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At least 19 records

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NASA NTRS1997

Alteration of mineral crystallinity and collagen cross-linking of bones in osteopetrotic toothless (tl/tl) rats and their improvement after treatment with colony stimulating factor-1

A common feature of various types of mammalian osteopetroses is a marked increase in bone mass accompanied by spontaneous bone fractures. The toothless (tl/tl) rat osteopetrotic mutation is characterized by drastically reduced bone resorption due to a profound deficiency of osteoclasts and their precursors. An altered bone morphology has also been observed. The mutants cannot be cured by bone marrow transplantation, but skeletal defects are greatly reduced after treatment with colony stimulating factor 1 (CSF-1). The objectives of this study were to characterize mineral and collagen matrices in cancellous and compact bone isolated from long bones of 6-week-old normal littermates, tl/tl osteopetrotic mutants and mutants (tl/tl) treated with CSF-1. There were no differences in bone mineral content, but a significant decrease in the crystallinity of mineral evaluated by the method based on electron paramagnetic resonance spectrometry was observed in all bones of tl/tl mutants as compared to that of controls. Within the collagen matrix, slight decreases in the labile cross-links, but significant increases in the content of the stable cross-links, pyridinoline, and deoxypyridinoline, were observed in both cancellous and compact bone of osteopetrotic mutants. In tl/tl mutants treated with human recombinant CSF-1, the normalization of the crystallinity of bone mineral as well as collagen cross-links was found. Our results indicate that remodeling of bone matrix in tl/tl mutants is highly suppressed, but that after treatment with CSF-1, this activity recovers significantly. Taken together, these data provide further support for the hypothesis that CSF-1 is an essential factor for normal osteoclast differentiation and bone remodelling.

NASA Discipline Musculoskeletal↗

NASA NTRS2000

Identification of Crystalline Minerals in Volcanic Alteration Products and Applications to the Surface of Mars

Visible, infrared and Mossbauer spectra have been measured for fine-grained alteration products of volcanic tephra and ash. Comparison of the spectral and chemical properties for different size separates and related samples provides information about the crystalline materials in these samples and how they may have formed. Hydrothermal processes can increase the alteration rates of the primary minerals and glass and provide S, Fe and/or water for formation of sulfates and hydrated minerals. Identification of crystalline alteration minerals on Mars may indicate hydrothermal alteration and sites of interesting geologic processes.

Bishop, J. L.↗

DOE OSTI2021

Rock weathering controls the potential for soil carbon storage at a continental scale

Abstract As rock-derived primary minerals weather to form soil, they create reactive, poorly crystalline minerals that bind and store organic carbon. By implication, the abundance of primary minerals in soil might influence the abundance of poorly crystalline minerals, and hence soil organic carbon storage. However, the link between primary mineral weathering, poorly crystalline minerals, and soil carbon has not been fully tested, particularly at large spatial scales. To close this knowledge gap, we designed a model that links primary mineral weathering rates to the geographic distribution of poorly crystalline minerals across the USA, and then used this model to evaluate the effect of rock weathering on soil organic carbon. We found that poorly crystalline minerals are most abundant and most strongly correlated with organic carbon in geographically limited zones that sustain enhanced weathering rates, where humid climate and abundant primary minerals co-occur. This finding confirms that rock weathering alters soil mineralogy to enhance soil organic carbon storage at continental scales, but also indicates that the influence of active weathering on soil carbon storage is limited by low weathering rates across vast areas.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1989

Infrared spectra of crystalline and glassy silicates and application to interstellar dust

The infrared spectra of crystalline minerals predicted in theoretical condensation sequences do not match the astronomical observations. Since the astronomical spectra are a closer match to glassy silicates, the authors undertook a study to measure the infrared spectra of glassy silicates that have compositions similar to silicate minerals predicted in theoretical condensation sequences. The data should support observations aimed at elucidating condensation chemistry in dust forming regions. The authors measured the mass absorption coefficients, from 2.5 to 25 microns, of ground samples of olivine, diopside, and serpentine and also smoke samples that were prepared from these minerals. The smoke samples prepared in this way are predominantly glassy with nearly the same composition as the parent minerals. The crystalline samples consisted of pure olivine ((Fe(0.1)Mg(0.9))(2)SiO(4)), serpentine, diopside. Sample purity was confirmed by x ray diffraction. Each mineral was ground for 10 hours and a measured mass of the powder was mixed with KBr powder for absorption measurements using the method of Borghesi et a. (1985). The smoke samples were prepared from the same samples used for grinding by vaporizing the minerals using pulsed laser radiation in air. The smoke samples formed by condensation of the resulting vapor. The smoke settled onto infrared transparent KRS-5 substrates and onto a quartz crystal microbalance used to obtain mass measurements. A description of the preparation method is given in Stephens (1980). The glassy diopside showed only diffuse electron diffraction peaks and hence was nearly amorphous, while the serpentine smoke showed a weak diffraction pattern corresponding to MgO. The smoke from olivine showed a weak diffraction pattern corresponding to Fe2O3 and/or Fe3O4. The mass absorption coefficients, from 2.5 to 25 microns, of crystalline diopside, olivine, and serpentine and their corresponding smoke samples are shown in figures.

Stephens, John R.↗

NASA NTRS2003

Aging of microstructural compartments in human compact bone

Composition of microstructural compartments in compact bone of aging male subjects was assessed using Raman microscopy. Secondary mineralization of unremodeled fragments persisted for two decades. Replacement of these tissue fragments with secondary osteons kept mean composition constant over age, but at a fully mineralized limit. Slowing of remodeling may increase fracture susceptibility through an increase in proportion of highly mineralized tissue. In this study, the aging process in the microstructural compartments of human femoral cortical bone was investigated and related to changes in the overall tissue composition within the age range of 17-73 years. Raman microprobe analysis was used to assess the mineral content, mineral crystallinity, and carbonate substitution in fragments of primary lamellar bone that survived remodeling for decades. Tissue composition of the secondary osteonal population was investigated to determine the composition of turned over tissue volume. Finally, Raman spectral analysis of homogenized tissue was performed to evaluate the effects of unremodeled and newly formed tissue on the overall tissue composition. The chemical composition of the primary lamellar bone exhibited two chronological stages. Organic matrix became more mineralized and the crystallinity of the mineral improved during the first stage, which lasted for two decades. The mineral content and the mineral crystallinity did not vary during the second stage. The results for the primary lamellar bone demonstrated that physiological mineralization, as evidenced by crystal growth and maturation, is a continuous process that may persist as long as two decades, and the growth and maturation process stops after the organic matrix becomes "fully mineralized." The average mineral content and the average mineral crystallinity of the homogenized tissue did not change with age. It was also observed that the mineral content of the homogenized tissue was consistently greater than the osteons and similar to the "fully mineralized" stage of primary bone. The results of this study demonstrated that unremodeled compartments of bone grow older through maturation and growth of mineral crystals in a protracted fashion. However, the secondary osteonal remodeling impedes this aging process and maintains the mean tissue age fairly constant over decades. Therefore, slowing of remodeling may lead to brittle bone tissue through accumulation of fully mineralized tissue fragments.

Non-NASA Center↗

NASA NTRS1999

Detection of Crystalline Hematite Mineralization on Mars by the Thermal Emission Spectrometer: Evidence for Near-surface Water

The Thermal Emission Spectrometer (TES) instrument on the Mars Global Surveyor (MGS) mission has discovered a remarkable accumulation of crystalline hematite ((alpha-Fe2O3) that covers an area with very sharp boundaries approximately 350 by 350-750 km in size centered near 2 S latitude between 0 and 5 W longitude (Sinus Meridiani). Crystalline hematite is uniquely identified by the presence of fundamental vibrational absorption features centered near 300, 450, and >525/cm, and by the absence of silicate fundamentals in the 1000/cm region. Spectral features resulting from atmospheric CO2, dust, and water ice were removed using a radiative transfer model. The spectral properties unique to Sinus Meridiani were emphasized by removing the average spectrum of the surrounding region. The depth and shape of the hematite fundamental bands show that the hematite is crystalline and relatively coarse grained (>5-10 micron). Diameters up to and greater than 100s of micrometers are permitted within the instrumental noise and natural variability of hematite spectra. Hematite particles <5-10 micron in diameter (either as an unpacked or hard-packed powders) fail to match the TES spectra. The spectrally-derived areal abundance of hematite varies with particle size from approximately 10% for particles >30 micron in diameter to 40-60% for unpacked 10 micron powders. The hematite in Sinus Meridiani is thus distinct from the fine-grained (diameter <5-10 micron), red, crystalline hematite considered, on the basis of visible, near-IR data, to be a minor spectral component in Martian bright regions like Olympus-Amazonis. Sinus Meridiani hematite is closely associated with a smooth, layered, friable surface that is interpreted to be sedimentary in origin. This material may be the uppermost surface in the region, indicating that it could be a late-stage sedimentary unit, or it could be a layered portion of the heavily cratered plains units. We consider five possible mechanisms for the formation of coarse-grained, crystalline hematite. These processes fall into two classes depending on whether they require a significant amount of near-surface water: (1) chemical precipitation that includes origin by (a) precipitation from oxygenated, Fe-rich water (iron formations), (b) hydrothermal extraction and crystal growth.

Christensen, P. R.↗

DOE OSTI2020

Black carbon enriches short-range-order ferrihydrite in Amazonian Dark Earth: Interplay mechanism and environmental implications

Our study underpins the mechanism of organo-mineral interaction between black carbon (BC, biochar) and associated minerals in the historical BC-rich Amazonian Dark Earth (ADE) by using synchrotron-based microscopic (TXM), microspectroscopic (μFTIR) and spectroscopic (XAS and μ-diffraction) approaches. The BC-rich ADE contained over 100% more poorly crystalline minerals than the adjacent tropical soil. Linear combination fitting of k-spacing in the X-ray Absorption Spectra (XAS) revealed that ferrihydrite contributed to 81.1% of the Fe-minerals in BC. A small but distinct peak was observed at 5.7 Å –1 in the extended X-ray absorption fine structure k oscillation of BC, revealing the presence of Fe—C (including Fe-O-C) covalent bonds. No Fe—C path was yielded by the XAS fitting when an obvious peak downshift of the first (Fe—Fe 1 ) shell was observed, suggesting that the availability of inner-sphere Fe—C complexation was limited to the BC surface and interphase region. In this study, the main minerals for organo-mineral complexation were short-range-order (SRO) ferrihydrite on BC instead of corner-sharing FeO 6 octahedra. Compared to ADE, the coordination number of the first (Fe—Fe 1 ) and second (Fe—Fe 2 ) shell was higher in BC, revealing a higher degree of order in coordination between the neighboring Fe mineral crystals. Black C limited the progressive aging of amorphous Fe phases and greatly enriched SRO ferrihydrite in the redox-fluctuating and high-leaching environment. The transformation of SRO ferrihydrite into the more crystalline Fe oxides was controlled by the local pH environment. A strong signal from the complexed phenolic group (aryl-OH, 1241 cm –1 ) and a distinct band of inner-sphere complexation (Fe-aryl C, 1380–1384 cm –1 ) were identified in the FTIR spectra. The enrichment of poorly crystalline minerals can have positive feedback on the long-term stabilization of BC. The scale-up application of biochar to agricultural and ecological systems may have a long-lasting impact on the enrichment and transformation of the SRO minerals in the soil.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRSDate not supplied

High Resolution Imaging and Analysis of Terrestrial Impact Glass: Amorphous Materials, Phyllosilicates and Everything in Between

Introduction: Impact cratering is one of the most ubiquitous geologic processes shaping the surface of all solid bodies in our solar system. Impacts are also a major source of clay minerals, poorly crystalline clay-like phases and amorphous (i.e., lacking long-range atomic order) materials on Earth and Mars. Phyllosilicates and amorphous materials have consistently formed a major component (~20-70 wt%) of every single drilled rock and soil sample in Gale Crater on Mars, as determined by the CheMin instrument on Curiosity. The origin of the amorphous component is speculative, but could be primary impact or volcanic-produced glass(es) deposited via aeolian or fluvial processes, secondary aqueous alteration products or chemical precipitates; it is likely to be a combination of all three possibilities. Efforts to determine the composition of these materials across the rover’s traverse through Gale Crater are ongoing. Naturally occurring amorphous phases are found in a variety of environments on Earth, and terrestrial analogue studies may help shed light on how they may have formed on Mars. Primary and altered impact glass are likely widespread on Mars and may have contributed to the amorphous component found throughout Gale Crater. In its pristine, unaltered state, impact glass (i.e., melt glass) is considered amorphous. However, truly unaltered glass is rarely preserved in crater fill impactites as it quickly alters in the post-impact environ-ment, commonly forming a mixture of hydrated aluminosilicate phases whose structures are not always discernable at the microscale (i.e., they may be amorphous or contain short-range order). These phases are part of an incredibly complex group of materials; differences in their composition and crystalline structure (or lack thereof) and genetic relationship to the more well-crystalline clay minerals are often only discernable at the nanoscale, beyond the resolution of traditional X-ray diffractometers (XRD) and scanning electron microscopes/microprobes (SEM/EPMA) alone. In this contribution, we summarize recent results from ongoing characterization of clay minerals, poorly crystalline clay-like phases, and amorphous materials preserved in altered terrestrial impact glass from the Chicxulub (~66 Ma) and Ries (~15 Ma) impact structures. This work has been performed using a combination of high-resolution transmission electron microscopy (HR-TEM), SEM, microprobe/EPMA, Raman spectroscopy and XRD.

Impact crater↗

NASA NTRS2015

Great New Insights from Failed Experiments, Unanticipated Results and Embracing Controversial Observations

Experimental data and observations, whether telescopic or analytical, are never wrong, though data derived from such sources can be misinterpreted or applied inappropriately to derive conclusions that are incorrect. Given that nature always behaves according to the laws of physics and chemistry, rather than according to currently popular models and theories, experimental results should always be considered correct even when the results are far from those that one might initially expect. We discuss a number of cases where the results of experiments, even one carried out as a simple calibration measure, produced wildly different results that generally required many years of effort or contemplation to understand. On the positive side, exploration of the circumstances that produced the errant results often led to new and interesting insights concerning processes that might occur in natural environments and that were well worth the effort involved. Specifically, we show how an experiment that "failed" due to a broken conductor led to experiments that made the first refractory oxide solids containing mass independently fractionated oxygen isotopes and to 1998 predictions of the oxygen isotopic composition of the sun that were confirmed by the analysis of Genesis samples in 2011. We describe a calibration experiment that unexpectedly produced single magnetic domain iron particles. We discuss how tracking down a persistent source of "contamination" in experiments intended to produce amorphous iron and magnesium silicate smokes led to a series of studies on the synthesis of carbonaceous grain coatings that turn out to be very efficient Fischer-Tropsch catalysts and have great potential for trapping the planetary noble gases found in meteorites. We describe how models predicting the instability of silicate grains in circumstellar environments spurred new measurements of the vapor pressure of SiO partially based on previous experiments showing unexpected but systematic non-equilibrium behavior instead of the anticipated equilibrium products resembling meteoritic minerals. We trace the process that led from observations of the presence of crystalline minerals detected in the comae of some comets to the 1999 prediction of large-scale circulation of materials from the hot, innermost regions of the solar nebula out to the cold dark nebular environments where comets form. This large-scale circulation was ultimately confirmed by analyses of highly refractory Stardust samples collected from the Kuiper Belt Comet Wild 2. Finally we discuss a modern and still unresolved conflict between the assumptions built into three well known processes: the CO Self Shielding Model for mass independent isotopic fractionation of oxygen in solar system solids, rapid and thorough mixing within the solar nebula, and the efficient conversion of CO into organic coatings and volatiles on the surfaces of nebular grains via Fischer-Tropsch-type processes.

controversial↗

DOE OSTI2022

Minerals limit the deep soil respiration response to warming in a tropical Andisol

Tropical regions hold one third of the world’s soil organic carbon, but few experiments have warmed tropical soils in situ. The vulnerability of these soils to climate change-induced losses is uncertain with many hypothesizing these soils would be less sensitive to climate change because already-high temperatures in tropical systems might limit microbial sensitivity or due to increased mineral protection of organic carbon in highly weathered tropical soils. Here we present the results of a deep soil (0–100 cm) warming experiment in a tropical Andisol. Andisols can store large, persistent pools of soil carbon that are protected from decomposition by poorly and non-crystalline minerals (PNCM). In 20 cm depth intervals, we measured key soil properties including carbon, nitrogen, pH, PNCM, bacterial and fungal richness along with temperature, moisture, and CO 2 production. Over a year of soil warming, CO 2 production significantly increased by 50–300% per degree of warming, but only in the top 40 cm of the soil profile in contrast to the results of other deep soil warming experiments. Multimodal analysis supported our hypothesis that high concentrations of PNCM was the primary driver of the lack of CO 2 response, followed by high relative soil moisture and low bacterial richness, which may be a proxy for organic carbon availability. The lack of elevated CO 2 production in response to warming suggests a limited positive feedback to climate change in Andisols driven by their strong mineral protection of organic matter. Therefore, Andisols should be considered high priority restoration or protection areas when considering the management of soil carbon stocks as part of climate action.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2006

Comet Mineralogy as Inferred from Infrared Spectra of Comets

For most comets, infrared (IR) spectroscopy (remote sensing) is the method through which we diagnose the mineralogy and size distribution of dust in their comae. The shape and contrast of the IR spectral features depend on the particle size: optically active minerals (absorbing of visible and near-IR solar photons) and submicron solid grains or highly porous (> 90% vacuum) grains primarily contribute to the shapes of the observed resonances. Comet mineralogies typically are determined by fitting thermal emission models of ensembles of discrete mineral grains to observed IR spectral energy distributions. The absorptivities (Q-abs) and scattering efficiencies (Q-scat) of the discrete mineral grains are computed using Mie scattering, Maxwell-Garnet mixing, Discrete Dipole Approximation, and Multi-Layered Sphere codes. These techniques when applied to crystalline minerals, specifically olivine (Mg_x, Fe_1-x)2 Si04, x>0.9, require the use of ellipsoidal shaped particles with elongated axial ratios or hollow spheres to produce the shapes of the resonances observed both from comet comae and laboratory samples. The wavelength positions of the distinct resonances from submicron-radii crystalline silicates, as well as their thermal equilibrium temperatures, constrain the crystalline olivine to have a relatively high Mg-content (x>0.9, or Fo>90). Only resonances computed for submicron Mg-rich crystalline olivine and crystalline orthopyroxene match the observed IR spectral features. However, this has led to the interpretation that micron-radii and larger crystals are absent from comet comae. Furthermore, the mass fraction of silicate crystals is dependent upon whether just the submicron portion of the size distribution is being compared or the submicron crystals compare to the aggregates of porous amorphous silicates that are computationally tractable as porous spheres. We will discuss the Deep Impact results as examples of these challenges to interpreting mid-IR spectra of short-period comets.

Wooden, Diane H.↗

DOE OSTI2024

Compositional zoning of the Otowi Member of the Bandelier Tuff, Valles caldera, New Mexico, USA

The Otowi Member of the Bandelier Tuff erupted at ca. 1.60 Ma from the Valles caldera (New Mexico, USA). It consists of as much as 400 km 3 (dense rock equivalent) of strongly differentiated high-silica rhyolite and shows systematic upward variations in crystallinity, mineral chemistry, and trace element concentrations through its thickness, but the major element composition is almost constant and is near the low-pressure granite minimum. Incompatible trace elements in whole pumice fragments and glasses show well-correlated linear covariations. Upward zoning to lower abundances of incompatible trace elements is accompanied by development of overgrowths on quartz and alkali feldspar, although earlier-formed interiors of quartz and feldspar have near-constant compositions throughout the tuff, modified by cation diffusion in the case of feldspar. Melt inclusions in remnant quartz cores show diverse Pb isotope ratios, pointing to a wide range of distinct protoliths that contributed rhyolitic melt to the Otowi magma. Mineral thermometers suggest a modest temperature gradient through the melt body, perhaps of 40 °C, at the time of eruption. Chemical, textural, and mineralogical variations and volume-composition relations through the tuff are consistent with an origin for zoning by melting of a high-crystallinity cumulate layer beneath cognate supernatant liquid to produce denser, remobilized liquid of accumulative composition (i.e., the “modified mush model”). Melting may have occurred in several episodes. The latest of these episodes, probably thousands of years prior to eruption, introduced new rhyolitic liquid into the system and was associated with a thermal excursion, recorded in core compositions of pyroxene, during which much of the earlier crystal mass was dissolved. This left inherited cores and interiors of accumulated quartz and feldspar mantled with new growth having less-evolved compositions (higher Ti, Sr, and Ba). Changing solubility of zircon during cumulate melting produced a reversal of Zr concentrations. There is no clear petrologic evidence of a recharge eruption trigger; nonetheless, compositional zoning resulted mainly from repeated recharge-induced remobilization of quartz-feldspar cumulate. The Otowi system was built, evolved, and modified by several events over the course of a few hundred thousand years.

Wolff, J. A.↗

DOE OSTI2015

Bench-scale electrokinetic remediation for cesium-contaminated sediment at the Hanford Site, USA

Electrokinetic (EK) remediation has been applied to extract various contaminants such as radionuclides, heavy metals, and organic compounds from contaminated sediment and soil using electric currents. We conducted a laboratory experiment to investigate the efficiency of EK remediation method for Hanford sediment (76% sand and 24% silt-clay) after artificial contamination with nonradioactive 133Cs (0.01 M CsNO3) as a surrogate for radioactive 137Cs. The initial 133Cs concentration in the bulk sediment was 668 mg kg-1, with a higher 133Cs concentration for the silt-clay fraction (867 mg kg-1) than for the sand fraction (83 mg kg-1). A significant removal of cationic 133Cs from the sediment occurred from the cathode side (-), whereas the removal was negligible from the anode side (+) during the EK remediation process for 68 days. Based on microwave-assisted total digestion, 312 mg kg-1 of 133Cs was removed from the bulk sediment, which corresponds to the removal efficiency of 47%. The EK method was significantly more efficient for the silt-clay fraction than for the sand fraction. X-ray diffraction (XRD) and scanning electron microscopy-electron dispersive spectroscopy (SEM-EDS) analyses indicate that change in major crystalline mineral phases was insignificant during the EK remediation and the removal of 133Cs from the Hanford sediment by the EK method is attributed mainly to cation exchange with K in clay minerals. The experimental results suggest that the EK method can effectively remove radioactive Cs from the surface or subsurface sediment contaminated by radioactive materials in the Hanford Site, Washington, USA.

Cation exchange↗

DOE OSTI2026

Synchrotron resolved microscale mineralogy and elemental composition of individual plinthic and manganiferous nodules from agricultural soils

Iron and manganese oxides are strong sorbents and elemental scavengers in the environment that can form macroscopic nodules in soils. Despite their importance in the geochemical cycling of nutrients and contaminants, nodules are rarely characterized. When analyzed, they are often combined into bulk samples, obscuring individual characteristics. This study investigates the composition and mineralogy of individual plinthic and manganiferous nodules in soil from cropping systems in the Farming Systems Project in Beltsville, Maryland. Elemental composition indicates the accumulation of contaminants and nutrients, including copper in all nodules and high levels of phosphorus in select nodules. Sequential extractions determine that highly crystalline minerals comprise the nodules, locking away these nutrients and contaminants. Bulk X-ray diffraction (XRD) demonstrated distinct mineralogies in the plinthic and manganiferous nodules, with the former comprised of quartz, goethite, and kaolinite, and the latter consisting of quartz, Mn 2 O 3 , and hematite. Synchrotron and laboratory-based X-ray fluorescence (XRF) mapping gives critical insight into the elemental distribution within the nodules and elucidates spatial elemental associations, including the coupling of manganese and iron in the manganiferous nodules. XRF maps paired with µXRD provide microscale spatial resolution in mineralogy, which resolved several phases not apparent in bulk XRD, manganese’s association with goethite, and minerals indicative of redox transformations, including magnetite and maghemite. These novel results provide critical insight into the microscale mineralogy and individual elemental composition of plinthic and manganiferous nodules, as well as how they alter bulk soil geochemistry in ways largely unaccounted for in research on soil systems.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Synthesis of magnesiowüstite nanocrystallites embedded in an amorphous silicate matrix via low energy multiple ion implantations

The synthesis process is presented for experimentally simulating modifications in cosmic dust grains using sequential ion implantations or irradiations followed by thermal annealing. Cosmic silicate dust analogues were prepared via implantation of 20–80 keV Fe - , Mg - , and O - ions into commercially available p-type silicon (100)wafers. The as-implanted analogues are amorphous with a Mg/(Fe+Mg) ratio of 0.5 tailored to match theoretical abundances in circumstellar dusts. Before the ion implantations were performed, Monte-Carlo-based ion-solid interaction codes were used to model the dynamic redistribution of the implanted atoms in the silicon substrate. 600 keV helium ion irradiation was performed on one of the samples before thermal annealing. Two samples were thermally annealed at a temperature appropriate for an M-class stellar wind, 1000 K, for 8.3 h in a vacuum chamber with a pressure of 1 x 10 -7 torr. The elemental depth profiles were extracted utilizing Rutherford Backscattering Spectrometry (RBS) in the samples before and after thermal annealing. X-ray diffraction (XRD)analysis was employed for the identification of various phases in crystalline minerals in the annealed analogues. Transmission electron microscopy (TEM) analysis was utilized to identify specific crystal structures. RBS analysis shows redistribution of the implanted Fe, Mg, and O after thermal annealing due to incorporation into the crystal structures for each sample type. XRD patterns along with TEM analysis showed nanocrystalline Mg and Fe oxides with possible incorporation of additional silicate minerals.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2023

The diversity of aluminum-based drinking water treatment residuals for use in environmental remediation

Drinking water treatment residuals (DWTRs) are complex mixtures of organic and inorganic phases generally disposed of as waste materials. However, their strong sorptive properties could be further exploited to immobilize contaminants. To characterize these materials, we applied a range of analytical techniques to a set of aluminum-based DWTRs. Here we determined surface areas, elemental compositions using CHNS analysis and X-ray fluorescence (XRF), performed thermogravimetric analyses paired with mass spectrometry (TGA-MS), and used synchrotron-based methods: X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Elemental analyses and specific surface area measurements – that vary between 7.23 ± 0.03 and 197.6 ± 0.9 m 2 g –1 – indicate that non-coagulant additives must play an important role in controlling sorption. High resolution powder XRD reveals the presence of only a few crystalline minerals mostly derived from source waters or additives. Fe was detected by XRF in all samples, whereas Mn was present in significant levels in samples with potassium permanganate as additive. The chemical speciation of these elements was characterized by performing spectral decompositions of XAS spectra. The spectral features of Fe are consistent with iron(III) oxides/hydroxides and structural iron in clays. On the other hand, Mn is predominantly present under its reduced form, Mn(II).

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2015

Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria

Despite the regular occurrence of both magnetite and iron-metabolizing bacteria in the same environments, it is currently unknown whether the iron(II) and iron(III) in magnetite can be cycled between different bacteria and whether or how magnetic properties are affected by this metabolic activity. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizer Rhodopseudomonas palustris TIE-1 can oxidize solid-phase magnetite nanoparticles using light energy, leading to a decrease in the measured magnetic susceptibility (MS). This process likely occurs at the surface and is reversible in the dark by the Fe(III)-reducer Geobacter sulfurreducens resulting in an increase in MS. These results show that iron ions bound in highly crystalline mineral magnetite are bioavailable as electron stores and electron sinks under varying environmental conditions, making magnetite a potential “biogeobattery” during day/night cycles. These findings are relevant for environmental studies and reinforce the impact of microbial redox processes on the global iron cycle.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2021

Deeply Rooted: Evaluating Plant Rooting Depth as a Means for Enhanced Soil Carbon Sequestration (Full Technical Report)

Soils store three times as much carbon (C) as the atmosphere, but are not at capacity, and enhanced soil C storage is considered an essential strategy to mitigate rising atmospheric CO 2 levels. Agricultural soils have experienced substantial C loss in the past century due to poor agricultural practices and erosion. A shift towards deep-rooting crops and low-impact soil management could potentially increase long-term sequestration of C fixed by plants and stored in their root tissues, particularly for crops that have naturally deep root systems (>1 meter). A substantial amount of the CO 2 taken up by plants is allocated to their root systems, and because C deposited in deep soil layers has a longer residence time (up to millennia, in contrast to C deposited in topsoils), C increases at depth may have better long-term C sequestration potential than topsoils. However, the accrual, turnover, and stabilization of C in subsoils is a critical knowledge gap. We investigated a deeply rooted plant, switchgrass (Panicum virgatum), as a means of increasing carbon stocks in marginal and agricultural soils. We hypothesized that deep (>30 cm) SOC stocks would be greater under bioenergy crops relative to stocks under shallow-rooted conventional crop cover. To test this hypothesis, we compared soil depth profiles beneath deeply rooted switchgrass (cultivated for 4-30 years) and paired shallowrooted annual controls. We studied 12 field sites, 3 that were collected in 2018 before the start of the project as part a Department of Energy (DOE) Sustainable Biofuels study, and 9 that we collected in 2019 on a national field sampling campaign across the eastern US. In our publication from the 2018 study, which was written in collaboration with the LLNL Soil Microbiome Scientific Focus Area (SFA), we found that C stocks increased under switchgrass, but that the increases were dependent on soil texture. In the 2019 study, we found that carbon accrual tended to occur most consistently in low C soil in the southern US, which could indicate that perennial grasses may be a viable strategy to increase SOC in marginals soils in this region. We have published two studies from the 2019 sampling campaign thus far, we measured microbial growth parameters that will aid in modeling subsoil carbon cycling, and we found that switchgrass appears to move water upward in the soil profile and could promote drought tolerance, which a phenomenon commonly performed by trees known as ‘hydraulic redistribution;’ our study is the first to show this can occur in deep-rooted grasses. Finally, we published a modeling paper in collaboration with the LLNL Soil Microbiome SFA, where we found that poorly crystalline minerals are abundant and strongly correlated with organic C in geographically limited zones with enhanced weathering rates. Our results will inform technological development in the agricultural carbon sequestration sector as well as future negative emissions policies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗