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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Model‐Based Interpretation of Solute Exports and Carbon Partitioning During Shale Weathering in a Mountainous Hillslope

The weathering of sedimentary rocks in high-elevation catchments influences freshwater quality and the global carbon cycle. While individual biogeochemical mechanisms involved in this process are relatively well understood, quantifying their contributions to solute export and carbon fluxes under natural, transient conditions remains challenging. Here, we implement a numerical multidimensional and multiphase model to simulate coupled hydrological and biogeochemical processes in a shale-underlain, snow-dominated hillslope in the Rocky Mountains, Colorado. The model captures the dynamic interplay between soil respiration, mineral weathering, and climate-driven hydrological forcing, reproducing observed soil CO 2 dynamics, groundwater chemistry, and subsurface flow. Our results reveal that seasonal snowmelt enhances carbonate weathering by promoting the infiltration of CO 2 -rich water to depth, while pyrite oxidation is primarily sensitive to low water saturation that facilitates O 2 diffusion through the regolith. Topography modulates the spatial distribution of shale weathering, as steeper slopes enhance lateral drainage, favoring the delivery of reactants to greater depths. While shale weathering at our site acts as a transient carbon sink, with silicates and carbonates buffering acidity and promoting atmospheric CO 2 consumption (1% of soil-derived CO 2 ), the exported dissolved inorganic carbon is predominantly geogenic (∼73%). Consequently, when accounting for long-term marine carbonate precipitation. The current weathering regime represents a net source of carbon to the atmosphere. The oxidation of pyrite and petrogenic organic carbon together release approximately 0.9 mol·m −2 ·yr −1 of CO 2 . Our findings highlight the role of topography, hydroclimate, and the coupling between acid-base reactions in shaping the carbon balance and the solute exports in mountainous critical zones.

carbon cycling↗
DOE OSTI2022

Ecological Quality Evolution and Its Driving Factors in Yunnan Karst Rocky Desertification Areas

Rocky desertification is a key element affecting regional ecological quality. Rocky desertification in Southwest China directly affects the ecological security of the Yangtze River and Pearl River basins and also restricts regional economic and social development. In order to clarify the evolution laws and key influencing factors of ecological quality in Yunnan karst rocky desertification areas, a quantitative analysis based on the remote sensing-based ecological index (RSEI) model was conducted to explore the overall evolution characteristics and change laws of ecological quality in Yunnan karst rocky desertification areas in the past 30 years. The correlation between RSEI, rock outcrop rate (Fr), and driving factors was determined by redundancy analysis. The results showed the following: (1) RSEI in Yunnan karst rocky desertification areas generally showed a decreasing trend, with a fluctuation in the mid-term, followed by a tendency to recover. It fell into three stages: decline, trough, and recovery, with fitting coefficients of -0.121, -0.057, and 0.157, respectively. In contrast, Fr showed an opposite tendency, illustrating the inverse relationship between RSEI and Fr, and the rate of sequential succession was much faster than that of the reverse succession under human measures of intervention. (2) The mean value of RSEI of Yunnan karst rocky desertification areas was generally lower than that of the total Yunnan Province land areas and Yunnan non-karst rocky desertification areas, but the mean value of Fr was generally more than that of both the above-mentioned areas. In addition, the RSEI and Fr of Yunnan karst rocky desertification areas both showed lower stability values than those of both the above-mentioned areas. This generally suggested a low ecological quality and a high degree of desertification under a low stability in Yunnan karst rocky desertification areas. (3) The correlation of RSEI and Fr with driving factors followed the order of topographic factors, soil factors > water factors > anthropogenic factors. Anthropogenic factors were the driving force changing the state of rocky desertification, geological factors such as topography and soil to a larger extent determined the original macroscopic ecological relationship of rocky desertification, and water factors lay between the above two. The findings of this research will provide theoretical support and a basis for the improvement of ecological quality and comprehensive control of karst rocky desertification in Yunnan Province.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2022

The Zn, S, and Cl Isotope Compositions of Mare Basalts: Implications for the Effects of Eruption Style and Pressure on Volatile Element Stable Isotope Fractionation on the Moon

We compare the stable isotope compositions of Zn, S, and Cl for Apollo mare basalts to better constrain the sources and timescales of lunar volatile loss. Mare basalts have broadly elevated yet limited ranges in δ(66)Zn, δ(34)S, and δ(37)Cl_(SBC+WSC) values of 1.27 ± 0.71, 0.55 ± 0.18, and 4.1 ± 4.0‰, respectively, compared to the silicate Earth at 0.15, –1.28, and 0‰, respectively. We find that the Zn, S, and Cl isotope compositions are similar between the low- and high-Ti mare basalts, providing evidence of a geochemical signature in the mare basalt source region that is inherited from lunar formation and magma ocean crystallization. The uniformity of these compositions implies mixing following mantle overturn, as well as minimal changes associated with subsequent mare magmatism. Degassing of mare magmas and lavas did not contribute to the large variations in Zn, S, and Cl isotope compositions found in some lunar materials (i.e., 15‰ in δ(66)Zn, 60‰ in δ(34)S, and 30‰ in δ(37)Cl). This reflects magma sources that experienced minimal volatile loss due to high confining pressures that generally exceeded their equilibrium saturation pressures. Alternatively, these data indicate effective isotopic fractionation factors were near unity. Our observations of S isotope compositions in mare basalts contrast to those for picritic glasses (Saal and Hauri 2021), which vary widely in S isotope compositions from –14.0 to 1.3‰, explained by extensive degassing of picritic magmas under high-P/P_(Sat) values (>0.9) during pyroclastic eruptions. The difference in the isotope compositions of picritic glass beads and mare basalts may result from differences in effusive (mare) and explosive (picritic) eruption styles, wherein the high-gas contents necessary for magma fragmentation would result in large effective isotopic fractionation factors during degassing of picritic magmas. Additionally, in highly vesiculated basalts, the δ(34)S and δ(37)Cl values of apatite grains are higher and more variable than the corresponding bulk-rock values. The large isotopic range in the vesiculated samples is explained by late-stage low-pressure “vacuum” degassing (P/P-(Sat) ~ 0) of mare lavas wherein vesicle formation and apatite crystallization took place post-eruption. Bulk-rock mare basalts were seemingly unaffected by vacuum degassing. Degassing of mare lavas only became important in the final stages of crystallization recorded in apatite—potentially facilitated by cracks/fractures in the crystallizing flow. We conclude that samples with wide-ranging volatile element isotope compositions are likely explained by localized processes, which do not represent the bulk Moon.

Halogens↗
NASA NTRS2022

Abundant phosphorus expected for possible life in Enceladus’s ocean

Saturn’s moon Enceladus has a potentially habitable subsurface water ocean that contains canonical building blocks of life (organic and inorganic carbon, ammonia, possibly hydro-gen sulfide) and chemical energy (disequilibria for methanogenesis). However, its habit-ability could be strongly affected by the unknown availability of phosphorus (P). Here, we perform thermodynamic and kinetic modeling that simulates P geochemistry based on recent insights into the geochemistry of the ocean–seafloor system on Enceladus. We find that aqueous P should predominantly exist as orthophosphate (e.g., HPO422), and total dissolved inorganic P could reach 1027to 1022mol/kg H2O, generally increasing with lower pH and higher dissolved CO2, but also depending upon dissolved ammonia and silica. Levels are much higher than<10210mol/kg H2Ofrompreviousestimatesand close to or higher than∼1026mol/kg H2O in modern Earth seawater. The high P concentration is primarily ascribed to a high (bi)carbonate concentration, which decreases the concentrations of multivalent cations via carbonate mineral formation, allowing phosphate to accumulate. Kinetic modeling of phosphate mineral dissolution suggests that geologically rapid release of P from seafloor weathering of a chondritic rocky core could supply millimoles of total dissolved P per kilogram of H2Owithin105y, much less than the likely age of Enceladus’s ocean (108to 109y). These results provide further evidence of habitable ocean conditions and show that any oceanic life would not be inhibited by low P availability.

Enceladus ocean↗
DOE OSTI2025

Selectivity of tris complexation for Ni(II), Co(II), and Fe(II) and its effect on carbonate precipitation under alkaline conditions

Simultaneous critical element recovery and ex-situ carbon mineralization of low-grade ultramafic deposits have garnered increasing interest. Understanding the selectivity of metal complexing organic ligands for various divalent metals present in ultramafic rocks during carbonate mineralization is required to optimize this process. Here we evaluate 2-amino-2-(hydroxymethyl)-1,3-propanediol (i.e., Tris) as a model for bidentate ligands that bind divalent metals with both amine and alcohol groups in alkaline conditions (pH 8–10.5) at 25 °C and 80 °C in carbonate-buffered solutions. Protonated Tris forms a stronger complex with metal ions and is selective for trace metals with Ni(II) > Co(II) > Fe(II) during carbonate precipitation, with the rates decreasing but selectivity increasing at lower temperature and lower pH. At 25 °C, metastable amorphous hydrated carbonates form, regardless of the amount of Tris present or pH values. At 80 °C and pH 8, the Co and Fe carbonates that form are a mixture of rosasite-group minerals (Co 2 CO 3 (OH) 2 (H 2 O) and Fe 2 CO 3 (OH) 2 ) and pure carbonates (sphaerocobaltite: CoCO 3 and siderite: FeCO 3 ), with the latter more stabilized with increasing Tris concentration. In mixed metal solutions without Tris at 25 °C where Fe:Ni or Fe:Co is 2:1, Fe increases the rates of Ni or Co carbonate precipitation. However, with increasing Tris concentration the presence of Ni or Co inhibits Fe carbonate precipitation. At 80 °C without Tris, Ni or Co substitute into the iron chukanovite (Fe 2 CO 3 (OH) 2 ) lattice, increasing Ni or Co carbonate precipitation rates. Increasing Tris concentration only slightly inhibits Fe and Co precipitation, but slows Ni precipitation up to 10 times, with Fe progressively partitioning into more pure carbonate phases with distinct crystalline morphologies. These findings suggest bidentate amine-bearing ligands may be effective at Ni and Co recovery during carbon mineralization of Fe-bearing ultramafic deposits at relatively low temperatures and slightly alkaline pH.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Failure Analysis–Informed Risk Assessment Framework for Geological Carbon Storage Using Numerical Simulation and Machine Learning

Geological carbon storage (GCS) is recognized as a critical technology for achieving large-scale reductions in anthropogenic carbon dioxide (CO 2 ) emissions. Ensuring long-term containment and safety requires robust risk assessment frameworks that account for geological uncertainty and identify potential failure scenarios. Among various indicators, the area of review (AoR) serves as a key metric for evaluating storage performance, regulatory compliance, and monitoring design, as it delineates the spatial extent impacted by pressure buildup and plume migration. However, conventional AoR-based risk assessments typically perturb parameters within narrow uncertainty bounds, potentially overlooking rare but high-impact events arising from extreme geological conditions. In this study, we present a failure analysis–informed risk assessment framework for large-scale GCS projects to improve site prescreening and monitoring design. A suite of 300 numerical simulations was generated using stochastic geological models that vary five key parameters: net-to-gross ratio, anisotropy azimuth, porosity multiplier, permeability multiplier, and vertical-to-horizontal permeability ratio. Among these, 200 realizations represent normal geological uncertainty, while 100 additional cases explore extreme yet plausible conditions for failure-case analysis. The AoR was simulated and computed from pressure and CO 2 saturation fields, where the baseline AoR boundary, representing the extent predicted under typical geological uncertainty, was defined as the union of 200 normal-range simulations, and failure was identified when extreme-range cases exceeded this baseline. Results show that incorporating broader parameter uncertainty produces significantly larger AoR extents, underscoring the potential underestimation of risk under conventional uncertainty ranges. Furthermore, spatial probability maps derived from failure-induced AoR exceedance identify regions requiring enhanced monitoring attention. Various machine learning (ML)–based classifiers were developed to predict failure occurrence from geological parameters, with the random forest model achieving the highest performance (F1-score of 0.986). Consistent findings from correlation coefficient, feature importance, and Sobol sensitivity analyses reveal that low net-to-gross ratios and permeability multipliers are the dominant risk drivers, reflecting reduced reservoir connectivity and limited pressure dissipation. Altogether, these results provide a novel framework for risk-informed site prescreening and monitoring design that explicitly considers rare but high-impact geological scenarios in GCS projects.

25 ENERGY STORAGE↗
DOE OSTI2026

Comprehensive earthquake catalogue update and spatiotemporal distribution analysis for Iraq and surrounding regions, northeastern Arabian Plate

The updated earthquake catalogue for Iraq covers the period from 1900 to the end of 2021 and includes over 37 000 recorded earthquakes. To create this comprehensive catalogue, five key steps were taken: compiling bulletins, calculating moment magnitudes, harmonizing magnitudes, establishing empirical conversion relations and evaluating the completeness of the catalogue. A notable enhancement in this update is the direct calculation of moment magnitudes for approximately 2800 earthquakes, achieved through the coda envelope technique and waveform data from the Mesopotamian Seismological Network (MPSN) in Iraq. This updated catalogue serves as a valuable resource for examining the spatiotemporal distribution of earthquakes, with respect to earthquake density, maximum moment magnitude and seismogenic depths. Additionally, the Gutenberg–Richter relationship was applied to calculate the a- and b-values specific to Iraq. The findings show that the Zagros Fold-Thrust Belt has a seismogenic layer (source) that ranges from 2 to 33 km deep and experiences high seismic activity. In contrast, the Mesopotamian Foredeep has a seismogenic layer ranging from 1 to 25 km deep and has lower seismic activity. The greatest seismic activity is concentrated around the Mandili-Badra-Teeb fault, which has experienced significant ruptures over time. The Outer Arabian Platform is identified as the main area of seismic activity, while additional activity occurs on the Inner Arabian Platform. Three major tectonic boundaries define the distribution of earthquakes in the northeastern Arabian Plate. These boundaries are defined by the Main Zagros Reverse Fault, the Zagros Foredeep Fault and the Anah Graben and Abu Jir-Euphrates Fault Zone. These boundaries highlight variations in seismicity levels and the spatial distribution of deformation in the region. The updated earthquake catalogue presented in this study is expected to play a vital role in regional seismicity assessments and seismic hazard analyses for Iraq and its surrounding areas.

58 GEOSCIENCES↗
NASA NTRS1989

Land altimetry using satellite data from the GEOSAT sea altimeter

Several techniques are proposed or assessed from the GEOSAT sea altimeter, and changes are recommended in future RADAR altimeters. The first technique tried was to cross-correlate each waveform with the preceding one. Then the position giving the maximum correlation was taken as the correct placement of the new waveform in its data window. The resulting altitude profile was slightly more variable than that of the on-board tracker over flat rock (Salar de Uyuni), so apparently successive waveforms are too dissimilar to correlate. When cross-correlation failed, compensation was made for averaging. Raw waveforms are averaged in groups of 100 and it is these average waveforms which are available for ground processing. But while the 100 are being received, the window position is moved in time, at different constant rates for the first 50 and last 50. Assuming an unchanging waveform and a single window rate for the 100, first and last waveforms were obtained. Averaging their half-height arrival times gave an altitude profile similar to the median and centroid methods. The variability of this altitude profile suggests that even raw waveforms in a group of 100 may be too dissimilar to correlate. In other techniques, the pulse was judged to have arrived when one of these criteria was met: the wave amplitude meets a certain absolute threshold; wave amplitude meets a certain relative threshold; certain fraction of the area of the waveform has passed; and centroid of the waveform has passed. All methods gave altitude profiles at least as variable as the on-board tracker, and all were biased at least 0.5 meter to low altitudes, except the threshold detector. The threshold detector can be filtered spatially to resemble the on-board tracker, and perhaps it could be implemented without feedback. For operating over land, these changes are recommended in future altimeters: The window should not move while raw waveforms are being averaged; some of the raw waveforms should be telemetered to earth for study, placing the waveform in the window should allow for shape variety; and some form of threshold detector might be used to find the signal and place it.

Luft, Philip E.↗
DOE OSTI2024

Characterization of the Triassic Newark Basin of New York and New Jersey for Geologic Storage of Carbon Dioxide

The project Characterization of the Triassic Newark Basin of New York and New Jersey for Geologic Storage of Carbon Dioxide is one of 9 site characterization projects that were implemented as part of ARRA (American Recovery and Reinvestment Act). Data from this project was used to improve resolution of data in NATCARB in the area of study. Data related to this study has already been incorporated in NATCARB Atlas. Sandia Technologies, LLC, and co-investigator Conrad Geoscience Corporation, examined the potential for large-scale, permanent CO2 storage in sedimentary strata within the Newark Rift Basin. The Newark Rift Basin underlies an industrialized, developed region comprising parts of New York, New Jersey, and Pennsylvania. The project characterized and investigated the suitability of Triassic age sedimentary formations for potential geologic CO2 storage. The project team drilled and cored two test wells to define the sedimentary geologic formations underlying the basin and to document or reach basement rock. With this geologic characterization phase, an integration of seismic, geologic, borehole, and formation core results provided a higher resolution assessment of CO2 storage potential. The Stockton Formation is known to be a potentially favorable geologic storage formation in the basin. In 2011, the 1-NYSTA Tandem Lot stratigraphic test well was drilled to a depth of 6,855 feet in the northern portion of the Newark Basin in southern New York State. Approximately 9 miles south-southeast on the Lamont Doherty Campus, TW-4 was drilled and cored in 2013 to a depth of 1,802 feet and contacted apparent igneous basement at a depth of 1,712 feet. Both wells penetrated the Palisades Sill ranging from 800 feet thick in the eastern well to approximately 1,800 feet in thickness at the 1-NYSTA Tandem Lot deep drill site. A diabase sill can provide an excellent seal and dense confining layer for potential CO2 storage reservoirs and flow layers that are situated beneath it within the Stockton Sandstone. The Stockton Sandstone was encountered beneath the sill in the TW-4 well on the Lamont campus, and data integration suggests that it was likely observed near total depth in the deep 1-NYSTA Tandem Lot well. The test wells confirm and define reservoirs are present beneath the sill and offer CO2 storage potential. The integration of geologic and reservoir characterization of well logs, formation cores, and formation fluids indicated Triassic age lacustrine playa lake and mudbank shales of the Upper Passaic Group can provide an effective seal for the porous and permeable underlying sandstone reservoir layers. This project acquired seismic data, drilled borehole well logs, acquired core samples, and integrated these findings to provide a better understanding of the subsurface geologic formations in the Newark Rift Basin. These findings have contributed to a higher degree of accuracy in predicting potential geologic storage opportunities, while refining geologic storage capacity estimates for the indicated reservoirs and flow units.

.las↗
NASA NTRS2016

Preserving, Enhancing, and Continuing the Scientific Legacy of the Apollo Sample Suite

From 1969 to 1972, Apollo astronauts collected 382 kg of rocks, soils, and core samples from six geologically diverse locations on the Moon. In the nearly 50 years since the samples were collected, over 3000 different studies have been conducted using the nearly 2200 different Apollo samples. Despite the maturity of the sample collection, many new studies of lunar samples are undertaken each year, with an average of more than 55 requests and more than 600 distinct subsamples allocated annually over the past five years. The Apollo samples are a finite resource, however. Although new studies are encouraged, it is important that new studies do not duplicate previous studies, and where possible, leverage previous results to inform and enhance the current studies. This helps to preserve the samples and scientific funding, both of which are precious resources. We have initiated several new efforts to rescue some of the early analyses from these samples, including unpublished analytical data. We are actively scanning NASA documentation in paper form that is related to the Apollo missions and sample processing, and we are collaborating with IEDA to establish a geochemical data base called MoonDB. To populate this database, we are actively working with about a dozen prominent lunar PIs to organize and transcribe years of both published and unpublished data, making it available to all researchers. This effort will also take advantage of new online analytical tools like PetDB. There have already been tangible results from the MoonDB data rescue effort. A pilot project involving the rescue of geochemical data of John Delano on Apollo pyroclastic glasses has already been referenced in multiple Apollo sample requests, and in fact, the compiled data was used as part of one of the new studies. Similarly, scanned sample handling reports have been utilized to find previously analyzed samples that were appropriate to fulfill new sample requests. We have also begun to image the Apollo samples using (1) micro‐CT scanning to document the interior structure of samples, and (2) comprehensive high resolution photography of samples, enabling high resolution 3D reconstructions of the samples. Both efforts will provide comprehensive access to these samples and allow for more targeted requests, and thus better curation of the samples for decades to come.

Zeigler, Ryan↗
NASA NTRSDate not supplied

X-Ray Computed Tomography During Preliminary Examination of Apollo Drive Tube 73001

Introduction: Starting in 2019, the Apollo Next Generation Sample Analysis (ANGSA) Program has enabled consortium studies of specially curated Apollo samples that were previously unstudied (or under studied). This began with unsealed core tube 73002 [1,2] that is the upper part of a station 3 double drive tube. More recently the pro-gram extended to the study of a variety of frozen Apollo 17 samples [3], as well as the gas extraction [4] and dis-section [5] of 73001, the lower half of the station 3 double drive tube, that was sealed under vacuum on the Moon. In this abstract we will examine the role of X-ray Computed Tomography (XCT) during the preliminary examination process for sealed core 73001, including: (1) engineering scans to aid in understanding the gas extraction process, whole-core scanning prior to opening to inform extrusion and dissection work, and (3) individual particle scanning to characterize rock fragment lithologies for follow on studies. Methodology: Sample 73001 is a 33 cm long, 4 cm diameter regolith sample collected inside a drive tube (~1 mm aluminum walls). That drive tube was sealed inside a 0.5 mm thick stainless steel (SS) Core Sample Vacuum Container (CSVC). XCT scans for engineering purposes were done on the Nikon XTH 320 system at Johnson Space Center using the 225 kV multi-metal reflection source at 215 kV, 179 A, and a 38.49 m voxel size. Individual >4 mm particles separated from the core during processing (then triply sealed in Teflon bags) were also scanned at JSC using the 180 kV source at 90 kV, 33 A, and a 2.98 – 10.65 m voxel size. Whole-core scans were done at the University of Texas High-Resolution X-ray Computed Tomography Facility (UTCT) on the 225 kV reflection source on the North Star Imaging cabinet XCT system. These scans included: (1) a series of 9 overlapping super-resolution scans each covering a ~4 cm length of the tube at 190 kV, 180 µA, and a 12.9 µm voxel size and (2) a lower resolution continuous helical scan of the entire core at 190 kV, 180 µA, and a 51.8 µm voxel size. Progress and Results: Before piercing and extracting the gas from sample 73001, an XCT scan of the bottom portion of the CSVC was used to confirm the location of the Teflon cap on the inner drive tube, to ensure it was not accidentally pierced during gas extraction. Similarly, after piercing, the bottom and top portions of the CSVC were scanned in order to capture engineering knowledge about the results of the piercing process, as well as the metal knife edge vacuum seal (SS into In-Ag alloy). Both scans will provide constraints on future work of this type, particularly for samples collected during the Artemis mission. Another finding from these "engineering" scans was that the device in the drive tube that immobilizes the regolith (the keeper) was not seated in the tube properly. This meant that (1) the drive tube could not be removed from the CSVC for the trip to UTCT, and (2) the procedure for opening and extruding the drive tube had to be modified. Had either of these things not been known prior to opening the CSVC, it could have led to an inability to XCT scan the whole core at high resolution and/or potential disruption of the core stratigraphy during extrusion. At UTCT, the entire length of the core was scanned at high resolution (12.9 microns per voxel). This scan serves multiple purposes: (1) A lower resolution (and uncorrected) version of these scans stitched together was used to help inform the processors of potential pitfalls during extrusion and dissection; and (2) the full resolution corrected data will serve as the permanent in situ record of the stratigraphy of the sample and will enable future researchers to perform a variety of analyses. So far, 92 of the 121 >4 mm particles separated during dissection pass 1 of sample 73001 have been individually scanned. These scans clearly show the lithology of each particle while keeping the particles in pristine condition. Because of the dust adhering to particle exteriors it would otherwise be impossible to determine lithologies in a non-contaminating way. Thus far the types of lithologies seen in sample 73001 (e.g., regolith breccias, impact-melt breccias, agglutinates, and basalts) are similar to those previously identified in sample 73002 [2]. By the time of the meeting, all particles from all 3 dissection passes will have been scanned and statistics on the different lithologies in 73001 compiled. References: [1] Shearer et al. (2020) 51st LPSC, abstract 1181. [2] Zeigler et al. (2020) 51st LPSC, abstract 3023. [3] Kent et al. (2022) This Volume. [4] McDonald et al. (2022) European Lunar Symposium. [5] Gross et al (2022) This volume.

Moon↗
DOE OSTI2022

Lithological controls on soil geochemistry and clay mineralogy across Spodosols in the coastal temperate rainforest of southeast Alaska

The interaction of similar soil forming factors with different parent materials determines soil chemical weathering, influencing soil processes and properties. In the coastal temperate rainforests of southeast Alaska, Spodosols is the dominant soil order in well-drained parent materials regardless of the lithology. Yet, the role of lithology on chemical weathering, base cation depletion, and mineral transformation during pedogenesis remains elusive. Here, we established a lithosequence comprised of soils derived from tonalite, phyllite, slate, and metavolcanic rocks to test the hypothesis that despite the soils in southeast Alaska presenting similar taxonomy and morphology, the influence of lithology in chemical weathering intensity and mineralogy can be detected. We evaluated physicochemical properties, clay mineralogy, Fe-Al oxides, chemical weathering, and elemental mass balance on eleven Spodosols sampled along the lithosequence. We also propose a new weathering index, the Weathering Index for Spodosols (WISP), suitable to evaluate the weathering degree of soils with Al mobility and base-rich parent materials. This index fills a gap in traditional weathering indices that uses Al as an immobile element and/or does not evaluate the leaching of main base cations. We found the pedons across the lithosequence expressed similar physicochemical properties, with predominantly thick profiles, presenting andic properties, relatively thick spodic horizons, and thin E horizons. Podzolization imposed similar mineral transformation trends, mainly dissolution of chlorite, mica alteration to interstratified mica-vermiculite, and formation of smectite in E horizons. Kaolinite was detected in the soils from all lithologies, but only in trace amounts in phyllite soils. Fe oxides depth distribution was similar but with a higher concentration in the slate (44.5 ± 4.2 g/kg), followed by metavolcanic (31.6 ± 4.0 g/kg), phyllite (27.9 ± 3.8 g/kg), and tonalite soils (19.9 ± 5.7 g/kg) and predominantly as organometallic complexes (extracted by Na-pyrophosphate). The stronger weathering of chlorite and mica in the E horizons was reflected in larger losses of Mg and K, while Ca and Na were more depleted in the spodic horizons, suggesting plagioclase weathering. Slate soils were the most depleted in base cations, followed by phyllite, tonalite, and metavolcanic soils. The more depleted status of slate soils was supported by the higher WISP values (WISP = 62), followed by phyllite (WISP = 55), tonalite (WISP = 53), and metavolcanic soils (WISP = 45). Our results demonstrated that lithology controlled elemental depletion intensities, Fe oxide concentrations, and partially the clay fraction mineralogy in addition to podzolization acting as a dominant pedogenic process across all sites. These findings advance our understanding of the role of lithology on soil mineralogy/geochemistry that impacts critical soil functions, such as the soil carbon cycle, elemental fluxes, organo-mineral interactions, and solid-solution reactions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration

In this work, we present findings on the mechanisms of hysteresis in lithium-rich cathode oxides. It is generally reported that the energy inefficiency, observed during electrochemical cycling of Li-rich electrodes, is a direct result of anion redox processes. Similarly, the coupled phenomenon of cation migration has been cited as being a mere consequence of that process with no essential ramification to hysteresis. Such works, however, have only shown correlations and not causation. Specifically, studies that clearly preclude the complete absence of either anion redox or cation migration (down to defect-level concentrations) are not reported yet. Herein, we present first principles calculations and experimental data on a bespoke Li-rich system that is indubitably immune to oxygen activity but yet exhibits significant energy inefficiency. Additionally, the results directly implicate transition metal migration as the fundamental, sole process responsible for hysteresis in this material. This study is of particular importance to the design and development of new Li-rich materials aimed at eliminating the role of oxygen and enhancing the effective cationic redox contribution to the capacity and points out the essential need to develop materials devoid of transition metal migration to interstitial sites in both layered and disordered oxides alike.

25 ENERGY STORAGE↗
NASA NTRS2017

40 Years of Collecting Martian Meteorites

This year marks the 40th anniversary of the first Martian meteorite found in Antarctica by ANSMET, ALH 77005. Since then, an additional 14 Martian meteorites have been found by the ANSMET team making for a total of 15 Martian meteorites in the Antarctic collection at Johnson Space Center. Of the 15 meteorites, some have been paired so the 15 meteorites actually represent a total of approximately 9 separate meteorites. The first Martian meteorite found by ANSMET was ALH 77005 (482.500 g), a lherzolitic shergottite. When collected, this meteorite was split as a part of the joint expedition with the National Institute of Polar Research (NIPR) Japan. Originally classified as an "achondrite-unique", it was re-classified as a Martian lherzolitic shergottites in 1982 [1]. This meteorite has been allocated to ~125 scientists for research and there are 181.964 g remaining at Johnson Space Center (JSC). Two years later, one of the most significant Martian meteorites of the collection at JSC was found at Elephant Moraine, EET 79001 (7942.000 g), a shergottite. This meteorite is the largest in the Martian collection at JSC and was the largest stony meteorite sample collected during the 1979 season. In addition to its size, this meteorite is of particular interest because it contains a linear contact separating two different igneous lithologies, basaltic and olivine-phyric. EET 79001 has glass inclusions that contain chemical compositions that are proportionally identical to the Martian atmosphere, as measured by the Viking spacecraft [2]. This discovery helped scientists to identify where the "SNC" meteorite suite had originated, and that we actually possessed Martian samples. This meteorite has been allocated to ~195 scientists for research and there are 5304.770 g of sample is available. Five years later, ANSMET found ALH 84001 (1930.900 g), the only Martian orthopyroxenite. This meteorite was initially classified as a diogenite but was reclassified as being a Martian meteorite in 1993 [3,4]. ALH 84001 is known as the "Life on Mars" meteorite, sparked debate about whether it contained evidence of Martian life [5] and significantly influenced the field of astrobiol-ogy. This sample has been allocated to 173 scientists for research and has 1426.694 g remaining at JSC. In 1988, another lherzolitic shergottite was found, LEW 88516, (13.203 g). This meteorite wasn't recognized in the field as an achondrite until it was broken during processing 2 years later. LEW 88516 has been allocated to 43 scientists for research and 5.351 g of this meteorite remains at JSC. Six years later a basaltic shergottite was found in the Queen Alexandra Range, QUE 94201 (12.020 g). This meteorite was believed to be of terrestrial origin until maskelynite was seen in a thin section. QUE 94201 has been allocated to 57 scientists for research and there are 3.629 g of this meteorite left at JSC. In 2003, the NASA Mars Exploration Program joined the ANSMET team with the hopes of finding another Martian mete-orite. During this expedition, MIL 03346 (715.200 g) was found. This meteorite is a nakhlite. MIL 03346 has been allocated to 98 scientists for research and there are 579.046 g of this sample remaining at JSC. Six years later, 3 more meteorites that have been paired with MIL 03346 were found, MIL 090030 (452.630 g), 090032 (532.190 g ) and 090136 (170.980 g). MIL 090030 has been allocated to 21 scientists for research and has 434.420 g remaining at JSC, MIL 090032 has been allocated to 21 scientists for re-search and has 508.710 g remaining at JSC and MIL 090136 has been allocated to 14 scientists for research and has 156.790 g remaining at JSC. During the 2004 expedition, 2 identical meteorites where found together on the ice, RBT 04261 (78.763 g) and RBT 04262 (204.600 g). These paired meteorites are olivine-phyric shergottites. RBT 04261 has been allocated to 33 scientists for research and has 32.335 g remaining at JSC. RBT 04262 has been allocated to 46 scientists for research and has 171.886 g remaining. In 2006, another olivine-phyric shergottite was found, LAR 06319 (78.572 g). This meteorite has 61.414 g remaining at JSC and has been allocated to 39 scientists for research. During the 2012 season, 3 more olivine-phyric shergottites were found at Larkman Nunatak, LAR 12011 (701.170 g), LAR 12095 (133.132 g) and LAR 12240 (57.596 g). LAR 12011 is paired with LAR 06319 and LAR 12095 and LAR 12240 are paired with each other. LAR 12011 has been allocated to 43 scientists for research and there are 685.778 g of LAR 12011 remaining at JSC. LAR 12095 has been allocated to 18 scientists for research and has 119.744 g remaining at JSC. LAR 12240 has been allocated to 10 scientists for research and has 52.231 g remaining at JSC. Martian meteorites are the only samples available from Mars because no mission has returned samples from there to date. All Martian meteorites are crustal rocks with most of them being crystallized magmas, so they are an important source for under-standing Martian geological history and volcanism. The ANSMET program has greatly contributed to the scientific community by collecting these meteorites

Funk, R. C.↗
DOE OSTI2023

The iron oxidation state of Ryugu samples

The Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb-type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x-ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross-calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI-type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe 3+ /Fe tot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe 3+ /Fe tot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so-called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon-rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing <35% of Fe 3+ , a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe 3+ /Fe tot > 65%) and mainly contains octahedral ferric iron. In conclusion, this finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid.

58 GEOSCIENCES↗
NASA NTRS2011

Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

Spatiotemporal variability in the carbon isotope composition of sedimentary organic matter (OM) preserves information about the evolution of the biosphere and of the exogenic carbon cycle as a whole. Primary compositions, and imprints of the post-depositional processes that obscure them, exist at the scale of individual sedimentary grains (mm to micron). Secondary ion mass spectrometry (SIMS) (1) enables analysis at these scales and in petrographic context, (2) permits morphological and compositional characterization of the analyte and associated minerals prior to isotopic analysis, and (3) reveals patterns of variability homogenized by bulk techniques. Here we present new methods for in situ organic carbon isotope analysis with sub-permil precision and spatial resolution to 1 micron using SIMS, as well as new data acquired from a suite of Archean rocks. Three analytical protocols were developed for the CAMECA ims1280 at WiscSIMS to analyze domains of varying size and carbon concentration. Average reproducibility (at 2SD) using a 6 micron spot size with two Faraday cup detectors was 0.4 %, and 0.8 % for analyses using 1 micron and 3 micron spot sizes with a Faraday cup (for C-12) and an electron multiplier (for C-13). Eight coals, two ambers, a shungite, and a graphite were evaluated for micron-scale isotopic heterogeneity, and LCNN anthracite (delta C-13 = -23.56 +/- 0.1 %, 2SD) was chosen as the working standard. Correlation between instrumental bias and H/C was observed and calibrated for each analytical session using organic materials with H/C between 0.1 and 1.5 (atomic), allowing a correction based upon a C-13H/C-13 measurement included in every analysis. Matrix effects of variable C/SiO2 were evaluated by measuring mm to sub-micron graphite domains in quartzite from Bogala mine, Sri Lanka. Apparent instrumental bias and C-12 count rate are correlated in this case, but this may be related to a crystal orientation effect in graphite. Analyses of amorphous Archean OM suggest that instrumental bias is consistent for 12C count rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, approximately 2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, approximately 2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, approximately 2.6 Ga), and SV1 (n=1; Tumbiana Fm, approximately 2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, delta C-13 varies between -53.1 and -28.3 % and offsets between in situ and bulk compositions range from -8.3 to 18.8%. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for gradients of oxidation with depth in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of previously reported Archean OM will be discussed.

Williford, Kenneth H.↗
NASA NTRS1999

Diagnostic Clast-Texture Criteria for Recognition of Impact Deposits

It is difficult to find definitive evidence for impact in the geological record because there are many endogenous geological processes that can produce diamictites similar to those generated by impact ejecta. The classic impact criteria of shock fabrics in certain minerals, and iridium layers, for example, may be either difficult to find, or long-since erased from the impact site (shock fabrics also anneal with time). It is important to be able to recognize impact-generated materials in order to understand earth's crustal development and biological evolution. In future exploration of Mars and other solar-system bodies, recognition of impact materials will be important for elucidating planetary evolution, planetary volatile inventories, and exobiological issues. The cobble depicted is typical of many that have been found in diamictite deposits in Belize generated by the Chicxulub K-T impact event. The pebbles are roughly-hewn in general shape with smoothed corners and edges. Surfaces are almost uniformly frosted (on both protuberances and hollows), but some asperities are glazed. Optical microscopy and thin-section petrographic microscopy reveal the frosting to be only a few microns thick, with a well-defined granular structure; grains are the same size as those composing the bulk of the limestone, but their clearer appearance may represent annealing. One or two adjacent pebble faces are often decorated with striated gouges and closely-spaced hemispherical depressions representing indentation hollows produced by well-rounded impacting clasts of up to 0.5 cm in diameter. Some of the impactors are still embedded in the cobble surface. Non-destructive x-ray diffraction techniques showed the impactors to be of the same mineralogy as the target cobble. We believe this unusual glazing and frosting to be related to the impact event, but this must be reconciled with its survival for over 60 my. since it is composed of one of the most alterable substances, CaCO3. We focus, however, on the non-fractured rounded pebbles that appear to have impacted the larger cobble as a swarm of clasts, probably encountered during ballistic flight. It cannot be defined whether the cobble swept through the pebble cloud, or the pebbles rained upon a slowermoving cobble. Two interesting questions arise: (1) Where did large numbers of such well rounded pebbles come from in the ejecta curtain?, and (2) How did they embed themselves in a nominally brittle rock without suffering damage? Are the well-rounded pebbles crystalline (devitrified) melt spherules? Further investigations are in progress. If the cobble was cold and brittle, impact of well-rounded pebbles would have produced Hertzian fracture patterns (a) in the virtually elastically isotropic cobble target. For penetration depths of about 0.5 of the impactor diameter, the pebbles would require a relative impact velocity sufficient to cause pebble fragmentation and crushing, and the development of a complex Hertzian-Boussinesq fracture field (b) involving deep fracturing and lateral surface spalling (impact velocities > 50 m/s). The existing relationship could only evolve by the impact of cold, hard pebbles into a soft, plastic cobble surface (c). For limestone to have been plastic, it must have been at elevated temperature, but to prevent calcification of the material, the ambient pressure must also have been elevated. This would be possible either in the impact's gas plume, or within the confines of a thin aerodynamically-produced shock bow generated by supersonic ballistic motion of the cobble. In the latter case, it is implied that the cobble swept through the pebbles rather than vice-versa. Although there are high T-P conditions associated with volcanism, such textures have not been reported on volcaniclastic materials, nor from other high T-P environments; e.g., metamorphic (as far as the authors are aware). We propose that this very easily recognizable embedding and indentation surface texture can be used as a diagnostic criterion for the recognition of impact ejecta. The term "peening texture" is suggested, because it is absolutely analogous to the plastic-deformation induced, metal-surface textures generated by ball-bearing bombardment used in engineering metallurgy to work-harden metal surfaces. Additional information is contained in the original (Figures).

Marshall, J. R.↗