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Probing Active Sites in Cu x Pd y Cluster Catalysts by Machine-Learning-Assisted X-ray Absorption Spectroscopy

Size-selected clusters are important model catalysts because of their narrow size and compositional distributions, as well as enhanced activity and selectivity in many reactions. Still, their structure-activity relationships are, in general, elusive. The main reason is the difficulty in identifying and quantitatively characterizing the catalytic active site in the clusters when it is confined within subnanometric dimensions and under the continuous structural changes the clusters can undergo in reaction conditions. Using machine learning approaches for analysis of the operando X-ray absorption near-edge structure spectra, we obtained accurate speciation of the Cu x Pd y cluster types during the propane oxidation reaction and the structural information about each type. As a result, we elucidated the information about active species and relative roles of Cu and Pd in the clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Contaminant Migration within a Dynamic River Corridor through Field Experiments and Reactive Transport Modeling

The behavior of a persistent uranium plume within an extended river corridor at the DOE Hanford site is dominantly controlled by river stage fluctuations in the adjacent Columbia River. The plume behavior is further complicated by substantial heterogeneity in physical and geochemical properties of the host aquifer sediments. Multi-scale field and laboratory experiments and reactive transport modeling were integrated to understand the complex plume behavior influenced by highly variable hydrologic and geochemical conditions in time and space. In this paper, we (1) describe multiple data sets from field-scale uranium adsorption and desorption experiments performed at our experimental well-field, (2) develop a reactive transport model that incorporates hydrologic and geochemical heterogeneities characterized from multi-scale and multi-type datasets and a surface complexation reaction network based on laboratory studies, and (3) compare the modeling and observation results to provide insights on how to refine the conceptual model and reduce prediction uncertainties. The experimental results revealed significant spatial variability in uranium adsorption/desorption behavior, while modeling demonstrated that ambient hydrologic and geochemical conditions and heterogeneities in sediment physical and chemical properties both contributed to complex plume behavior and its persistence. This research underscores the great challenges in adequately characterizing this type of site to model the reactive transport processes over scales of 10 m or more. Our analysis provides important insights into the characterization, understanding, modeling, and remediation of groundwater contaminant plumes influenced by dynamic surface water and groundwater interactions.

Chen, Xingyuan↗

Pantex Plant Ogallala Aquifer and Perched Groundwater Contingency Plan

The Pantex Plant Ogallala Aquifer and Perched Groundwater Contingency Plan has been developed in accordance with the requirements identified in the: • Interagency Agreement for the Pantex Superfund Site, Article 8.5 Work to be Performed, • Compliance Plan Provision of Hazardous Waste Permit No. 50284, and • Record of Decision for Groundwater, Soil, and Associated Media, Pantex Plant. A Long‐Term Monitoring System Design has been designed to monitor conditions in the perched groundwater including changes in the perched aquifer as a result of implementing the response actions. Monitoring is required for verifying the effectiveness of perched groundwater response actions (i.e., conditions in the perched aquifer are being affected as intended) and for confirming that the perched aquifer and Ogallala Aquifer characterization as defined in the Resource Conservation and Recovery Act Facility Investigation Report and the Corrective Measure Studies/Feasibility Study remains accurate. If monitoring results obtained through the monitoring network identify an unexpected condition or deviation, contingent actions will be considered and implemented as necessary to ensure continued protection of the Ogallala Aquifer and human health and the environment. Potential deviations to expected technology performance may be encountered for each of the four primary response actions that compose the selected remedy for perched groundwater; Playa 1 Pump and Treat System, Southeast Area Pump and Treat System, Southeast Area In‐Situ Bioremediation System (comprised of the Southeast In‐Situ Bioremediation System Original System, Southeast Area In‐Situ Bioremediation System Extension System, Offsite In‐Situ Bioremediation System, Perchlorate/Chromium ISB, Northeast ISB and County Road 8 ISB), and Zone 11 In‐Situ Bioremediation System. Monitoring will also be conducted to determine if there are deviations to the expected characterization, e.g., contaminants not expected as a result of the RCRA Facility Investigation characterization. Deviations to expected conditions in the Ogallala Aquifer could also be encountered if the response actions in the perched groundwater are not performing as expected, i.e., preventing contaminants from migrating to the Ogallala Aquifer. Currently, Pantex has begun investigation of detections of high explosives above groundwater protection standards in wells on the Texas Tech University property and a plume that is moving to the northeast from that area. Due to those detections, this Plan recognizes the fact that future detections in the Ogallala will be focused on first‐ time detections of analytes. After a remedy is determined, this Plan will require modification to address-deviations and contingent actions. This Plan was developed to identify the contingent actions necessary to mitigate impacts resulting from deviations to site conditions or response action performance. The Plan defines the environmental problem being addressed by the response actions, clarifies the expected conditions and objectives of the response actions, and identifies the potential deviations to the response actions (due to site conditions or technology performance) that could be encountered. The deviations were evaluated to determine the likelihood of occurrence, potential impact, and time to respond to avoid impact. The Plan also identifies the monitoring outlined in the Long‐Term Monitoring System Design Report (Consolidated Nuclear Security, 2024) and Sampling Analysis Plan (PanTeXas Deterrence, 2024) that will be used to detect the deviations. Lastly, the Plan specifies the contingent actions that could be implemented in response to the deviations. Because each response focuses on a discrete portion of the perched aquifer and contaminant plume, each response action has a different set of expected conditions, and therefore differing impacts from deviations to the site and technology expectations. As a result, the contingent actions are identified for each response action and potential deviation including specific constituents, location, and conditions. If deviations are encountered that impact the ability of the response action to meet performance objectives, the contingent actions will be focused on ensuring the response action can meet the performance objective. Contingent actions may be implemented as interim actions (ISMs/removal actions) in accordance with the Record of Decision, Interagency Agreement, and Hazardous Waste Permit‐50284, if warranted by the specific circumstances. For deviations to site characterization expected conditions, the contingent action will focus on determination of the source of the deviation, determination of the appropriate response, and evaluation of additional work to be completed. However, if the deviation to characterization impacts the performance of the response action, the contingent action will again focus on ensuring performance objectives can be met. Early source term removals and cleanup actions have been implemented to protect the Ogallala Aquifer. Because of these actions and based on modeling results, the expected conditions in the Ogallala Aquifer are that constituents of concern will not be detected above the Groundwater Protection Standards (GWPSs) nor will they reach potential points of exposure above the GWPS. The primary deviation of concern for the Ogallala is if constituents are detected in the Ogallala Aquifer near or above GWPSs. If it occurs, this change in expected conditions would require further evaluation of site and contaminant characteristics to determine an appropriate course of action. The evaluation would include additional monitoring, source identification, implementation of interim protective measures (if necessary), and delineation of extent. These evaluations are necessary to determine an appropriate response action for the Ogallala. The primary goal of the Plan is to provide for the continued protection of the Ogallala Aquifer and the health of its consumers. In recognition, this Plan presents a flexible and rational approach for making future decisions associated with confirming the change in perched and Ogallala aquifer conditions and identifying a response (technical activities, changes to response actions, regulatory oversight, and public involvement).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Apollo 17 Soil Characterization for Reflectance Spectroscopy

It is the fine fractions that dominate the observed spectral signatures of bulk lunar soil, and the next to the smallest size fractions are the most similar to the overall properties of the bulk soil. Thus, our Lunar Soil Characterization Consortium has concentrated on understanding the inter-relations of compositional, mineralogical, and optical properties of the <45-micron size fraction and its component sizes (20-44 micron, 10-20 micron, and <10 micron size fractions). To be able to generalize our results beyond the particular sample set studied, it is necessary to quantitatively identify the observed effects of space weathering and evaluate the processes involved. For this, it is necessary to know the chemistry of each size fraction, modal abundances of each phase, average compositions of the minerals and glasses, I(sub s)/FeO values, reflectance spectra, and the physical makeup of the individual particles and their patinas. This characterization includes the important dissection of the pyroxene minerals into four separate populations, with data on both modes and average chemical compositions. Armed with such data, it should be possible to effectively isolate spectral effects of space weathering from spectral properties related to mineral and glass chemistry. Four mare soils from the Apollo 17 site were selected for characterization based upon similarities in bulk composition and their contrasting maturities, ranging from immature to submature to mature. The methodology of our characterization has been discussed previously. Results of the Apollo 17 mare soils, outlined herein, are being prepared for publication in MAPS. As shown, with decreasing grain size, the agglutinitic (impact) glass content profoundly increases. This is the most impressive change for the mare soils. In several soils we have examined, there is an over two-fold increase in the agglutinitic glass contents between the 90-150- micron and the 10-20-micron size fractions. Accompanying this increase in agglutinitic glass is a definite decrease in pyroxenes and to lesser extents, the oxides (ilmenite), volcanic glass, and olivine. Unexpectedly, however, the absolute plagioclase abundances stay relatively constant throughout the different grain sizes, although the abundance of plagioclase relative to the mafic minerals increases with decreasing particle size. These soils were chosen for study based upon their similarities in FeO and Ti02 content, allowing for direct comparisons between evolutions of chemistry between size fractions and among different maturities of soils. The bulk chemistry of these fractions was determined by EMP analyses of fused glass beads. In contrast to the systematic variations in bulk chemistry discussed below, the relatively uniform composition of agglutinitic glass with grain size and soil maturity is illustrated. The composition of the bulk fraction of each size fraction becomes more feldspathic with increasing maturity, with the effect being most pronounced for the finest fractions. The composition of the agglutinitic glass, however, is relatively invariant and more feldspathic (i.e., rich in Al2O3) than even the <10-micron fraction. This relation not only strengthens the "fusion of the finest fraction" (F(sup 3)) hypothesis, but also highlights the important role of plagioclase in the formation of agglutinitic glass. With decreasing grain size, FeO, MgO, and TiO2 contents decrease, whereas CaO, Na2O, and Al2O3 (plag components) increase for all soils. These chemical variations would appear to be coupled with the significant increase in agglutinitic glass and decrease in oxide (ilmenite),pyroxene, and volcanic glass. These changes in chemistry do not appear to be due to distinct changes in the compositions of individual phases but to their abundances. Values of I(sub s)/FeO increase with decreasing grain size, even though the bulk FeO contents decrease. That is, the percentage of the total Fe that is present as nanophase Fe(sup O) has increased substantially in the smaller size fraction. Note that the increase in nanophase FeO in smaller size fractions is significantly greater than the increase in agglutinitic glass content, with its single-domain FeO component. This would seem to indicate that at least some of the FeO is surface correlated. To illustrate this effect, if it is assumed that the nanophase FeO is entirely surface correlated, then equal masses of 15-micron and 6-micron spheres should have about 3x as much FeO in the finer fraction. The recent findings of Kelleret al. of the major role of vapor-deposited, nanophase FeO-containing patinas on most soil particles is a major breakthrough in our understanding of the distribution of FeO within agglutinitic glass and upon grain surfaces. Bidirectional reflectance spectra for a representative Apollo 17 soil (70181) are shown. The size separates all have similar albedo in the blue and follow a regular sequence in which the continuum slope increases, ferrous bands weaken, and albedo, increases with decreasing particle size. The bulk <45-micron soil is typically close to the 10-20 micron spectrum. It is important to note that although the finest fraction (<10 micron) is close in composition to the abundant agglutinitic glass in each size fraction, this size fraction is relatively featureless and does not dominate the spectrum of the bulk <45-micron soil. It has long been suspected that agglutinitic glass, to a large extent, is the product of melting of the finest fraction of the soils, with a dominance of plagioclase. Given the low abundance of pyroxene in the finest fractions of each soil the source of the FeO in these Apollo 17 agglutinitic glasses is not fully identified. We suspect the abundant volcanic glass in these samples may be a significant contributor and this hypothesis will be tested with the suite under study from other Apollo sites.

Taylor, L. A.↗

Worswick Hot Springs: A Radioactive Hydrothermal Field Site

We report on a systematic characterization of the radiation environment and water temperatures of Worswick Hot Springs, which is in support of companion biochemical and microbial investigations of iron respiration in the ‘extreme’ microbial systems found at the field site. We have discovered localized areas of elevated radioactivity that are approximately four to five times greater than background radiation. Additionally, we have observed that both the radiation environment and the temperature of the spring waters vary over time. Because localized “hot spots” of elevated radiation and biofilms are easily accessible, various biological studies of radiation resistance and biosignature formation are possible, making this field site relevant for analog field studies that consider microbiology, geochemistry, and ionizing radiation. In addition to Worswick being a natural radiation biology laboratory that may also be relevant for space biology applications, we assert that these unusual environmental conditions may inform us about locations on Mars that are also enriched in radioactive elements and their potential for hosting biosignatures.

Jon C. Rask↗

Connecting cation site location to alkane dehydrogenation activity in Ni/BEA catalysts

Ni-modified beta zeolite (Ni/BEA) catalysts activate carbon-hydrogen bonds in light alkanes, as demonstrated through isobutane reaction testing. Controlled synthesis of Ni/BEA allows for efficient introduction of ion-exchanged Ni sites at varying Ni loadings (0.43% - 1.8%). These catalysts exhibit site time yields (STY) for H2 production that increase with increasing Ni loading. A detailed analysis of secondary reactions and carbon deposition based on the relative molar flowrates of product C and H indicates that the observed increase in H2 STY with increasing Ni loading is likely attributed to both increasing alkane activation activity and increasing formation of hydrogen-deficient aromatic products retained within the catalyst pores. In situ diffuse-reflectance UV-visible-NIR absorbance and X-ray absorption spectroscopies indicate isolated, 4-coordinate Ni(2+) species for all loadings. Quantum mechanics/molecular mechanics modeling identifies two distinct Ni(2+) sites consistent with the structural characterization, but with differing relative stabilities due to their coordination environment. Computed reaction energetics for isobutane dehydrogenation demonstrate that the more stable Ni(2+) species at a six-membered 4Si-2Al ring, Ni-6MR, is less active for isobutane dehydrogenation than the less stable Ni(2+) at the five-membered 3Si-2Al ring, Ni-5MR. The differing local structure of the isolated cationic Ni sites in Ni/BEA offers a possible rationalization for the increased H2 STY observed at greater Ni loadings.

catalysts↗

Absence of moment fragmentation in the mixed B -site pyrochlore Nd 2 GaSbO 7

Nd-based pyrochlore oxides of the form Nd 2 GaSbO 7 have garnered a significant amount of interest owing to the moment fragmentation physics observed in Nd 2 GaSbO 7 and speculated in Nd 2 GaSbO 7 . Notably this phenomenon is not ubiquitous in this family, as it is absent in Nd 2 GaSbO 7 , which features a smaller ionic radius on the B site. Here, we explore the necessary conditions for moment fragmentation in the Nd pyrochlore family through a detailed study of the mixed B-site pyrochlore Nd 2 GaSbO 7 . Furthermore, the B site of this system is characterized by significant disorder and an extremely small average ionic radius. Similarly to Nd 2 GaSbO 7 , we find no evidence for moment fragmentation through our bulk characterization and neutron scattering experiments, indicating that chemical pressure (and not necessarily the B-site disorder) plays a key role in the presence or absence of this phenomenon in this material family. Surprisingly, the presence of significant B-site disorder in Nd 2 GaSbO 7 does not generate a spin-glass ground state and instead the same all-in-all-out magnetic order identified in other Nd pyrochlores is found here.

36 MATERIALS SCIENCE↗

Milestone Report for MS8: Extend Quantitative Brine and CO 2 Leakage Calculations

This report summarizes results of the risk analysis and characterization of CO 2 and brine leakage potential of Farnsworth Unit (FWU) wells. U.S. DOE’s National Risk Assessment Partnership (NRAP) program works on quantitatively assess long-term environmental risks amidst significant geologic uncertainty and variability. NRAP risk assessment and computational tools are developed to quantify uncertainties and calculate risk associated with geologic sequestration of carbon dioxide (CO 2 ). For this study, we have developed a workflow from University of Utah’s physics-based reservoir simulators to performing leakage calculations using NRAP Tools. NRAP tools (NRAP-IAM-CS, RROM-Gen) are used to conduct leakage risk analysis based on Eclipse simulation results, and characterize wellbore leakage at the Farnworth Site. This report summarizes results of the risk analysis and characterization of CO 2 and brine leakage potential of Farnsworth Unit (FWU) wells.

54 ENVIRONMENTAL SCIENCES↗

A multi-criteria CCUS screening evaluation of the Gulf of Mexico, USA

Continued research into reservoir characterization along with offshore carbon dioxide (CO 2 ) transportation and infrastructure assets is needed to facilitate development of safe and successful carbon capture, utilization, and storage (CCUS) projects. This paper outlines a multi-criteria evaluation methodology that incorporates disparate sets of quantitative, spatially variable data into a decision-making framework for screening the Gulf of Mexico (GOM) outer continental shelf (OCS) for potentially viable CO 2 storage and enhanced oil recovery (EOR) sites. Criteria categories include favorable geologic characteristics, logistics, and potential risks. Data compiled for 14 criteria from several publicly available geographic information system (GIS) layers was aggregated over 2559 spatially balanced points across the study area using the National Energy Technology Laboratory (NETL)-developed Cumulative Spatial Impact Layers™ (CSIL) GIS tool. Criteria are weighted by qualitative expert opinion relative to their perceived importance to given scenarios— the output of combined criteria values and weights enables regional CO 2 storage suitability differentiation. The methodology considers both technical and non-technical factors impacting CCUS decision-making. The flexible methodology enables a systematic approach to regional ranking at high spatial resolution over a large study domain. Additionally, the framework enables high-grading of priority sites that warrant further characterization and follow-on analysis. Areas along the Louisiana coast and Mississippi River Delta consistently rank high for all scenarios largely a result of the favorable geology with the potential for stacked storage, as well as the density of existing pipelines and platforms, and proximity to several onshore CO 2 sources. High-graded regions for the CO 2 EOR-related scenarios are typically located further offshore towards the middle and edge of the OCS compared to higher priority regions for the geologic storage scenarios which fall closer to the Louisiana coastline.

54 ENVIRONMENTAL SCIENCES↗

Ar-40 - Ar-39 Geochronology on Apollo 12 Regolith

The Apollo 12 landing site in Oceanus Procellarum is located about 400 km south of the rim of Copernicus. The geochemical and petrographical characterization of the Apollo 12 lunar samples have been extensively studied. The site is characterized by a high proportion of nonmare material with KREEP composition and mare basalts low in Th. Recent studies have focused on the geochemistry of the nonmare material and on inferring the origin of these materials. Previous geochronological investigations of Apollo 12 mare basalts have yielded ages ranging from 3.1 to 3.3 Ga. On the other hand, nonmare materials have yielded older ages between 3.8 to 4.0 Ga; with the sole exception of a single lunar granite fragment from sample 12033. This granite sample has an Ar-40 - Ar-39 age of 800 +/- 15 Ma. This resetting age has been interpreted as the age of the Copernicus crater since a ray from this crater crosses the landing site. Here we present new 40Ar-39Ar geochronological data on three samples of nonmare material from the Apollo 12 regolith in order to further constrain the age and source of this material.

Barra, F.↗

Genesis of Active Pt/CeO 2 Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters

Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide- supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. Here the results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Jezero Crater, Mars, as a Compelling Site for Future In Situ Exploration

Jezero is a approximately 45 km diameter impact crater located in the Nili Fossae region of Mars. Jezero is an outstanding site to address key questions of ancient Mars climate, habitability, and volcanic history because: (a) It hosted an open-basin lake during the era of valley network formation [1,2], which ceased at approximately the Noachian-Hesperian boundary [3]. (b) It contains two delta deposits [1,4] with Fe/Mg-smectite and Mg-carbonate sediment [4-7] (the only exposure of lacus-trine shoreline carbonates seen so far on Mars). (c) The depositional environment and mineral assemblage of the delta are promising for the concentration and preservation of organic matter [5,8]. (d) The diverse geologic units in Jezero are in clear stratigraphic context [7]. The Jezero paleolake system has been thoroughly investigated at a variety of scales, including work on: the mineralogy of the delta deposits [4-6] and watershed [7], as well as the morphology and sedimentology of the basin [9] and delta deposits [1,4]. The geologic context of Jezero is also well-studied given the broad suite of alteration minerals exposed in the ancient stratigraphies of the Nili Fossae region [e.g., 6,10-13]. Here we present an overview of the units accessible for exploration in the Jezero basin, including questions and hypotheses that can be tested through analysis in situ and of returned samples. This is particularly timely given the upcoming Mars 2020 mission, for which Jezero is one of the final eight landing sites [14]. Primary science objectives for Mars 2020 are to: (1) characterize the geologic history of a site with "evidence of an astrobiologically-relevant ancient environment and geologic diversity"; (2) assess the habitability and "potential evidence of past life" in units with "high biosignature preservation potential"; and (3) cache scientifically compelling samples for potential return to Earth [15].

Mars↗

Additional characterization of Libya-4 in support of post-launch vicarious calibration of satellite imagers

Libya-4 (28.55° N and 23.39° E) is one of the most characterized and utilized Pseudo Invariant Calibration Site (PICS) for post-launch radiometer drift monitoring and sensor pair radiometric scaling. Libya-4 is one of the driest and most reflective PICS located in an extensive sand dune region void of any vegetation with an elevation of 118 m. It is positioned near the northeast border with Egypt. With minimal cloud cover and the monthly mean precipitation of ~ 1mm, Libya-4 is one of the temporally, spectrally, and spatially stable CEOS recommended PICS and Cosnefroy et al. 1996 identified sites. The Libya-4 PICS has been extensively used for post-launch radiometric calibration and validation of high-, medium, and low-resolution satellite imagers, including Landsat, MODIS, VIIRS, and Meteosats. The CERES Imager and Geostationary Calibration Group (IGCG) at NASA LaRC utilizes Libya-4 to perform an independent assessment of the radiometric stability of the MODIS and VIIRS L1B products. The site is also used for absolute radiometric scaling between MODIS, VIIRS, and geostationary imagers to ensure consistent cloud and radiative flux retrievals. Multi-year Terra-MODIS, Aqua-MODIS , NPP-VIIRS and Metoesat-7 observations over Libya-4 show very similar TOA reflectance temporal variability. Although, the surface reflectance and atmospheric column varies seasonally, the inter-annual variability of the seasonal cycle should be small. Especially during 2013, the Libya-4 TOA reflectance was found to be greater than usual in all 4 satellite records. Preliminary comparisons with mean wind speed and aerosol optical depth (AOD) indicate that the year 2013 is marked by elevated levels of both conditions. The goal of this study is to tie the Libya-4 visible reflectance inter-annual variability with corresponding meteorological measurements to further improve the characterization of the site.

David R. Doelling↗

Structural Interconversion between Agglomerated Palladium Domains and Mononuclear Pd(II) Cations in Chabazite Zeolites

Palladium-exchanged zeolites are candidate materials for passive NO x adsorption in automotive exhaust aftertreatment, where mononuclear Pd cations behave as precursors to the purported NO x adsorption sites. Yet, the structures of zeolite lattice binding sites capable of stabilizing mononuclear Pd 2+ ions, and the mechanisms that interconvert agglomerated PdO and Pd domains into mononuclear Pd 2+ ions during Pd redispersion treatments, remain incompletely understood. In this work, we use a suite of spectroscopic methods and quantitative site titration techniques to characterize mononuclear and agglomerated Pd species on zeolites with varying material properties and treatment history. Aqueous-phase methods to introduce Pd onto NH 4 -form zeolites initially form mononuclear [Pd(NH 3 ) 4 ] 2+ complexes, but subsequent thermal treatments (573–723 K; air) lead to in situ formation of H 2 that first reduces Pd 2+ to metallic Pd domains, which are then oxidized by air to PdO domains. Progressive treatment of Pd-zeolites in air to higher temperatures (723–1023 K) converts larger fractions of agglomerated PdO to mononuclear Pd 2+ , as quantified by H 2 temperature programmed reduction, because higher temperature treatments facilitate Pd redispersion toward deeper locations within chabazite (CHA) crystallites, which is corroborated by complementary titrimetric and spectroscopic data. Pd-CHA zeolites synthesized with similar bulk Pd and framework Al content, but varying framework Al arrangement, provide evidence that six-membered rings (6-MR) hosting paired Al sites (Al–O–(Si–O) x –Al, x = 1, 2) stabilize Pd 2+ ions and that otherwise isolated Al sites can stabilize [PdOH] + species, identifiable by an IR OH stretch at 3660 cm –1 . These findings clarify the underlying chemical processes and gas environments that cause Pd agglomeration in zeolites and their subsequent redispersion to mononuclear Pd 2+ ions, which prefer binding at 6-MR paired Al sites in CHA, and indicate that higher temperature air treatments lead to more uniform Pd spatial distributions throughout zeolite crystallites.

36 MATERIALS SCIENCE↗

Improved LOLA Elevation Maps for South Pole Landing Sites: Error Estimates and Their Impact on Illumination Conditions

We present new high-resolution topographic models of 4 high-priority lunar south pole landing sites based exclusively on the laser altimetry data acquired by the Lunar Orbiter Laser Altimeter (LOLA) onboard the Lunar Reconnaissance Orbiter. By iteratively adjusting the LOLA tracks to the LOLA-based digital elevation model (LDEM) in a self-consistent fashion, we reduce the orbital geolocation errors by over a factor of 10 such that the new ground track geolocation uncertainty is ~10–20 ​cm horizontally and ~2–4 ​cm vertically over each 16 ​× ​16 km region. These new and improved 5 ​m/pix LDEMs will be useful to constrain higher-resolution topographic models derived from imagery, which are not as well controlled geodetically and which can be hindered by shadows. We developed a method to estimate surface height uncertainty in the new LDEMs, which accounts for the reduced orbital errors and interpolation errors by assuming a fractal behavior for the short-scale topography. The LDEM surface height and slope uncertainties have typical RMS values of ~0.30–0.50 ​m and ~1.5–2.5°, respectively. Finally, we examine how height uncertainties propagate to variations in horizon elevation and thus the predicted illumination conditions at these polar latitudes, and we show how this error characterization can inform landing site studies.

Michael K Barker↗

Turbulence in The Marine Boundary Layer and Air Motions Below Stratocumulus Clouds at the ARM Eastern North Atlantic Site

Marine stratocumulus clouds are intimately coupled to the turbulence in the boundary layer and drizzle is known to be ubiquitous within them. Six years of data collected at the Atmospheric Radiation Measurement (ARM)’s Eastern North Atlantic site are utilized to characterize turbulence in the marine boundary layer and air motions below stratocumulus clouds. Profiles of variance of vertical velocity binned by wind direction (wdir) yielded that the boundary layer measurements are affected by the island when the wdir is between 90° and 310° (measured clockwise from North where air is coming from). Data collected during the marine conditions (wdir<90 or wdir>310) showed that the variance of vertical velocity was higher during the winter months than during the summer months due to higher cloudiness, wind speeds, and surface fluxes. Furthermore, during marine conditions the variance of vertical velocity and cloud fraction exhibited a distinct diurnal cycle with higher values during the nighttime than during the daytime. Detailed analysis of 32 cases of drizzling marine stratocumulus clouds showed that for a similar amount of radiative cooling at the cloud top, within the sub-cloud layer 1) drizzle increasingly falls within downdrafts with increasing rain rates, 2) the strength of the downdrafts increases with increasing rain rates, and 3) the correlation between vertical air motion and rain rate is highest in the middle of the sub-cloud layer. The results presented herein have implications for climatological and model evaluation studies conducted at the ENA site, along with efforts of accurately representing drizzle-turbulence interactions in a range of atmospheric models.

54 ENVIRONMENTAL SCIENCES↗

NASA's Space Launch System: Deep-Space Delivery for Smallsats

Designed for human exploration missions into deep space, NASA's Space Launch System (SLS) represents a new spaceflight infrastructure asset, enabling a wide variety of unique utilization opportunities. While primarily focused on launching the large systems needed for crewed spaceflight beyond Earth orbit, SLS also offers a game-changing capability for the deployment of small satellites to deep-space destinations, beginning with its first flight. Currently, SLS is making rapid progress toward readiness for its first launch in two years, using the initial configuration of the vehicle, which is capable of delivering 70 metric tons (t) to Low Earth Orbit (LEO). On its first flight test of the Orion spacecraft around the moon, accompanying Orion on SLS will be small-satellite secondary payloads, which will deploy in cislunar space. The deployment berths are sized for "6U" CubeSats, and on EM-1 the spacecraft will be deployed into cislunar space following Orion separate from the SLS Interim Cryogenic Propulsion Stage. Payloads in 6U class will be limited to 14 kg maximum mass. Secondary payloads on EM-1 will be launched in the Orion Stage Adapter (OSA). Payload dispensers will be mounted on specially designed brackets, each attached to the interior wall of the OSA. For the EM-1 mission, a total of fourteen brackets will be installed, allowing for thirteen payload locations. The final location will be used for mounting an avionics unit, which will include a battery and sequencer for executing the mission deployment sequence. Following the launch of EM-1, deployments of the secondary payloads will commence after sufficient separation of the Orion spacecraft to the upper stage vehicle to minimize any possible contact of the deployed CubeSats to Orion. Currently this is estimated to require approximately 4 hours. The allowed deployment window for the CubeSats will be from the time the upper stage disposal maneuvers are complete to up to 10 days after launch. The upper stage will fly past the moon at a perigee of approximately 100km, and this closest approach will occur about 5 days after launch. The limiting factor for the latest deployment time is the available power in the sequencer system. Several NASA Mission Directorates were involved in the development of programs for the competition, selection, and development of EM-1 payloads that support directorate priorities. CubeSat payloads on EM-1 will include both NASA research experiments and spacecraft developed by industry, international and potentially academia partners. The Human Exploration and Operations Mission Directorate (HEOMD) Advanced Exploration Systems (AES) Division was allocated five payload opportunities on the EM-1 mission. Near Earth Asteroid (NEA) Scout is designed to rendezvous with and characterize a candidate NEA. A solar sail, an innovation the spacecraft will demonstrated for the CubeSat class, will provide propulsion. Lunar Flashlight will use a green propellant system and will search for potential ice deposits in the moon's permanently shadowed craters. BioSentinel is a yeast radiation biosensor, planned to measure the effects of space radiation on deoxyribonucleic acid (DNA). Lunar Icecube, a collaboration with Morehead State University, will prospect for water in ice, liquid, and vapor forms as well as other lunar volatiles from a low-perigee, highly inclined lunar orbit using a compact Infrared spectrometer. Skyfire, a partnership with Lockheed Martin, is a technology demonstration mission that will perform a lunar flyby, collecting spectroscopy, and thermography data to address questions related to surface characterization, remote sensing, and site selection. NASA's Space Technology Mission Directorate (STMD) was allocated three payload opportunities on the EM-1 mission. These slots will be filled via the Centennial Challenges Program, NASA's flagship program for technology prize competitions, which directly engages the public, academia, and industry in open prize competitions to stimulate innovation. The NASA Science Mission Directorate (SMD) was allocated two payload opportunities on the EM-1 mission. The CubeSat Mission to Study Solar Particles (CuSP) payload will study the sources and acceleration mechanisms of solar and interplanetary particles in near-Earth orbit, support space weather research by determining proton radiation levels during Solar Energetic Particle (SEP) events and identifying suprathermal properties that could help predict geomagnetic storms. The LunaH-Map payload will help scientists understand the quantity of H-bearing materials in lunar cold traps (~10 km), determine the concentration of H-bearing materials with 1m depth, and constrain the vertical distribution of H-bearing materials. The final three payload opportunities for the EM-1 mission were allocated for NASA's international space agency counterparts. The flight opportunities are intended to benefit the international space agency and NASA as well as further the collective space exploration goals. ArgoMoon is sponsored by ESA/ASI and will fly along with the ICPS on its disposal trajectory to perform proximity operations with the ICPS post-disposal, take external imagery of engineering and historical significance, and perform an optical communications demonstration. EQUULEUS, sponsored by JAXA, will fly to a libration orbit around the Earth-Moon L2 point and demonstrate trajectory control techniques within the Sun-Earth- Moon region for the first time by a nano spacecraft. The mission will also contribute to the future human exploration scenario by understanding the radiation environment in geospace and deep space, characterizing the flux of impacting meteors on the far side of the moon, and demonstrating the future deep space exploration scenario using the "deep space port" at Lagrange points. OMOTENASHI, also sponsored by JAXA, will land the smallest lunar lander to date on the lunar surface to demonstrate the feasibility of the hardware for distributed cooperative exploration system. Small landers will enable multi-point exploration, which is complimentary with large-scale human exploration. Once on the lunar surface, the OMOTENASHI spacecraft will observe the radiation and soil environments of the lunar surface by active radiation measurements and soil shear measurements. Following EM-1, Space Launch System will evolve to the more-powerful Block 1B configuration, which uses a new Exploration Upper Stage to increase the vehicle's LEO payload capability from 70 t to 105 t. With that transition, the Orion Stage Adapter, which will carry the secondary payloads on EM-1, will be phased out, and a new Universal Stage Adapter will be introduced, creating opportunities for flying larger secondary payloads. This paper will provide a brief status of SLS progress toward first launch; an overview of smallsat accommodations, integration, and operations on EM-1; information about the specific payloads flying on that launch; and a discussion of future accommodations and opportunities for secondary payloads on SLS for Exploration Mission-2 and beyond.

Robinson, Kimberly F.↗

NASA's Space Launch System: Deep-Space Opportunities for SmallSats

Designed for human exploration missions into deep space, NASA's Space Launch System (SLS) represents a new spaceflight infrastructure asset, enabling a wide variety of unique utilization opportunities. While primarily focused on launching the large systems needed for crewed spaceflight beyond Earth orbit, SLS also offers a game-changing capability for the deployment of small satellites to deep-space destinations, beginning with its first flight. Currently, SLS is making rapid progress toward readiness for its first launch in two years, using the initial configuration of the vehicle, which is capable of delivering 70 metric tons (t) to Low Earth Orbit (LEO). On its first flight test of the Orion spacecraft around the moon, accompanying Orion on SLS will be small-satellite secondary payloads, which will deploy in cislunar space. The deployment berths are sized for "6U" CubeSats, and on EM-1 the spacecraft will be deployed into cislunar space following Orion separate from the SLS Interim Cryogenic Propulsion Stage. Payloads in 6U class will be limited to 14 kg maximum mass. Secondary payloads on EM-1 will be launched in the Orion Stage Adapter (OSA). Payload dispensers will be mounted on specially designed brackets, each attached to the interior wall of the OSA. For the EM-1 mission, a total of fourteen brackets will be installed, allowing for thirteen payload locations. The final location will be used for mounting an avionics unit, which will include a battery and sequencer for executing the mission deployment sequence. Following the launch of EM-1, deployments of the secondary payloads will commence after sufficient separation of the Orion spacecraft to the upper stage vehicle to minimize any possible contact of the deployed cubesats to Orion. Currently this is estimated to require approximately 4 hours. The allowed deployment window for the cubesats will be from the time the upper stage disposal maneuvers are complete to up to 10 days after launch. The upper stage will fly past the moon at a perigee of approximately 100km, and this closest approach will occur about 5 days after launch. The limiting factor for the latest deployment time is the available power in the sequencer system. Several NASA Mission Directorates were involved in the development of programs for the competition, selection, and development of EM-1 payloads that support directorate priorities. CubeSat payloads on EM-1 will include both NASA research experiments and spacecraft developed by industry, international and potentially academia partners. The Human Exploration and Operations Mission Directorate (HEOMD) Advanced Exploration Systems (AES) Division was allocated five payload opportunities on the EM-1 mission. Near Earth Asteroid (NEA) Scout is designed to rendezvous with and characterize a candidate NEA. A solar sail, an innovation the spacecraft will demonstrated for the CubeSat class, will provide propulsion. Lunar Flashlight will use a green propellant system and will search for potential ice deposits in the moon's permanently shadowed craters. BioSentinel is a yeast radiation biosensor, planned to measure the effects of space radiation on deoxyribonucleic acid (DNA). Lunar Icecube, a collaboration with Morehead State University, will prospect for water in ice, liquid, and vapor forms as well as other lunar volatiles from a low-perigee, highly inclined lunar orbit using a compact Infrared spectrometer. Skyfire, a partnership with Lockheed Martin, is a technology demonstration mission that will perform a lunar flyby, collecting spectroscopy, and thermography data to address questions related to surface characterization, remote sensing, and site selection. NASA's Space Technology Mission Directorate (STMD) was allocated three payload opportunities on the EM-1 mission. These slots will be filled via the 2 Centennial Challenges Program, NASA's flagship program for technology prize competitions, which directly engages the public, academia, and industry in open prize competitions to stimulate innovation. The NASA Science Mission Directorate (SMD) was allocated two payload opportunities on the EM-1 mission. The CubeSat Mission to Study Solar Particles (CuSP) payload will study the sources and acceleration mechanisms of solar and interplanetary particles in near-Earth orbit, support space weather research by determining proton radiation levels during Solar Energetic Particle (SEP) events and identifying suprathermal properties that could help predict geomagnetic storms. The LunaH-Map payload will help scientists understand the quantity of H-bearing materials in lunar cold traps (~10 km), determine the concentration of H-bearing materials with 1m depth, and constrain the vertical distribution of H-bearing materials. The final three payload opportunities for the EM-1 mission were allocated for NASA's international space agency counterparts. The flight opportunities are intended to benefit the international space agency and NASA as well as further the collective space exploration goals. ArgoMoon is sponsored by ESA/ASI and will fly along with the ICPS on its disposal trajectory to perform proximity operations with the ICPS post-disposal, take external imagery of engineering and historical significance, and perform an optical communications demonstration. EQUULEUS, sponsored by JAXA, will fly to a libration orbit around the Earth-Moon L2 point and demonstrate trajectory control techniques within the Sun-Earth-Moon region for the first time by a nano spacecraft. The mission will also contribute to the future human exploration scenario by understanding the radiation environment in geospace and deep space, characterizing the flux of impacting meteors on the far side of the moon, and demonstrating the future deep space exploration scenario using the "deep space port" at Lagrange points. OMOTENASHI, also sponsored by JAXA, will land the smallest lunar lander to date on the lunar surface to demonstrate the feasibility of the hardware for distributed cooperative exploration system. Small landers will enable multi-point exploration, which is complimentary with large-scale human exploration. Once on the lunar surface, the OMOTENASHI spacecraft will observe the radiation and soil environments of the lunar surface by active radiation measurements and soil shear measurements. Following EM-1, Space Launch System will evolve to the more-powerful Block 1B configuration, which uses a new Exploration Upper Stage to increase the vehicle's LEO payload capability from 70 t to 105 t. With that transition, the Orion Stage Adapter, which will carry the secondary payloads on EM-1, will be phased out, and a new Universal Stage Adapter will be introduced, creating opportunities for flying larger secondary payloads. This paper will provide a brief status of SLS progress toward first launch; an overview of smallsat accommodations, integration, and operations on EM-1; information about the specific payloads flying on that launch; and a discussion of future accommodations and opportunities for secondary payloads on SLS for Exploration Mission-2 and beyond.

Robinson, Kimberly F.↗