been performedover the last several years for lunar ISRU, to reach theenvisioned future for ISRU, a lot more work isrequired at the technology level leading to bothsystems and technology demonstrations in the nearfuture. To guide investments within NASA, industry,and academia, 5 specific areas of high priority wereidentified. These are:1.Complete development of the Water and Oxygen Mining Paths and close technology gaps, with emphasis on oxygen extraction from Highland regolith and parallel paths for polar water mining.2.Expand development of metal extraction and feedstock for manufacturing and construction, with emphasis on aluminum and initial/easy to obtain/make construction feedstocks leading to more refined metals and other regolith resources. Also, evaluate biologically inspired/derived technologies in bio-mining, bio-plastic, and other feedstock commodities.3.Ensure the resource assessment needed for future ISRU commercial operations is coordinated with both near/long-term science objectives as well as Artemis mission locations of interest.4.Initiate NASA and industry-led system-level analyses, integration, and testing activities for ISRU capabilities. While significant work has been performed at the technology and subsystemlevel, it is now important to understand how these technology investments can be leveraged and utilized in actual systems and applications5.Initiate lunar ISRU technology flight demonstrations leading to initial ‘Pilot Plant’ end-to-end production capability demonstrations, led by industry

ISRU↗

The solubility of La hydroxide and stability of La 3+ and La hydroxyl complexes at acidic to mildly acidic pH from 25 to 250 °C

The mobility of rare earth elements (REE) in natural hydrothermal systems can be assessed using geochemical modeling, which requires reliable thermodynamic data of relevant aqueous species. In this study, we evaluate the controls of pH and temperature on La speciation and the role of hydroxyl complexes in REE transport at hydrothermal conditions. Batch-type hydrothermal solubility experiments were conducted using synthetic La hydroxide powders equilibrated in perchloric acid-based aqueous solutions at temperatures between 150 and 250 °C and starting pH of 2 to 5. The La hydroxide solubility is retrograde with temperature and displays a strong pH dependence with a decrease in La concentrations from acidic to mildly acidic pH spanning between 3 and 5 orders of magnitude (e.g. log La molality of –2.5 to –7.2 at 250 °C). Thermodynamic optimizations using GEMSFITS allow to retrieve the standard partial molal Gibbs energies for the La 3+ aqua ion and the formation constants for the La hydroxyl species (i.e., LaOH 2+ , La(OH) 2 + , La(OH) 3 0 ) between 25 and 250 °C. A comparison between the experimentally derived thermodynamic properties with the calculated values from the Helgeson-Kirkham-Flowers equation of state parameters indicates an increased divergence with temperature. Discrepancies in standard partial molal Gibbs energies range between ~ 1 – 12 kJ/mol and result in a predicted La hydroxide solubility differing by up to 3 orders of magnitude at 250 °C. Speciation calculations indicate a higher stability of La 3+ and LaOH 2+ over the other La hydroxyl species in the studied pH range of 3.4 to 6. Here, the optimized thermodynamic properties for La aqueous species have important implications for modeling the solubility of REE minerals such as monazite and the mobility of REE in hydrothermal systems.

58 GEOSCIENCES↗

The Stability of Nd Hydroxyl Complexes at Near Neutral to Alkaline pH from 25 to 75 °C: Implications for Monazite Solubility in Hydrothermal Aqueous Fluids

Speciation of rare earth elements (REE) in aqueous fluids controls their mobilization during fluid-rock interaction. Thermodynamic modeling provides important insights into the factors controlling REE mobility and fractionation in aqueous fluids, in which aqueous REE hydroxyl complexes are particularly important across a broad pH range. However, the stability of these REE hydroxyl complexes remains poorly determined due to limited experimental data above ambient temperature. In this work, UV–vis spectrophotometry experiments were conducted to determine the cumulative hydrolysis constants for neodymium (Nd) from 25 to 75 °C in near-neutral to alkaline solutions. The color indicator m -cresol purple was used to determine in situ pH. Alkaline NaOH-bearing aqueous solutions were doped with varying initial Nd concentrations (0 to ∼0.155 mmol/kg), which resulted in the release of protons (H + ) and pH decrease during hydrolysis of Nd 3+ according to Nd 3+ + n H 2 O = Nd(OH) n 3– n + H + . The average OH – ligand number coordinated to Nd 3+ was found to increase from 1.0 to 1.6 at 25 °C and from 1.2 to 2.8 at 75 °C over a pH range from 6.3 to 9.0. The measured speciation shows an increased predominance of Nd(OH) 3 0 over the Nd(OH) 2 + and Nd(OH) 2+ species with increased temperature and pH. The increasing cumulative formation constants (log*β° n , n = 1 to 3) retrieved from 25 to 75 °C differ by 0.1 to 1.9 logarithmic units in comparison to existing thermodynamic databases. These updated thermodynamic data have important implications for geochemical modeling of the speciation of Nd hydroxyl complexes and the solubility of monazite as a function of pH.

58 GEOSCIENCES↗