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X-ray Properties of an Unbiased Hard X-ray Detected Sample of AGN

The SWIFT gamma ray observatory's Burst Alert Telescope (BAT) has detected a sample of active galactic nuclei (AGN) based solely on their hard X-ray flux (14-195keV). In this paper, we present for the first time XMM-Newton X-ray spectra for 22 BAT AGXs with no previously analyzed X-ray spectra. If our sources are a representative sample of the BAT AGN, as we claim, our results present for the first time global X-ray properties of an unbiased towards absorption (n(sub H) < 3 x 10(exp 25)/sq cm), local (< z >= 0.03), AGN sample. We find 9/22 low absorption (n(sub H) < 10(exp 23)/sq cm), simple power law model sources, where 4 of these sources have a statistically significant soft component. Among these sources, we find the presence of a warm absorber statistically significant for only one Seyfert 1 source, contrasting with the ASCA results of Reynolds (1997) and George et al. (1998), who find signatures of warm absorption in half or more of their Seyfert 1 samples at similar redshifts. Additionally, the remaining sources (13122) have more complex spectra, well-fit by an absorbed power law at E > 2.0 keV. Five of the complex sources (NGC 612, ESO 362-G018, MRK 417, ESO 506-G027, and NGC 6860) are classified as Compton-thick candidates. Further, we find four more sources (SWIFT J0641.3+3257, SWIFT J0911.2+4533, SWIFT J1200.8+0650, and NGC 4992) with properties consistent with the hidden/buried AGN reported by Ueda et al. (2007). Finally, we include a comparison of the XMM EPIC spectra with available SWIFT X-ray Telescope (XRT) observations. From these comparisons, we find 6/16 sources with varying column densities, 6/16 sources with varying power law indices, and 13/16 sources with varying fluxes, over periods of hours to months. Flux and power law index are correlated for objects where both parameters vary.

Winter, Lisa M.↗

Does Collection Time Bias the Ecology of Cleanroom Air Samples?

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

A. B. Regberg↗

Say where you sample: Increasing site selection transparency in urban ecology

Urban ecological studies have the potential to extend our understanding of socio-ecological systems beyond that of an individual city or region. Cross-comparative empirical work and synthesis are imperative to develop a general urban ecological theory. This can be achieved only if studies are replicable and generalizable. Transparency in methods reporting facilitates generalizability and replicability by documenting the decisions scientists make during the various steps of research design; this is particularly true for sampling design and selection because of their impact on both internal and external validity and the potential to unintentionally introduce bias. Three interdependent aspects of sample design are study sample selection (e.g., specific organisms, soils, or water), sample specification (measurement of specific variable of interest), and site selection (locations sampled). Of these, documentation of site selection—the where component of sample design—is underrepresented in the urban ecology literature. Using a stratified random sample of 158 papers from 12 major urban ecology journals, we investigated how researchers selected study sites in urban ecosystems and evaluated whether their site selection methods were transparent. We extracted data from these papers using a 50-question, theory-based questionnaire and a multiple-reviewer approach. Our sample represented almost 45 years of urban ecology research across 40 different countries. We found that more than 80% of the papers read were not transparent in their site selection methodology. We do not believe site selection methods are replicable for 70% of the papers read. Key weaknesses include incomplete descriptions of populations and sampling frames, urban gradients, sample selection methods, and property access. Low transparency in reporting the where methodology limits urban ecologists’ ability to assess the internal and external validity of studies’ findings and to replicate published studies; it also limits the generalizability of existing studies. The challenges of low transparency are particularly relevant in urban ecology, a field where standard protocols for site selection and delineation are still being developed. These limitations interfere with the fields’ ability to build theory and inform policy. We conclude by offering a set of recommendations to increase transparency, replicability, and generalizability.

54 ENVIRONMENTAL SCIENCES↗

A Practical Methodology for Quantifying Random and Systematic Components of Unexplained Variance in a Wind Tunnel

This paper documents a check standard wind tunnel test conducted in the Langley 0.3-Meter Transonic Cryogenic Tunnel (0.3M TCT) that was designed and analyzed using the Modern Design of Experiments (MDOE). The test designed to partition the unexplained variance of typical wind tunnel data samples into two constituent components, one attributable to ordinary random error, and one attributable to systematic error induced by covariate effects. Covariate effects in wind tunnel testing are discussed, with examples. The impact of systematic (non-random) unexplained variance on the statistical independence of sequential measurements is reviewed. The corresponding correlation among experimental errors is discussed, as is the impact of such correlation on experimental results generally. The specific experiment documented herein was organized as a formal test for the presence of unexplained variance in representative samples of wind tunnel data, in order to quantify the frequency with which such systematic error was detected, and its magnitude relative to ordinary random error. Levels of systematic and random error reported here are representative of those quantified in other facilities, as cited in the references.

Deloach, Richard↗

Factors controlling pore network development of thermally mature Early Palaeozoic mudstones from the Baltic Basin (N Poland)

Understanding the formation of pore space, especially in low porosity shales (as source rocks and as unconventional resources), is critical to the oil and gas industry, since pores control the space available for hydrocarbon and participate in hydrocarbon transport. We examined 87 Ordovician and Silurian mudstone samples collected from four wells located in the Pomeranian part of the Baltic Basin (northern Poland), one of the primary Polish targets for hydrocarbon exploration. These samples represent the Pelplin, the Paslek, the Jantar, the Prabuty, and the Sasino Formations, which still requires more detailed porosity studies. Our study aimed to identify factors controlling porosity development, by applying bulk techniques (organic petrology and TOC analyses, quantitative mineralogy, and porosimetry) as well as nano- to microscale techniques (thin section petrography, electron microscopy). The studied samples are mainly argillaceous mudstones. The results of porosimetry measurements, combined with image analysis, indicate that the pores of all studied rocks are dominated by micropores (pores < 2 nm in diameter), mesopores (2-50 nm in diameter) and small macropores. The SEM images showed three main pore types: a) voids related to clay mineral aggregates, b) pores inside organic matter particles, and c) pores between other mineral grains. In the Jantar and Sasino mudstones, the organic matter content and its thermal maturity control porosity. The occurrence of solid bitumen in the rocks from these formations reduces samples’ mesoporosity because of the pore-clogging effect. In contrast, in the Paslek and Prabuty Formations, there is low organic matter content and specific surface area and the volume of mesopores increase with clay minerals content. In the Pelplin mudstones, there are no prevailing factors controlling porosity. As a result, we suggest that a combination of SEM image analysis and dual liquid porosity (DLP) measurements is a powerful method to assess porosity available for petroleum flow in mudstones.

03 NATURAL GAS↗

Completed SDSS-IV extended Baryon Oscillation Spectroscopic Survey: Cosmological implications from two decades of spectroscopic surveys at the Apache Point Observatory

We present the cosmological implications from final measurements of clustering using galaxies, quasars, and Lyα forests from the completed Sloan Digital Sky Survey (SDSS) lineage of experiments in large-scale structure. These experiments, composed of data from SDSS, SDSS-II, BOSS, and eBOSS, offer independent measurements of baryon acoustic oscillation (BAO) measurements of angular-diameter distances and Hubble distances relative to the sound horizon, r d , from eight different samples and six measurements of the growth rate parameter, fσ 8 , from redshift-space distortions (RSD). This composite sample is the most constraining of its kind and allows us to perform a comprehensive assessment of the cosmological model after two decades of dedicated spectroscopic observation. We show that the BAO data alone are able to rule out dark-energy-free models at more than eight standard deviations in an extension to the flat, ΛCDM model that allows for curvature. When combined with Planck Cosmic Microwave Background (CMB) measurements of temperature and polarization, under the same model, the BAO data provide nearly an order of magnitude improvement on curvature constraints relative to primary CMB constraints alone. Independent of distance measurements, the SDSS RSD data complement weak lensing measurements from the Dark Energy Survey (DES) in demonstrating a preference for a flat ΛCDM cosmological model when combined with Planck measurements. The combined BAO and RSD measurements indicate σ 8 =0.85±0.03, implying a growth rate that is consistent with predictions from Planck temperature and polarization data and with General Relativity. When combining the results of SDSS BAO and RSD, Planck, Pantheon Type Ia supernovae (SNe Ia), and DES weak lensing and clustering measurements, all multiple-parameter extensions remain consistent with a ΛCDM model. Regardless of cosmological model, the precision on each of the three parameters, Ω Λ , H 0 , and σ 8 , remains at roughly 1%, showing changes of less than 0.6% in the central values between models. In a model that allows for free curvature and a time-evolving equation of state for dark energy, the combined samples produce a constraint Ω K =-0.0022±0.0022. The dark energy constraints lead to w 0 =-0.909±0.081 and w a =$-0.49_{-0.30}^{+0.35}$, corresponding to an equation of state of w p =-1.018±0.032 at a pivot redshift z p =0.29 and a Dark Energy Task Force Figure of Merit of 94. The inverse distance ladder measurement under this model yields H 0 =68.18±0.79 km s -1 Mpc -1 , remaining in tension with several direct determination methods; the BAO data allow Hubble constant estimates that are robust against the assumption of the cosmological model. In addition, the BAO data allow estimates of H 0 that are independent of the CMB data, with similar central values and precision under a ΛCDM model. Our most constraining combination of data gives the upper limit on the sum of neutrino masses at Σm ν <0.115 eV (95% confidence). Finally, we consider the improvements in cosmology constraints over the last decade by comparing our results to a sample representative of the period 2000-2010. We compute the relative gain across the five dimensions spanned by w, Ω k , Σm ν , H 0 , and σ 8 and find that the SDSS BAO and RSD data reduce the total posterior volume by a factor of 40 relative to the previous generation. Finally, adding again the Planck, DES, and Pantheon SN Ia samples leads to an overall contraction in the five-dimensional posterior volume of 3 orders of magnitude.

79 ASTRONOMY AND ASTROPHYSICS↗

Comparison of Geochemical Reactivity of Marcellus and Caney Shale Based on Effluent Analysis

ABSTRACT: In this comparative study, we analyzed the changes in elemental concentrations of hydraulic fracturing fluids after interaction with the Marcellus and Caney Shale formations. The focus was on assessing the inherent risks and environmental implications associated with flowback waters, including their impact on soil, ground, and drinking water quality, and human health safety. The chemical compositions of effluents were determined through Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and Mass spectrometry (ICP-MS). The Marcellus Shale, showed concentrations of Cd, averaging 0.380 ppm far exceeding safe water thresholds. Significant levels of As, Se, B, and Pb were detected in both shales, raising concerns about soil and water contamination. Analyzing the effluents from representative samples of sections of the Marcellus (S2 and S7) and Caney (R1 and R2) indicates different geochemical responses over 4 weeks of experiments. This comparison underscores the chemical changes and environmental considerations linked to hydraulic fracturing across shale formations, suggesting the value of tailored monitoring and regulatory measures for each type. 1. INTRODUCTION The Caney and Marcellus shales, differing in geology and geochemistry, represent distinct unconventional reservoirs. The Caney shale, is more ductile, with higher produced water volumes, (Smith et al., 2022) contrasts with the brittle Marcellus shale known for lower brine production but significant data availability. This study aims to elucidate the possible environmental health and safety issues that may arise from the hydraulic fracturing processes. The interaction between fracturing fluids and clays presents a significant challenge. The primary base of these fluids is water, which, when introduced to clay, can induce swelling and constrict flow pathways. This phenomenon is attributed to water molecules infiltrating the layers of clay, particularly in 2:1-type clays, leading to an increased distance between layers. To counteract this, clay stabilizers are employed (Awejori et al., 2021). Despite their effectiveness, these stabilizers are considered temporary solutions. Upon completion of the fracturing process, a concomitant amount of contaminated waters (flow back), with varied content is collected at the surface. From these, we can infer the geochemical reactions and the environmental challenges associated with these waters. Flowback waters can be reinjected or used for other purposes such as irrigation. This requires adequate screening and treatment for safe use.

Dje, L. B.↗

Evaluation of Satellite Remote Sensing Albedo Retrievals over the Ablation Area of the Southwestern Greenland Ice Sheet

MODerate resolution Imaging Spectroradiometer (MODIS) albedo products have been validated over spatially uniform, snow-covered areas of the Greenland ice sheet (GrIS) using the so-called single 'point-to-pixel' method. This study expands on this methodology by applying a 'multiple-point-to-pixel' method and examination of spatial autocorrelation (here using semivariogram analysis) by using in situ observations, high-resolution World- View-2 (WV-2) surface reflectances, and MODIS Collection V006 daily blue-sky albedo over a spatially heterogeneous surfaces in the lower ablation zone in southwest Greenland. Our results using 232 ground-based samples within two MODIS pixels, one being more spatial heterogeneous than the other, show little difference in accuracy among narrow and broad band albedos (except for Band 2). Within the more homogenous pixel area, in situ and MODIS albedos were very close (error varied from −4% to +7%) and within the range of ASD standard errors. The semivariogram analysis revealed that the minimum observational footprint needed for a spatially representative sample is 30 m. In contrast, over the more spatially heterogeneous surface pixel, a minimum footprint size was not quantifiable due to spatial autocorrelation, and far exceeds the effective resolution of the MODIS retrievals. Over the high spatial heterogeneity surface pixel, MODIS is lower than ground measurements by 4-7%, partly due to a known in situ undersampling of darker surfaces that often are impassable by foot (e.g., meltwater features and shadowing effects over crevasses). Despite the sampling issue, our analysis errors are very close to the stated general accuracy of the MODIS product of 5%. Thus, our study suggests that the MODIS albedo product performs well in a very heterogeneous, low-albedo, area of the ice sheet ablation zone. Furthermore, we demonstrate that single 'point-to-pixel' methods alone are insufficient in characterizing and validating the variation of surface albedo displayed in the lower ablation area. This is true because the distribution of in situ data deviations from MODIS albedo show a substantial range, with the average values for the 10th and 90th percentiles being −0.30 and 0.43 across all bands. Thus, if only single point is taken for ground validation, and is randomly selected from either distribution tails, the error would appear to be considerable. Given the need for multiple in-situ points, concurrent albedo measurements derived from existing AWSs, (low-flying vehicles (airborne or unmanned) and high-resolution imagery (WV-2)) are needed to resolve high sub-pixel variability in the ablation zone, and thus, further improve our characterization of Greenland's surface albedo.

Ablation zone↗

Experimental breakdown of selected anodized aluminum samples in dilute plasmas

Anodized aluminum samples representative of Space Station Freedom structural material were tested for electrical breakdown under space plasma conditions. In space, this potential arises across the insulating anodized coating when the spacecraft structure is driven to a negative bias relative to the external plasma potential due to plasma-surface interaction phenomena. For anodized materials used in the tests, it was found that breakdown voltage varied from 100 to 2000 volts depending on the sample. The current in the arcs depended on the sample, the capacitor, and the voltage. The level of the arc currents varied from 60 to 1000 amperes. The plasma number density varied from 3 x 10 exp 6 to 10 exp 3 ions per cc. The time between arcs increased as the number density was lowered. Corona testing of anodized samples revealed that samples with higher corona inception voltage had higher arcing inception voltages. From this it is concluded that corona testing may provide a method of screening the samples.

Grier, Norman T.↗

AR-40 AR-39 Age of an Impact-Melt Lithology in DHOFAR 961

The South Pole-Aitken (SPA) basin is the stratigraphically oldest identifiable lunar basin and is therefore one of the most important targets for absolute age-dating to help understand whether ancient lunar bombardment history smoothly declined or was punctuated by a cataclysm. The SPA basin also has another convenient property, a geochemically distinct interior, unobscured by extensive mare basalt fill. A case has been made for the possible origin of the Dhofar 961 lunar meteorite in the South Pole-Aitken (SPA) basin, based on comparing its composition with Lunar Prospector gamma-ray data for the interior of the SPA basin. Dhofar 961 contains several different impact-melt (IM) lithologies. Jolliff et al. described two classes of mafic impact-melt lithologies, one dominated by olivine (Lithology A) and the other by plagioclase (An 95-96.5) (Lithology B). Broad-beam analyses of these lithologies yielded (is) approximately 14.0 wt% FeO, 11.7 wt% MgO, and 15.4 wt% Al2O3. Lithologies A and B differ by approximately 2.5% Al2O3, 1.5% FeO and 1.5% MgO, consistent with the occurrence of olivine phenocrysts in A and plagioclase clasts in B. Both lithologies are considerably more mafic than the Apollo mafic impact-melt breccias, corresponding to olivine gabbronorite. Joy et al. used U-Pb dating to investigate phosphate fragments in the Dhofar 961 matrix and impact-melt clasts. Matrix phosphates have 4.34 to 4 Ga ages, consistent with ancient KREEP-driven magmatic episodes and Pre-Nectarian ((is) greater than 3.92 Ga). Phosphates found within Dhofar 961 crystalline impact melt breccia clasts range from 4.26 to 3.89 Ga, potentially recording events throughout the basin forming epoch of lunar history. The youngest reset ages in the Dhofar 961 sample represent an upper limit for the time of formation of the meteorite. Joy et al suggested this age represents the final impact that mixed and consolidated several generations of precursor rocks into the Dhofar meteorite group, although they note that further age dating of all the stones is required to test this hypothesis. We received a split of Dhofar 961 from R. Zeigler consisting of a large clast of IM Lithology B, with some light-colored, friable matrix clinging to the external margins of the impact-melt clast. This lithology was not present in the samples investigated by Joy et al. and thus does not have corresponding U-Pb ages on it. We created multiple subsplits of both the IM and matrix lithologies, each weighing several tens of micrograms. We conducted Ar-40 Ar-39 dating of this candidate SPA material by high-resolution step heating and comparing it with the regolith that surrounds it.

Lithology↗

Pulmonary Inflammatory Responses To Acute Meteorite Dust Exposures - Implications For Human Space Exploration

The previous manned missions to the Moon represent milestones of human ingenuity, perseverance, and intellectual curiosity. However, one of the major ongoing concerns is the array of hazards associated with lunar surface dust. Not only did the dust cause mechanical and structural integrity issues with the suits, the dust 'storm' generated upon reentrance into the crew cabin caused "lunar hay fever" and "almost blindness" (Figure 1). It was further reported that the allergic response to the dust worsened with each exposure. The lack of gravity exacerbated the exposure, requiring the astronauts to wear their helmet within the module in order to avoid breathing the irritating particles. Due to the prevalence of these high exposures, the Human Research Roadmap developed by NASA identifies the Risk of Adverse Health and Performance Effects of Celestial Dust Exposure as an area of concern. Extended human exploration will further increase the probability of inadvertent and repeated exposures to celestial dusts. Going forward, hazard assessments of celestial dusts will be determined through sample return efforts prior to astronaut deployment. Studies on the lunar highland regolith indicate that the dust is not only respirable but also reactive, and previous studies concluded that it is moderately toxic; generating a greater response than titanium oxide but a lower response than quartz. The presence of reactive oxygen species (ROS) on the surface of the dust has been implicated. However, there is actually little data related to physicochemical characteristics of particulates and pulmonary toxicity, especially as it relates to celestial dust exposure. As a direct response to this deficit, the present study evaluates the role of a particulate's innate geochemical features (e.g., bulk chemistry, internal composition, morphology, size, and reactivity) in generating adverse toxicological responses in vitro and in vivo. This highly interdisciplinary study evaluates the relative toxicity of six meteorite samples representing either basalt or regolith breccia on the surfaces of the Moon, Mars, and Asteroid 4Vesta; three potential candidates for future human exploration or colonization. Terrestrial mid-ocean ridge basalt (MORB) is also used for comparison as a control sample.

Harrington, A. D.↗

Advancing Chemical Separations: Unraveling the Structure and Dynamics of Phase Splitting in Liquid–Liquid Extraction

Liquid-liquid extraction (LLE), the go-to process for a variety of chemical separations, is limited by spontaneous organic phase splitting upon sufficient solute loading, called third phase formation. In this study we explore the applicability of critical phenomena theory to gain insight into this deleterious phase behavior with the goal of improving separations efficiency and minimizing waste. Here, a series of samples representative of rare earth purification were constructed to include each of one light and one heavy lanthanide (cerium and lutetium) paired with one of two common malonamide extractants (DMDOHEMA and DMDBTDMA). The resulting postextraction organic phases are chemically complex and often form rich hierarchical structures whose statics and dynamics near the critical point were probed herein with small-angle X-ray scattering and high-speed X-ray photon correlation spectroscopy. Despite their different extraction behaviors, all samples show remarkably similar critical behavior with exponents well described by classical critical point theory consistent with the 3D Ising model, where the critical behavior is characterized by fluctuations with a single diverging length scale. This unexpected result indicates a significant reduction in relevant chemical parameters at the critical point, indicating that the underlying behavior of phase transitions in LLE rely on far fewer variables than are generally assumed. The obtained scalar order parameter is attributed to the extractant fraction of the extractant/diluent mixture, revealing that other solution components and their respective concentrations simply shift the critical temperature but do not affect the nature of the critical fluctuations. These findings point to an opportunity to drastically simplify studies of liquid-liquid phase separation and phase diagram development in general while providing insights into LLE process improvement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Acute Meteorite Dust Exposure and Pulmonary Inflammation - Implications for Human Space Exploration

The previous manned missions to the Moon represent milestones of human ingenuity, perseverance, and intellectual curiosity. However, one of the major ongoing concerns is the array of hazards associated with lunar surface dust. Not only did the dust cause mechanical and structural integrity issues with the suits, the dust 'storm' generated upon reentrance into the crew cabin caused "lunar hay fever" and "almost blindness [1-3]" (Figure 1). It was further reported that the allergic response to the dust worsened with each exposure [4]. The lack of gravity exacerbated the exposure, requiring the astronauts to wear their helmet within the module in order to avoid breathing the irritating particles [1]. Due to the prevalence of these high exposures, the Human Research Roadmap developed by NASA identifies the Risk of Adverse Health and Performance Effects of Celestial Dust Exposure as an area of concern [5]. Extended human exploration will further increase the probability of inadvertent and repeated exposures to celestial dusts. Going forward, hazard assessments of celestial dusts will be determined through sample return efforts prior to astronaut deployment. Studies on the lunar highland regolith indicate that the dust is not only respirable but also reactive [2, 6-9], and previous studies concluded that it is moderately toxic; generating a greater response than titanium oxide but a lower response than quartz [6]. The presence of reactive oxygen species (ROS) on the surface of the dust has been implicated. However, there is actually little data related to physicochemical characteristics of particulates and pulmonary toxicity, especially as it relates to celestial dust exposure. As a direct response to this deficit, the present study evaluates the role of a particulate's innate geochemical features (e.g., bulk chemistry, internal composition, morphology, size, and reactivity) in generating adverse toxicological responses in vitro and in vivo. This highly interdisciplinary study evaluates the relative toxicity of six meteorite samples representing either basalt or regolith breccia on the surfaces of the Moon, Mars, and Asteroid 4Vesta (Table 1); three potential candidates for future human exploration or colonization. Terrestrial mid-ocean ridge basalt (MORB) is also used for comparison as a control sample.

Harrington, A. D.↗

FY25 Status Update on A709 Code Case Testing at ANL

This report provides an update on the status of the creep rupture testing on the precipitation-treated (PT) Alloy 709 samples fabricated from the first, the second and the third commercial heats, in support of the first, 100,000-hour Alloy 709 Code Case development under the American Society of Mechanical Engineers (ASME) Section III, Division 5 for high-temperature reactor construction. In Fiscal Year (FY) 25, no new tests were initiated, while 5 previously loaded tests were completed. This report presents an overview of the creep-rupture data gathered at Argonne National Laboratory (ANL) since FY21 that totaled 52 completed tests. Metallographic images showing crack morphologies in some representative samples ruptured in FY25 are also included. Key conclusions include: 1) the creep behavior of the three heats of Alloy 709 can be well described by the Larson-Miller relationship; 2) higher temperatures and larger stresses lead to shorter creep life and higher minimum creep rate; 3) Alloy 709 is overall very ductile under creep; 4) the crack morphologies near fracture surfaces are dependent on material’s grain size and test conditions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Red-green-bleached redox interfaces in the proximal Permian Cutler red beds: implications for regional fluid alteration

Siliciclastic strata of the Colorado Plateau attract attention for their striking red, green, bleached, and variegated colors that potentially record both early depositional and later diagenetic events. We investigated the proximal-most strata of the Paradox Basin, from their onlap contact with the Precambrian basement of the Uncompahgre Plateau to the younger Cutler strata exposed within 10 km of the Uncompahgre Plateau to attempt to understand the significance of the striking colors that occur here. These strata preserve a complex geology associated with buried paleorelief and sediment-related permeability variations at a major basin-uplift interface. Strata exposed within ~1.5 km of the onlap contact exhibit a pervasive drab color in contrast to the generally red colors that predominate farther from this front. In-between, strata commonly host variegated red/green/bleached intercalations. Thin-section petrography, SEM, XRD, Raman spectroscopy, Mössbauer spectroscopy, and whole-rock geochemistry of samples representing different color variations from demonstrate that water–rock interactions charged the rocks with Fe(II) that persists primarily in the phyllosilicate fraction. Color variations reflect grain-size differences that allowed the reduction of fluids from regional fault and basement/fill contacts to permeate coarser-grained Cutler sediments. Hematite and chlorite occur in both red and green sediments but are absent in the bleached sediments. Pervasive hematite in both red and green layers suggests that sediments were hematite-rich before later alteration. Chlorite and smectite are elevated in green samples and inversely correlated with biotite content. Green coloration is generally associated with 1) coarser grain sizes, 2) spatial association with basement contacts, 3) elevated smectite and/or chlorite, 4) less total Fe but greater Fe(II)/Fe(III) primarily in the phyllosilicate fraction, and 5) uranium enrichment. The bleached coloration reflects the removal of pigmentary Fe(III) oxide, while the green coloration is due to the removal of pigmentary hematite and the abundance of Fe(II)-bearing phyllosilicates. Abundant mixed-layer and swelling clays such as smectite, illite/smectite, and chlorite/smectite (including tosudite) dominate the mineralogy of the clay fraction. These results are consistent with other studies demonstrating fault-associated fluid alteration in the Paradox Basin region. However, the pervasive greening was not observed in many of these studies and appears to reflect the unique aspects of the paleovalley system and the importance of biotite alteration to Fe(II)-bearing phyllosilicates.

58 GEOSCIENCES↗

Molecular Characterization of Water-Soluble Brown Carbon Chromophores in Snowpack from Northern Xinjiang, China

This study reports molecular-level characterization of brown carbon (BrC) attributed to water-soluble organic carbon in six snowpack samples collected from northern Xinjiang, China. Here, the molecular composition and light-absorbing properties of BrC chromophores were unraveled by application of high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector and high-resolution mass spectrometry. The chromophores were classified into five major types, that is, (1) phenolic/lignin-derived compounds, (2) flavonoids, (3) nitroaromatics, (4) oxygenated aromatics, and (5) other chromophores. Identified chromophores account for ~23–64% of the total light absorption measured by the PDA detector in the wavelength range of 300–370 nm. In the representative samples from urban and remote areas, oxygenated aromatics and nitroaromatics dominate the absorption in the wavelengths below and above 320 nm, respectively. The highly polluted urban sample shows the most complex HPLC-PDA chromatogram, and more other chromophores contribute to the bulk absorption. Phenolic/ lignin-derived compounds are the most light-absorbing species in the soil-influenced sample. Chromophores in two remote samples exhibit ultraviolet–visible features distinct from other samples, which are attributed to flavonoids. Identification of individual chromophores and quantitative analysis of their optical properties are helpful for elucidating the roles of BrC in snow radiative balance and photochemistry.

54 ENVIRONMENTAL SCIENCES↗

Evidence for a Significant Kuiper Belt Dust Contribution to the Zodiacal Cloud

Interplanetary dust particles (IDPs) are important samples of dust-producing objects in the solar system including many primitive and organic-rich bodies that are not sampled by known meteorites. IDPs spiral in towards the Sun under the influence of Poynting-Robertson (P-R) drag forces and are exposed to solar energetic particles (SEPs) that leave tracks of ionization damage in anhydrous silicate grains. We determined the exposure ages of track-rich IDPs using a new calibration of the SEP track production rate and show that track-rich IDPs have long exposure ages (>1 My) that preclude an origin from main-belt asteroids (MBAs) and Jupiter-family comets (JFCs). We propose that track-rich IDPs represent samples of dust produced by collisions among Edgeworth-Kuiper Belt objects (EKBOs) and that appreciable amounts of EKBO dust are contributing to the Zodiacal cloud. Many track-rich IDPs also contain abundant secondary minerals that provide direct evidence for past aqueous activity on some EKBOs.

Lindsay P. Keller↗

Extending ROSAT Light Curves of Ecliptic Pole AGN Formation and Galaxy Evolution

In collaboration with UCLA graduate student Fred Baganoff, Professor Malkan has obtained the longest continuous light curves ever available for a large sample (# = 60) of active galactic nuclei. This was accomplished by using the ROSATAII-Sky Survey, which covered the ecliptic pole regions once every 9O-minute orbit. Using this Astrophysics Data Processing grant from NASA, we extended these light curves by combining the RASS data with pointed observations over the next several years of operation of the ROSAT PSPC. This lengthens the baselines of about half of the light curves from a few months up to a few years. The proportion of AGN showing variability increases substantially with this improvement. In fact most AGN in this representative sample are now shown to be significantly variable in the X-rays. We are also able to say something about the amplitudes of variability on timescales from days to years, with more detail than previously has been possible. We have also identified some dependence of the X-ray variability properties on a) the luminosity of the AGN; and b) The presence of a "Blazar" nucleus. By extending the ROSAT light curves, we are also able to learn more about the correlation of X-ray and optical emission on longer time-scales. It appears to be very weak, at best.

Malkan, Matthew A.↗