Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “leaching”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Short Range-Ordered Minerals: Insight into Aqueous Alteration Processes on Mars

Short range-ordered (SRO) aluminosilicates (e.g., allophane) and nanophase ferric oxides (npOx) are common SRO minerals derived during aqueous alteration of basaltic materials. NpOx refers to poorly crystalline or amorphous alteration products that can be any combination of superparamagnetic hematite and/or goethite, akaganeite, schwertmannite, ferrihydrite, iddingsite, and nanometer-sized ferric oxide particles that pigment palagonitic tephra. Nearly 30 years ago, SRO phases were suggested as alteration phases on Mars based on similar spectral properties for altered basaltic tephra on the slopes of Mauna Kea in Hawaii and Martian bright regions measured by Earth-based telescopes. Detailed characterization of altered basaltic tephra on Mauna Kea have identified a variety of alteration phases including allophane, npOx, hisingerite, jarosite, alunite, hematite, goethite, ferrihydrite, halloysite, kaolinite, smectite, and zeolites. The presence of npOx and other Fe-bearing minerals (jarosite, hematite, goethite) was confirmed by the M ssbauer Spectrometer onboard the Mars Exploration Rovers. Although the presence of allophane has not been definitely identified on Mars robotic missions, chemical analysis by the Spirit and Opportunity rovers and thermal infrared spectral orbital measurements suggest the presence of allophane or allophane-like phases on Mars. SRO phases form under a variety of environmental conditions on Earth ranging from cold and arid to warm and humid, including hydrothermal conditions. The formation of SRO aluminosilicates such as allophane (and crystalline halloysite) from basaltic material is controlled by several key factors including activity of water, extent of leaching, Si activity in solution, and available Al. Generally, a low leaching index (e.g., wet-dry cycles) and slightly acidic to alkaline conditions are necessary. NpOx generally form under aqueous oxidative weathering conditions, although thermal oxidative alteration may occasional be involved. The style of aqueous alteration (hydrolytic vs. acid sulfate) impacts which phases will form (e.g., oxides, oxysulfates, and oxyhydroxides). Knowledge on the formation processes of SRO phases in basaltic materials on Earth has allowed significant enhancement in our understanding of the aqueous processes at work on Mars. The 2011 Mars Science Laboratory (MSL) will provide an instrument suite that should improve our understanding of the mineralogical and chemical compositions of SRO phases. CheMin is an X-ray diffraction instrument that may provide broad X-ray diffraction peaks for SRO phases; e.g., broad peaks around 0.33 and 0.23 nm for allophane. Sample Analysis at Mars (SAM) heats samples and detects evolved gases of volatile-bearing phases including SRO phases (i.e., carbonates, sulfates, hydrated minerals). The Alpha Particle X-ray Spectrometer (APXS) and ChemCam element analyzers will provide chemical characterization of samples. The identification of SRO phases in surface materials on MSL will be challenging due to their nanocrystalline properties; their detection and identification will require utilizing the MSL instrument suite in concert. Ultimately, sample return missions will be required to definitively identify and fully characterize SRO minerals with state-of-the-art laboratory instrumentation back on Earth.

Ming, Douglas W.↗
NASA NTRS2012

Widespread Weathered Glass on the Surface of Mars

Low albedo sediments cover >10(exp 7) sq km in the northern lowlands of Mars, but the composition and origin of these widespread deposits have remained ambiguous despite many previous investigations. Here we use near-infrared spectra acquired by the Mars Express OMEGA (Observatoire pour la Mineralogie, l'Eau, les Glaces, et l'Activite') imaging spectrometer to show that these sediments exhibit spectral characteristics that are consistent with both high abundances of iron-bearing glass and silica-enriched leached rinds on glass. This interpretation is supported by observations of low-albedo soil grains with possible rinds at the Phoenix Mars Lander landing site in the northern lowlands. By comparison with the extensive glass-rich dune fields and sand sheets of Iceland, we propose an explosive volcanic origin for these glass-rich sediments. We also propose that the glassy remnant rinds on the sediments are the result of post-depositional alteration, as these rinds are commonly formed in arid terrestrial volcanic environments during water-limited, moderately acidic leaching. These weathered, glass-rich deposits in the northern lowlands are also colocated with the strongest concentrations of a major global compositional surface type previously identified in mid-infrared spectra, suggesting that they may be representative of global processes. Our results provide potential confirmation of models suggesting that explosive volcanism has been widespread on Mars, and also raise the possibilities that glass-rich volcaniclastics are a major source of eolian sand on Mars and that widespread surficial aqueous alteration has occurred under Amazonian climatic conditions.

Horgan, Briony↗
NASA NTRS2016

Acid Sulfate Alteration on Mars

A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Acid sulfate alteration has been identified at all three landing sites visited by NASA rover missions (Spirit, Opportunity, and Curiosity). Spirit landed in Gusev crater in 2004 and discovered Fe-sulfates and materials that have been extensively leached by acid sulfate solutions. Opportunity landing on the plains of Meridiani Planum also in 2004 where the rover encountered large abundances of jarosite and hematite in sedimentary rocks. Curiosity landed in Gale crater in 2012 and has characterized fluvial, deltaic, and lacustrine sediments. Jarosite and hematite were discovered in some of the lacustrine sediments. The high elemental abundance of sulfur in surface materials is obvious evidence that sulfate has played a major role in aqueous processes at all landing sites on Mars. The sulfate-rich outcrop at Meridiani Planum has an SO3 content of up to 25 wt.%. The interiors of rocks and outcrops on the Columbia Hills within Gusev crater have up to 8 wt.% SO3. Soils at both sites generally have between 5 to 14 wt.% SO3, and several soils in Gusev crater contain around 30 wt.% SO3. After normalization of major element compositions to a SO3-free basis, the bulk compositions of these materials are basaltic, with a few exceptions in Gusev crater and in lacustrine mudstones in Gale crater. These observations suggest that materials encountered by the rovers were derived from basaltic precursors by acid sulfate alteration under nearly isochemical conditions (i.e., minimal leaching). There are several cases, however, where acid sulfate alteration minerals (jarosite and hematite) formed in open hydrologic systems, e.g., in Gale crater lacustrine mudstones. Several hypotheses have been suggested for the aqueous formation of sulfate-bearing phases under acidic conditions on the surface of Mars including (1) sulfuric acid weathering of basaltic materials; (2) oxidative weathering of ultramafic igneous rocks containing sulfides; (3) acid fog weathering of basaltic materials, and (4) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity as iron was oxidized on exposure to O2 or photo-oxidized by ultraviolet radiation at the martian surface. Next, we briefly describe evidence for these hypothesis.

Ming, D. W.↗
NASA NTRS2016

Localized and Areally Extensive Alterations in Marathon Valley, Endeavour Crater Rim, Mars

Mars Exploration Rover Opportunity is exploring the rim of 22 km diameter, Noachian-aged Endeavour crater. Marathon Valley cuts through the central region of the western rim providing a window into the local lower rim stratigraphic record. Spectra from the Compact Reconnaissance Imaging Spectrometer for Mars show evidence for the occurrence of Fe-Mg smectite in this valley, indicating areally extensive and distinct lithologic units and/or styles of aqueous alteration. The Alpha Particle X-ray Spectrometer has determined the compositions of 59 outcrop targets on untreated, brushed and abraded surfaces. Rocks in the Marathon Valley region are soft breccias composed of mm- to cm-sized darker clasts set in a lighter-toned, finegrained matrix. They are basaltic in non-volatile-element composition and compositionally similar to breccias investigated elsewhere on the rim. Alteration styles recorded in the rocks include: (1) Enrichments in Si, Al, Ti and Cr in more reddish-colored rock, consistent with leaching of more soluble cations and/or precipitation of Si +/- Al, Ti, Cr from fluids. Coprecipitation of Ge-rich phases with Si occurred in the western area only; high water:rock is indicated. Pancam multispectral observations indicate higher nanophase ferric oxide contents, but the rocks have lower Fe contents. The highly localized nature of the red zones indicate they cannot be the source of the widespread smectite signature observed from orbit. (2) Outcrops separated by approximately 65 m show common compositional changes between brushed and abraded (approximately 1 mm deep) targets: increases in S and Mg; decreases in Al, Cl and Ca. These changes are likely due to relatively recent, surface-related alteration of valley rocks and formation of surface coatings under low water:rock. (3) One target, from the center of a region of strong CRISM smectite signature, shows modest differences in composition (higher Si, K; lower Mn) compared to most Marathon Valley rocks, while another target approximately 40 cm away on the same outcrop does not; a change towards smectite bulk compositions is not observed. The smectite signature likely resulted from alteration under low water:rock such that primary minerals were partially altered to phyllosilicates, but wholesale leaching of cations by fluids did not occur.

Mittlefehldt, David W.↗
NASA NTRS2016

Is Tridymite at Gale Crater Evidence for Silicic Volcanism on Mars?

The X-ray diffraction (XRD) instrument (CheMin) onboard the MSL rover Curiosity detected 17 wt% of the SiO2 polymorph tridymite (relative to bulk sample) for the Buckskin drill sample (73 wt% SiO2) obtained from sedimentary rock in the Murray formation at Gale Crater, Mars. Other detected crystalline materials are plagioclase, sanidine, cristobalite, cation-deficient magnetite, and anhydrite. XRD amorphous material constitutes approx. 60 wt% of bulk sample, and the position of its broad diffraction peak near approx. 26 deg. 2-theta is consistent with opal-A. Tridymite is a lowpressure, high-temperature mineral (approx. 870 to 1670 deg. C) whose XRD-identified occurrence on the Earth is usually associated with silicic (e.g., rhyolitic) volcanism. High SiO2 deposits have been detected at Gale crater by remote sensing from martian orbit and interpreted as opal-A on the basis H2O and Si-OH spectral features. Proposed opal-A formation pathways include precipitation of silica from lake waters and high-SiO2 residues of acid-sulfate leaching. Tridymite is nominally anhydrous and would not exhibit these spectral features. We have chemically and spectrally analyzed rhyolitic samples from New Mexico and Iwodake volcano (Japan). The glassy (by XRD) NM samples have H2O spectral features similar to opal-A. The Iwodake sample, which has been subjected to high-temperature acid sulfate leaching, also has H2O spectral features similar to opal-A. The Iwodake sample has approx. 98 wt% SiO2 and 1% wt% TiO2 (by XRF), tridymite (>80 wt.% of crystalline material without detectable quartz by XRD), and H2O and Si-OH spectral features. These results open the working hypothesis that the opal-A-like high-SiO2 deposits at Gale crater detected from martian orbit are products of alteration associated with silicic volcanism. The presence or absence of tridymite will depend on lava crystallization temperatures (NM) and post crystallization alteration temperatures (Iwodake).

Morris, Richard V.↗
NASA NTRS2017

Lead in Martian Meteorites-- Observations and Inconsistencies: I. Chassigny

The history of Pb isotope analyses of the martian meteorites (SNC) and their interpretations is laden with difficulties. Two different analytical groups have interpreted their ancient (≥ 4 Ga) shergottite Pb ages as primary [1-5]. A Nakhla age of approximately 4.3 Ga has been interpreted to be primary as well [2]. This is in stark contrast to the young (≤ 1.4 Ga) crystallization ages defined by the Rb-Sr, Sm-Nd, Lu-Hf, and KAr systems [6]. Possibly, a better interpretation for the ancient Pb ages is that they reflect the formation times of the various SNC source regions [7]. A difficulty in dealing with Pb is that terrestrial contamination is ubiquitous, unlike the other chronometer systems noted above. This issue is complicated by the fact that radioactive decay causes localized mineral damage. So washing and leaching to remove Pb contamination tends to remove in situ radiogenic Pb. This issue is further compounded because U and Th are often concentrated in phosphates and other minor phases, so the leaching process tends to remove these, especially phosphates. Another difficulty is that it is not clear whether the observed Pb isotopic variation in leachates, residues, and ion-microprobe analyses is due to terrestrial or to indigenous martian Pb contamination [e.g., 8]. A third difficulty is that the shergottites on the one hand, and the nakhlites and chassignites on the other, appear to have come from separate source regions with different chemical compositions [e.g., 7]. Thus, it is expected that their Pb isotopic characteristics would be different. And even if all these meteorite types came from the same source region, their igneous ages differ considerably. The nakhlites and chassignites are ~1.4 Ga and the shergottites are ≤ 600 Ma [e.g., 6]. This age difference alone should assure that the two distinct SNC groups have differing Pb isotopic signatures.

Jones, J. H.↗
NASA NTRS2017

Impact-Facilitated Hydrothermal Alteration in the Rim of Endeavour Crater, Mars

Endeavour crater, a Noachian-aged, 22 km diameter impact structure on Meridiani Planum, Mars, has been investigated by the Mars Exploration Rover Opportunuity for over 2000 sols (Mars days). The rocks of the western rim region (oldest to youngest) are: (i) the pre-impact Matijevic fm.; (ii) rim-forming Shoemaker fm. polymict impact breccias; (iii) Grasberg fm., fine-grained sediments draping the lower slopes; and (iv) Burns fm., sulfate-rich sandstones that onlap the Grasberg fm. The rim is segmented and transected by radial fracture zones. Evidence for fluid-mediated alteration includes m-scale detections of phyllosilicates from orbit, and cm-scale variations in rock/soil composition/mineralogy documented by the Opportunity instrument suite. The m-scale phyllosilicate detections include Fe(3+)-Mg and aluminous smectites that occur in patches in the Matijevic and Shoemaker fms. Rock compositions do not reveal substantial differences for smectite-bearing compared to smectite-free rocks. Interpretation: large-scale hydrothermal alteration powered by impact-deposited heat acting on limited water supplies engendered mineralogic transfomations under low water/rock, near-isochemical conditions. The cm-scale alterations, localized in fracture zones, occurred at higher water/rock as evidenced by enhanced Si and Al contents through leaching of more soluble elements, and deposition of Mg, Ni and Mn sulphates and halogen salts in soils. Visible/near infrared reflectance of narrow curvilinear red zones indicate higher nanophase ferric oxide contents and possibly hydration compared to surrounding outcrops. Broad fracture zones on the rim have reflectance features consistent with development of ferric oxide minerals. Interpretation: water fluxing through the fractures in a hydrothermal system resulting from the impact engendered alteration and leaching under high water/rock conditions. Late, localized alteration is documented by Ca-sulfate-rich veins that are not confined to fracture zones; some cross-cut the Grasberg fm. Interpretation: late fluid mobilization of soluble elements, likely in a later alteration event.

Mittlefehldt, D. W.↗
NASA NTRS2017

Investigating Weathering of Basaltic Materials in Gale Crater, Mars: A Combined Laboratory, Modeling and Terrestrial Field Approach

Recent observations from Gale Crater, Mars document past aqueous alteration both in the formation of the Stimson sandstone unit, as well as in the formation of altered fractures within that unit. Geochemical and mineralogical data from Curiosity also suggest Fe-rich amorphous weathering products are present in most samples measured to date. Here we interpret conditions of possible past weathering in Gale Crater using a combination of field, laboratory, and modeling work. In order to better understand secondary Fe-rich phases on Mars, we are examining formation of weathering products in high Fe and Mg and low Al serpentine soils in the Klamath Mountains, CA. We have isolated potential weathering products from these soils, and are analyzing them using synchrotron μXRF and μXRD as well as FullPat for a direct comparison to analyses from Gale Crater. In order to interpret the implications of the persistence of potential secondary Fe-containing phases on Mars, we are also measuring the dissolution rates of the secondary weathering products allophane, Fe-rich allophane, and hisingerite. Ongoing dissolution experiments of these materials suggest that they dissolve significantly more rapidly than more crystalline secondary minerals with similar chemical compositions. Finally, to quantify the specific conditions of past aqueous alteration in Gale Crater we are performing reactive transport modeling of a range of possible past environmental conditions. Specifically, we are testing the conditions under which a Stimson unit-like material forms from a parent material similar to Rocknest or Bagnold eolian deposits, and the conditions under which observed altered fracture zones form from a Stimson unit-like parent material. Our modeling results indicate that the formation of the Stimson unit is consistent with leaching of an eolian deposit with a solution of pH = 6-8, and that formation of the altered fracture zones is consistent with leaching with a very acidic (pH = 2-3) high sulfate solution containing Ca. These results suggest circumneutral pH conditions during authigenesis or early diagenesis in the Stimson formation sediments followed by diagenetic alteration by very acidic solutions along fracture zones.

Hausrath, Elisabeth↗
NASA NTRS2020

Modelling climate change impacts on maize yields under low nitrogen input conditions in sub‐Saharan Africa

Smallholder farmers in sub‐Saharan Africa (SSA) currently grow rainfed maize with limited inputs including fertilizer. Climate change may exacerbate current production constraints. Crop models can help quantify the potential impact of climate change on maize yields, but a comprehensive multimodel assessment of simulation accuracy and uncertainty in these low‐input systems is currently lacking. We evaluated the impact of varying [CO2], temperature and rainfall conditions on maize yield, for different nitrogen (N) inputs (0, 80, 160 kg N/ha) for five environments in SSA, including cool subhumid Ethiopia, cool semi‐arid Rwanda, hot subhumid Ghana and hot semi‐arid Mali and Benin using an ensemble of 25 maize models. Models were calibrated with measured grain yield, plant biomass, plant N, leaf area index, harvest index and in‐season soil water content from 2‐year experiments in each country to assess their ability to simulate observed yield. Simulated responses to climate change factors were explored and compared between models. Calibrated models reproduced measured grain yield variations well with average relative root mean square error of 26%, although uncertainty in model prediction was substantial (CV = 28%). Model ensembles gave greater accuracy than any model taken at random. Nitrogen fertilization controlled the response to variations in [CO2], temperature and rainfall. Without N fertilizer input, maize (i) benefited less from an increase in atmospheric [CO2], (ii) was less affected by higher temperature or decreasing rainfall and (iii) was more affected by increased rainfall because N leaching was more critical. The model inter-comparison revealed that simulation of daily soil N supply and N leaching plays a crucial role in simulating climate change impacts for low-input systems. Climate change and N input interactions have strong implications for the design of robust adaptation practices across SSA, because the impact of climate change will be modified if farmers intensify maize production with more mineral fertilizer.

Crop simulation model↗
NASA NTRSDate not supplied

Olivine Dissolution and Formation of Secondary phases in Ultramafic Soils

Introduction: Olivine has been proposed as an indicator for the duration of water-rock interaction within Martian rocks and sediments [1-3]. The use of olivine as a mineralogical indicator for past aqueous alteration on Mars requires interpretation of a complex combination of factors including pH, temperature, and composition [5,6]. Here, we examine the persistence of natural olivine within terrestrial ultramafic soils (Fe/Mg-rich, Al-poor) developing under different climatic conditions and the incipient dissolution of emplaced forsterite (Fo) and fayalite (Fa) surfaces to investigate environmental effects on incipient olivine dissolution, olivine persistence in soils, and formation of secondary phases. Methods: Field Sites. We examined olivine weathering and secondary material formation in ultramafic soils at 6 sites in the Klamath Mountains (KM) of northern California with a mean annual temperature of ~12.8℃ and precipitation of ~55.7-95.4 cm/year [7], and soil pH of ~6.5-7.3; 4 sites in the Tablelands (TB) of Newfoundland, Canada with a mean annual temperature of <3.9℃ and precipitation of ~120.0 cm/year [8], and soil pH of ~7.7; and at 3 sites at Pickhandle Gulch (PG), Nevada with a mean annual temperature of ~14.4℃ and precipitation of ~14.1 cm/year [7], and soil pH of ~8.5. Sampling sites span an age range of ~12.1-50+ kya in the Klamath Mountains [9,10] and ~13-30 kya in the Tablelands [11]. Pickhandle Gulch sites are undated. Parent Material and Soil Analyses. Polished thin sections of bulk soil prepared by Wagner Petrographic, Inc were carbon-coated and analyzed on a JEOL 2100 SEM in back-scattered electron mode in the EMIL lab at UNLV and at the 13-ID-E synchrotron beamline at Argonne National Laboratory using µXRF, µXRD, and XAS. Soil and parent material samples were powdered in a Fritsch pulverisette and analyzed by XRD and soil by VNIR. Soil preparation is further described in [12]. Disk Preparation, Burial, and Collection. Fo disks were cut from a column prepared via hot-pressing and Fa disks by sintering synthetic fayalite powder, see [13] for detail. Disks were polished to a 0.25-micron level with diamond grit. Disks were buried in 3 KM soils, 4 TB soils, and 3 PG soils, collected after exactly 365 days, and washed gently with 100% reagent grade ethanol to remove potential adhered soil material. Weathered disks and soil samples were stored in a -20℃ freezer until analysis. Unaltered control disks prepared identically to the buried disks were stored at -20℃ for the duration of the experiment. Disk Analyses. One Fo and Fa disk from each climate zone was analyzed on a variable pressure Zeiss Supra 40VP SEM at Northern Arizona University. A separate Fo and Fa disk from each climate zone was analyzed by XPS using a Physical Electronics VersaProbe II at the Penn State Univ. Materials Characterization Lab after a Na-dodecyl sulfate wash and ozonation to remove carbon contamination as in [14]. VNIR measurements were conducted at Johnson Space Center using an ASD FieldSpec3 under ambient lab conditions on a separate Fo and Fa disk from each climate zone. One separate Fo and Fa control sample was analyzed for each technique for comparison with weathered samples. XPS uncertainty was determined from 5 repeat measurements on controls. Results: Bedrock and Soil Results Olivine is present in the parent material in the KM and TB. Olivine is found in ~12.1 ka KM soils but is absent from all older soils, while persisting into the oldest (>20 ka) TB soil (Figure 1). In both locations, olivine is found as cores surrounded by a serpentine rind (Figure 2). VNIR spectra from the analyzed soils possess strong OH-associated spectral features at ~2.33 µm indicating the presence of Mg-rich phyllosilicates as well as ferric-oxide features at ~0.92 µm in the KM (Figure 3). Primary crystalline silicate grains mostly incorporate Fe2+, while poorly crystalline weathering rinds are best fit by ferric oxide XAS standards (Figure 4). µXRF also shows that Fe and Ni concentrate in weathering rinds and Cr remains within interior silicate grains (Figure 4). Buried Sample Results All Fo surfaces exhibited formation of dissolution features including shallow pitting not observed on controls. Dissolution features were most visually widespread on the KM disk (Figure 5). Leaching of Mg from KM and TB Fo disks was evident from <1.6 Mg/Si ratios measured by XPS (Figure 6). Fe-rich precipitates in SEM (Figure 5) and Fe presence in XPS scans (Figure 6) indicate Fe deposition onto KM and TB Fo disk surfaces. The appearance of a spectral feature at 0.55 µm in the VNIR spectra from the TB Fo suggests this Fe is ferric (Figure 7). The PG Fo appears least altered, with minimal formation of dissolution features in SEM (Figure 5), a Mg/Si ratio inconsistent with leaching (~2) (Figure 6), and VNIR spectra almost identical to the control sample. Analysis of Fa surfaces is ongoing. The higher temperatures and more acidic pH in the KM soils likely drive the faster dissolution of the Fo disks described above. While the TB soils experience greater precipitation than in the KM, the cooler temperatures and more basic soil pH facilitate observable but more limited alteration. The dry climate and basic soil pH at PG lead to minimal dissolution of the PG disk surfaces.

A D Feldman↗
NASA NTRSDate not supplied

Formation of Fe(III) (hydr)oxides from Fe(II) sulfides: Implications for akaganeite detection on Mars

Akaganeite (β-FeO(OH,Cl)) is a Fe(III) (hydr)oxide with a tunnel structure typically occupied by chloride. This mineral was first proposed to be present in Meridiani Planum and Gusev crater on Mars and akaganeite was subsequently detected by X-ray diffraction in Yellowknife Bay and Vera Rubin Ridge locations in Gale crater. Akaganeite in Gale crater has been proposed to form from Fe(II) sulfides but formation conditions remain unconstrained. We investigated akageneite formation by oxidative alteration of natural Fe(II) sulfide pyrrhotite exposed to HCl and oxidation-hydrolysis of Fe(II) HCl-leached from pyrrhotite at initial pH0 1.5, 2, 3, and 4. X-ray diffraction and Mössbauer analyses revealed formation of poorly-crystallized akageneite in oxidative alteration experiments. Air-exposure of the HCl-reacted dry pyrrhotite led to an increase in akageneite formation and precipitation of Fe(II) hydrated sulfates, goethite, and hydronium jarosite. Iron(II) oxidation-hydrolysis was sensitive to Si dissolved from phyllosilicates in one pyrrhotite sample. Akaganeite and goethite formed at pH0 1.5 and 2 with akageneite more abundant at dissolved Si/Fe ratio of 0.08 and goethite more abundant at Si/Fe of 0.01. Akaganeite formed together with hematite, ferrihydrite, and goethite at pH0 3, and formation was suppressed at pH0 4. Well-crystallized akageneite precipitated at pH0 1.5 while akaganeite of poorer crystallinity formed at pH0 2 and 3. Akageneite in Gale crater could form from sulfides by both mechanisms: oxidative alteration of sulfide minerals and oxidation-hydrolysis of leached Fe(II). The processes likely occurred during late diagenetic events triggered by interactions of acidic Cl-bearing groundwater with Fe(II) sulfides. Akaganeite in Yellowknife Bay, Gale crater could have formed by Fe(II) oxidation-hydrolysis either as a sole Fe(III) (hydr)oxide at pH<2 or along with ferrihydrite and hematite at 2<pH<4 in Si-enriched conditions. Akaganeite formation at Vera Rubin Ridge, Gale crater could have occurred through oxidative alteration of sulfides in Cl-bearing pH 1.2-1.5 solutions. The presence of well-crystalline akageneite in Vera Rubin Ridge indicates that Fe(II) oxidation-hydrolysis contributed to akageneite formation.

Mars gale crater akaganeite↗
NASA NTRSDate not supplied

3D Printed Materials Characterization for Rapid Prototyping and Plant Growth

Space Biology experimentation but their effects during plant growth and sanitation have not been documented. With further testing we can determine how certain 3D printed materials affect our plants. The way we tested germination included laying two pieces of germination paper down with the printed petri dish insert of the various material and 14 seeds of Outrageous lettuce to fit in the holes of the insert. We kept an even moisture in all parts by wrapping the petri dishes in two layers of parafilm tape. This project tests over 15 different materials to document performance during plant growth scenarios. This research will not only help space biology but also citizens who use these materials to understand the potential of leaching and ill effects. 3D printing is a recent generally accessed technology with new materials coming out every day. It is important to understand how materials could impact the way the plants grow, and the safety of the food grown. As we continue testing these materials, we will also test engineering properties like tension and elasticity. We have a microbiology team working on this project as well to test biofilm formation. From the germination tests we have completed we have seen little impact on germination rate of these seeds. However, some parts absorb moisture. An ideal material is one that doesn’t leach chemicals or microplastics, can withstand high tension and compression, and doesn’t promote microbial growth. This work is funded by NASA. M. Gandhi was funded by MAIANSE.

Mily Gandhi↗
DOE OSTI2026

Reconstruction and Dissolution of Copper Catalysts during Electrocatalytic Nitrate Reduction

Copper-based electrocatalysts are widely explored for electrochemical nitrate remediation, yet their stability under operating conditions remains poorly understood. While nanoscale and subnanoscale Cu motifs are known to restructure during the nitrate reduction reaction (NO 3 RR), how these transformations translate into irreversible material loss remains unclear. Here, we quantify Cu dissolution during NO 3 RR as a function of catalyst architecture and electrolyte chemistry using two model systems: single-atom Cu (Cu 1 ) and Cu nanoparticles (Cu NP ). Time-resolved leaching measurements, integrated with in situ X-ray absorption spectroscopy (XAS), reveal measurable Cu loss for both catalysts during NO 3 RR. Dissolution is concentrated at the initiation of electrolysis, coinciding with rapid restructuring, and depends strongly on morphology, with Cu NP consistently exhibiting greater Cu loss than Cu 1 . In situ XAS reveals that Cu 1 forms transient metallic clusters under reduction that largely redisperse upon returning to open-circuit voltage, whereas Cu NP undergoes reduction of an oxidized surface layer accompanied by sustained Cu loss during electrolysis. Notably, the presence of nitrate significantly intensifies restructuring and Cu loss, highlighting the critical role of electrolyte composition. Furthermore, these findings establish a direct link between electrochemical restructuring and Cu dissolution, unveiling electrolyte-dependent interactions as key determinants of catalyst durability in electrochemical nitrate conversion.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Constraints and Drivers of Dissolved Fluxes of Pyrogenic Carbon in Soil and Freshwater Systems: A Global Review and Meta‐Analysis

Abstract Pyrogenic carbon (PyC) is a significant component of the global soil carbon pool due to its longer environmental persistence than other soil organic matter components. Despite PyC's persistence in soil, recent work has indicated that it is susceptible to loss processes such as mineralization and leaching, with the significance and magnitude of these largely unknown at the hillslope and watershed scales. We present a review of the work concerning dissolved PyC transport in soil and freshwater. Our analysis found that the primary environmental controls on dissolved PyC (dPyC) transport are the formation conditions and quality of the PyC itself, with longer and higher temperature charring conditions leading to less transport of dPyC. While correlations between dPyC and dissolved organic carbon in rivers and other pools are frequently reported, the slope of these correlations was pool‐dependent (i.e., soil‐water, precipitation, lakes, streams, rivers), suggesting site‐specific environmental controls. However, the lack of consistency in analytical techniques and sample preparation remains a major challenge to quantifying environmental controls on dPyC fluxes. We propose that future research should focus on the following: (a) consistency in methodological approaches, (b) more quantitative measures of dPyC in pools and fluxes from soils to streams, (c) turnover times of dPyC in soils and aquatic systems, and (d) improved understanding of how mechanisms controlling the fate of dPyC in dynamic post‐fire landscapes interact. With more refined quantitative information about the controls on dPyC transport at the hillslope and landscape scale, we can increase the accuracy and utility of global carbon models.

58 GEOSCIENCES↗
DOE OSTI2024

Recycling of Lithium-Ion Batteries via Electrochemical Recovery: A Mini-Review

With the rising demand for lithium-ion batteries (LIBs), it is crucial to develop recycling methods that minimize environmental impacts and ensure resource sustainability. The focus of this short review is on the electrochemical techniques used in LIB recycling, particularly electrochemical leaching and electrodeposition. Our summary covers the latest research, highlighting the principles, progress, and challenges tied to these methods. By examining the current state of electrochemical recovery, this review intends to provide guidance for future advancements and enhance LIB recycling efficiency.

25 ENERGY STORAGE↗
NASA NTRS1978

Novel duplex vapor electrochemical method for silicon solar cells

Progress in the development of low-cost solar arrays is reported. Topics covered include: (1) development of a simplified feed system for the Na used in the Na-SiF4 reactor; (2) production of high purity silicon through the reduction of sodium fluosilicate with sodium metal; (3) the leaching process for recovering silicon from the reaction products of the SiF4-Na reaction; and (4) silicon separation by the melting of the reaction product.

Kapur, V.↗
NASA NTRS2022

Evapotranspiration Based Irrigation Trials Examine Water Requirement, Nitrogen Use, and Yield of Romaine Lettuce in the Salinas Valley

Cool season vegetables require adequate soil moisture to assure that maximum yield and quality are achieved. On California’s central coast, where the majority of cool season vegetables are produced in the US, long-term overpumping of irrigation water has reduced groundwater levels and led to environmental degradation. Two evapotranspiration (ET) based irrigation field trials were performed near Salinas CA (USA) to determine if ET-based irrigation scheduling could conserve water while producing romaine lettuce (cv. Sun Valley) of commercially viable yield. Sprinklers were used for seed germination and crop establishment. Four drip irrigation treatments were then imposed using a randomized complete block design with six replications. The CropManage decision support model was used to estimate the full (100%) crop water requirement based mainly on ET replacement. Other treatments included 50% 75% and 150% of the full water requirement. The 100% treatment received 185 mm of water in 2015 and 247 mm in 2016, both of which were well below prior guidance and grower reports. Yields from the 100% and 150% treatments were not significantly different and were similar to industry average, while yields were significantly lower for the 50% and 75% treatments. The 100% treatment had the highest water use efficiency, and the 100% and 150% treatments together had the highest nitrogen recovery efficiency. Irrigation of romaine near the 100% ET replacement level can potentially reduce environmental impacts associated with nitrate leaching and surface runoff.

CropManage decision support system↗
DOE OSTI2024

Formation and Detriments of Residual Alkaline Compounds on High-Nickel Layered Oxide Cathodes

High-nickel layered oxides LiNi x M 1-x O 2 (x ≥ 0.9) have emerged as promising cathode materials for automotive batteries due to their high energy density and lower cost. However, the formation and accumulation of surface alkaline compounds during storage hinder their mass production and commercialization. Here, in this study, a validated chemical method is employed to deconvolute and quantify the evolution of each residual lithium compound in four representative cathodes during ambient-air storage, viz., LiNiO 2 (LNO), LiNi 0.95 Co 0.05 O 2 (NC), LiNi 0.95 Mn 0.05 O 2 (NM), and LiNi 0.95 Al 0.05 O 2 (NA). Furthermore, the activation energy of the reaction between water and the cathode is determined by measuring the leached LiOH concentration at various temperatures. While residual lithium and time-of-flight secondary-ion mass spectrometry measurements collectively reveal that the air stability overall follows the trend of NM > NA ≈ NC > LNO, the aged NM exhibits the highest charge-transfer resistance and the worst electrochemical performance among the cathodes. In situ, X-ray diffraction and scanning transmission electron microscopy unveil that the aged NM is plagued by a large area of resistive spinel-like M 3–x Li x O 4 phases, leading to aggravated particle reaction heterogeneity. Finally, a one-step recalcination method is demonstrated effective in fully restoring the degraded cathodes. This work provides insights into overcoming air sensitivity issues of high-Ni cathodes.

(S)TEM↗