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DOE OSTI2019

Oxidation state and coordination environment of Pb in U-bearing minerals

This study examines the oxidation and coordination of lead (Pb) in the uranium (U) minerals uraninite (UO 2 ), coffinite (USiO 4 ), and brannerite (UTi 2 O 6 ), and minerals that have U as a minor constituent, zircon (ZrSiO 4 ) and titanite (CaTiSiO 5 ). The characterization of Pb was conducted through a combination of micro-synchrotron X-ray fluorescence mapping (µSXRF) and micro-X-ray absorption spectroscopy (µXAS), collected at the Pb L II and L III edge on characterized grains (electron microscopy and X-ray diffraction) from a range of geological settings and ages. For all minerals considered in this study, Pb L II and L III X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data indicate that Pb exists as Pb 2+ . In the case of uraninite, DFT structure optimization calculations suggest that the substitution of Pb 2+ for U 4+ is facilitated by the stereochemically active electron lone pair indicative of Pb 2+ , which effectively takes the place of an oxygen vacancy (coupled substitution Pb 2+ + = U 4+ + O 2- ). In detail, however, the EXAFS and XANES data, supported by first principle calculations of the XANES associated with Pb 2+ replacing U 4+ in the crystal lattice of uraninite, indicate that Pb 2+ is present in a less distorted coordination than suggested by DFT, which may reflect a yet to be characterized link between interstitial oxygen defects and Pb 2+ incorporation, rather than a simple oxygen vacancy. For coffinite, the XANES data demonstrate that Pb exists mainly as Pb 2+ in the form of galena, indicating limited stability of the isomorphous substitution in coffinite. In contrast, Pb is homogeneously distributed in the metamict mineral brannerite, which displays a distinct XANES spectrum suggestive of Pb 2+ bonded to oxygens in a highly distorted coordination environment. Pb L II XANES indicate that radiogenic Pb exists predominantly as Pb 2+ within the crystal lattice of zircon and as distinct mineral PbO nano-scale inclusions or domains. Additionally, Pb L II XANES measurements also indicate that Pb 2+ exists within titanite although the coordination environment is unclear. Overall, these data suggest that the previous indications of the presence of Pb 4+ in radioactive minerals need to be reconsidered. The nature of radiogenic Pb 2+ incorporation in U-bearing minerals controls the mobilization of Pb in hydrothermal fluids and the utility of a mineral as a geochronometer. The Pb valence and coordination data presented in this study provide fundamental constraints imperative for our understanding of the controls governing the mobilization of radiogenic Pb during water-rock interaction and metamorphism.

58 GEOSCIENCES↗

DOE OSTI2021

Iron, magnesium, and titanium isotopic fractionations between garnet, ilmenite, f ayalite, biotite, and tourmaline: Results from NRIXS, ab initio , and study of mineral separates from the Moosilauke metapelite

Interpreting isotopic signatures documented in natural rocks requires knowledge of equilibrium isotopic fractionation factors. Here, we determine equilibrium Fe isotope fractionation factors between several common rock-forming minerals using a comparative approach involving three independent methods: (i) isotopic analyses of natural minerals from a metapelite from Mt. Moosilauke, New Hampshire, for which equilibration temperature and pressure are well constrained to be near the aluminosilicate triple point (T ≃ 500 °C, P ≃ 4 kbar), (ii) Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements of Fe force constants of minerals, and (iii) Density Functional Theory (DFT) ab initio calculations of Fe force constants of minerals. The minerals studied for Fe isotopes include, in increasing order of their β-factors: garnet < ilmenite ≈ fayalite < biotite < tourmaline < muscovite ≈ plagioclase. Some of this ordering is affected by the presence of Fe 3+ in the minerals, which tends to form stiffer bonds and be associated with heavy Fe isotope enrichments relative to Fe 2+ . We are, however, able to assess the magnitude of the effect of the ratio Fe 3+ /ΣFe on equilibrium fractionation factors, notably on the ilmenite-hematite solid solution. Equilibrium Fe isotopic fractionation factors between garnet, ilmenite, biotite, tourmaline and fayalite are determined. We also report Mg and Ti isotopic compositions of selected Moosilauke minerals that allow us to better constrain the equilibrium fractionation factors for garnet-biotite-tourmaline (Mg isotopes) and biotite-ilmenite (Ti isotopes). We show how the newly determined equilibrium fractionation factors can be used to address diverse problems in Earth and planetary sciences, notably (i) Fe and Mg isotopic fractionation during anatexis, (ii) Fe isotopic fractionation in lunar ilmenite, and (iii) Ti isotopic fractionation during fluvial transport of minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Antibacterial Minerals: A geochemical approach to combating antibiotic resistance

The rapid rise of antibiotic resistant bacteria is seriously threatening our ability to treat lifethreatening infections. As a result, our approach to medicine and agriculture will require significant changes if we are to successfully maintain current levels of healthcare and food security. Certain naturally occurring clays have been shown to harbor antimicrobial properties and kill antibiotic resistant bacteria. These clays have been proposed as a new paradigm for fighting the potentially devastating effects of the post antibiotic era. However, natural samples, by their inherent properties, exhibit variable antibacterial effectiveness and the synthesis of minerals with reproducible antibacterial activity is needed. Our project focused on 3 specific aims; 1) develop synthetic versions of naturally occurring bactericidal minerals to control the chemical purity and antibacterial potency, 2) determine how effective these mineral formulations are at killing antibiotic resistant bacteria and 3) investigate the response of human skin cell cultures to these antibacterial minerals. Utilizing hydrothermal based methods our team was able to reproduce the antibacterial activity observed in natural antibacterial minerals, while eliminating unwanted elemental impurities. Importantly, we were able to create a mineral based bactericide that has reproducible reactivity that could provide a consistent dose response. These antibacterial mineral formulations are effective at killing common hospital acquired antibiotic resistant bacteria while providing minimal toxicity to human fibroblasts. Our research has optimized the antibacterial properties of antibacterial minerals to allow greater efficacy from a public health perspective.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Pore architecture controls on mineral reactivity

Mineral dissolution rates measured in natural environments are much slower than those measured in laboratory settings. This project tested the hypothesis that the way fluid flows through rocks in natural systems creates areas where mineral dissolution is fast and areas where mineral dissolution is slow. This hypothesis was tested with a combination of laboratory experiments and numerical simulation. We demonstrated a separation of fluid flow pathways and rates of mineral dissolution in laboratory experiments for the first time using an experimental approach where we created synthetic rocks that have different ratios of connected and dead-end pathways for fluid flow. In laboratory experiments with higher proportions of dead-end pathways, the mineral dissolution rates were slower. We found that where fluid flows through connected pathways the continuous refreshing of fluid at the mineral surface creates conditions where dissolution is fast. In contrast, where fluid either flows slowly through poorly connected pathways or is stagnant in dead-end pathways, mineral dissolution is slow. The results from this project suggest that the overall slowing of rates of mineral dissolution is important when the proportion of dead-end pathways is greater than ~40%. This project informs our understanding of the way that fluids react with rocks in carbon dioxide sequestration and enhanced geothermal projects where fluids are purposefully injected into rocks for energy applications.

58 GEOSCIENCES↗

DOE OSTI2022

King City Asbestos Corporation (KCAC) Mine Carbon Mineralization Field Test (Final Combined Report)

The overall objective of the KCAC carbon mineralization project is to determine the most successful approaches to CO 2 mineralization of asbestos-bearing serpentinite rocks and mine waste at the closed KCAC asbestos mine. The objectives of Budget Period 1 (BP1) are to characterize the site including, mineralogical and geochemical variability in site materials, baseline conditions including CO 2 flux and local climate, and to establish the designs for the second, experimental phase of the project. As described in Section 3 of this report, all tasks outlined in the Statement of Project Objective (SOPO) have been completed or are on schedule to be completed by the end of BP1. As described in Section 4, all success criteria and milestones have been met or will be met by the end of BP1. We conclude that the findings of BP1 strongly support moving to the second phase of the project to investigate methods to increase the rate of CO 2 mineralization. CO 2 flux monitoring during BP1 established an estimated baseline uptake of CO 2 over the 142,193 m 2 KCAC mine site of 147 and 179 metric tons CO 2 /yr using dynamic closed chamber and eddy covariance monitoring methods, respectively. Mineralogical analysis shows that the loose surficial waste material contains pyroaurite and minor hydromagnesite, indicating past carbon mineralization. Sediment samples at depths below 60 cm contained ~3 wt% brucite and localized high brucite contents of ~24 wt% were measured at depth, indicating significant unreacted material at relatively shallow depths. Together, these results demonstrate that despite prolonged exposure to the atmosphere, reactive material is still present and accessible and is naturally taking up atmospheric CO 2 . However, these natural rates are still well below rates that can be achieved by applying practices that can accelerate the CO 2 mineralization reaction. Designs for the Field-Testing Phase (BP2) of the project have been established, incorporating the findings of BP1. Based on results to date we have selected two methods to accelerate the rate of CO 2 mineralization, which we refer to as the Tilling Method and the Greenhouse Method. We hypothesize that these methods can increase the CO 2 mineralization rate by up to 5 times greater than the natural background rate measured in BP1. An Initial Lifecyle Assessment (LCA) and techno-economic analysis (TEA) were conducted for these two methods. The LCA concluded that the baseline version of the Greenhouse and Tilling methods at commercial scale are expected to achieve a CDR efficiency of 97% and 71%, respectively (cumulative, over 30 years of operation). Incorporating the net CO 2 removal rates calculated in the LCA, the TEA found the levelized, 30-year costs of the baseline Greenhouse and Tilling methods to be $\$$95/t-CO 2 and $\$$119/t-CO 2 , respectively, and that costs could be brought to well below $\$$100/t-CO 2 for either method by scaling up the volume of rock utilized. An initial EH&S Risk Assessment, evaluating the potential EH&S risks of the proposed carbon mineralization methods at commercial scale, was completed by LLNL EH&S professionals for these two methods.

58 GEOSCIENCES↗

DOE OSTI2024

Mapping Geothermal Indicator Minerals Using Fusion of Target Detection Algorithms

Mineral mapping from satellite images provides valuable insights into subsurface mineral alteration for geothermal exploration. In previous studies, eight fundamental algorithms were used for mineral mapping utilizing USGS spectra, a collection of reflectance spectra containing samples of minerals, rocks, and soils created by the USGS. We used an ASD FieldSpec 4 Hi-RES NG portable spectrometer to collect spectra for analyzing ASTER images of the Coso Geothermal Field. Then, we established the ground-truth information and the spectral library by analyzing 97 samples. Samples collected from the field were analyzed using the CSIRO TSG (The Spectral Geologist of the Commonwealth Scientific and Industrial Research Organization). Based on the mineralogy study, multiple high-purity spectra of geothermal alteration minerals were selected from collected data, including alunite, chalcedony, hematite, kaolinite, and opal. Eight mineral spectral target detection algorithms were applied to the preprocessed satellite data with a proposed local spectral library. We measured the highest overall accuracy of 87% for alunite, 95% for opal, 83% for chalcedony, 60% for hematite, and 96% for kaolinite out of these eight algorithms. Three, four, five, and eight algorithms were fused to extract mineral alteration with the obtained target detection results. The results prove that the fusion of algorithms gives better results than using individual ones. In conclusion, this paper discusses the significance of evaluating different mapping algorithms. It proposes a robust fusion approach to extract mineral maps as an indicator for geothermal exploration.

Cavur, Mahmut↗

DOE OSTI2015

Predicting the mineral composition of dust aerosols – Part 1: Representing key processes

Soil dust aerosols created by wind erosion are typically assigned globally uniform physical and chemical properties within Earth system models, despite known regional variations in the mineral content of the parent soil. Mineral composition of the aerosol particles is important to their interaction with climate, including shortwave absorption and radiative forcing, nucleation of cloud droplets and ice crystals, heterogeneous formation of sulfates and nitrates, and atmospheric processing of iron into bioavailable forms that increase the productivity of marine phytoplankton. Here, aerosol mineral composition is derived by extending a method that provides the composition of a wet-sieved soil. The extension accounts for measurements showing significant differences between the mineral fractions of the wet-sieved soil and the emitted aerosol concentration. For example, some phyllosilicate aerosols are more prevalent at silt sizes, even though they are nearly absent at these diameters in a soil whose aggregates are dispersed by wet sieving. We calculate the emitted mass of each mineral with respect to size by accounting for the disintegration of soil aggregates during wet sieving. These aggregates are emitted during mobilization and fragmentation of the original undispersed soil that is subject to wind erosion. The emitted aggregates are carried far downwind from their parent soil. The soil mineral fractions used to calculate the aggregates also include larger particles that are suspended only in the vicinity of the source. We calculate the emitted size distribution of these particles using a normalized distribution derived from aerosol measurements. In addition, a method is proposed for mixing minerals with small impurities composed of iron oxides. These mixtures are important for transporting iron far from the dust source, because pure iron oxides are more dense and vulnerable to gravitational removal than most minerals comprising dust aerosols. Finally, a limited comparison to measurements from North Africa shows that the model extensions result in better agreement, consistent with a more extensive comparison to global observations as well as measurements of elemental composition downwind of the Sahara, as described in companion articles.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1982

Mars weathering analogs - Secondary mineralization in Antarctic basalts

Alkalic basalt samples from Ross Island, Antarctica, are evaluated as terrestrial analogs to weathered surface materials on Mars. Secondary alteration in the rocks is limited to pneumatolytic oxidation of igneous minerals and glass, rare groundmass clay and zeolite mineralization, and hydrothermal minerals coating fractures and vesicle surfaces. Hydrothermal mineral assemblages consist mainly of K-feldspar, zeolites (phillipsite and chabazite), calcite, and anhydrite. Low alteration rates are attributed to cold and dry environmental factors common to both Antarctica and Mars. It is noted that mechanical weathering (aeolian abrasion) of Martian equivalents to present Antarctic basalts would yield minor hydrothermal minerals and local surface fines composed of primary igneous minerals and glass but would produce few hydrous products, such as palagonite, clay or micas. It is thought that leaching of hydrothermal vein minerals by migrating fluids and redeposition in duricrust deposits may represent an alternate process for incorporating secondary minerals of volcanic origin into Martian surface fines.

Berkley, J. L.↗

NASA NTRS1988

Automatic mineral map generation procedure from imaging spectrometer data

An airborne imaging spectrometer collected data for 128 wave length channels covering from near to short wavelength infrared across a 320 m swath, to help obtain a mineral map of an area based on reflectance spectral signatures of the area. Minerals have distinctive crystal structures and chemical contents which can be identified by their light absorption characteristics, and an optimized automatic mineral map generation procedure for imaging spectrometer data was developed. The procedure generates two types of mineral maps, a mineral distribution map showing spatial layout of various minerals and a mineral composition map showing the percentage composition of a selected mineral.

Lee, M.↗

NASA NTRS1999

Mineralization and growth of cultured embryonic skeletal tissue in microgravity

Microgravity provides a unique environment in which to study normal and pathological phenomenon. Very few studies have been done to examine the effects of microgravity on developing skeletal tissue such as growth plate formation and maintenance, elongation of bone primordia, or the mineralization of growth plate cartilage. Embryonic mouse premetatarsal triads were cultured on three space shuttle flights to study cartilage growth, differentiation, and mineralization, in a microgravity environment. The premetatarsal triads that were cultured in microgravity all formed cartilage rods and grew in length. However, the premetatarsal cartilage rods cultured in microgravity grew less in length than the ground control cartilage rods. Terminal chondrocyte differentiation also occurred during culture in microgravity, as well as in the ground controls, and the matrix around the hypertrophied chondrocytes was capable of mineralizing in both groups. The same percentage of premetatarsals mineralized in the microgravity cultures as mineralized in the ground control cultures. In addition, the sizes of the mineralized areas between the two groups were very similar. However, the amount of 45Ca incorporated into the mineralized areas was significantly lower in the microgravity cultures, suggesting that the composition or density of the mineralized regions was compromised in microgravity. There was no significant difference in the amount of 45Ca liberated from prelabeled explants in microgravity or in the ground controls.

NASA Discipline Developmental Biology↗

NASA NTRS1993

Mineral and organic matrix interaction in normally calcifying tendon visualized in three dimensions by high-voltage electron microscopic tomography and graphic image reconstruction

To define the ultrastructural accommodation of mineral crystals by collagen fibrils and other organic matrix components during vertebrate calcification, electron microscopic 3-D reconstructions were generated from the normally mineralizing leg tendons from the domestic turkey, Meleagris gallopavo. Embedded specimens containing initial collagen mineralizing sites were cut into 0.5-micron-thick sections and viewed and photographed at 1.0 MV in the Albany AEI-EM7 high-voltage electron microscope. Tomographic 3-D reconstructions were computed from a 2 degree tilt series of micrographs taken over a minimum angular range of +/- 60 degrees. Reconstructions of longitudinal tendon profiles confirm the presence of irregularly shaped mineral platelets, whose crystallographic c-axes are oriented generally parallel to one another and directed along the collagen long axes. The reconstructions also corroborate observations of a variable crystal length (up to 170 nm measured along crystallographic c-axes), the presence of crystals initially in either the hole or overlap zones of collagen, and crystal growth in the c-axis direction beyond these zones into adjacent overlap and other hole regions. Tomography shows for the first time that crystal width varies (30-45 nm) but crystal thickness is uniform (approximately 4-6 nm at the resolution limit of tomography); more crystals are located in the collagen hole zones than in the overlap regions at the earliest stages of tendon mineralization; the crystallographic c-axes of the platelets lie within +/- 15-20 degrees of one another rather than being perfectly parallel; adjacent platelets are spatially separated by a minimum of 4.2 +/- 1.0 nm; crystals apparently fuse in coplanar alignment to form larger platelets; development of crystals in width occurs to dimensions beyond single collagen hole zones; and a thin envelope of organic origin may be present along or just beneath the surfaces of individual mineral platelets. Implicit in the results is that the formation of crystals occurs at different sites and times by independent nucleation events in local regions of collagen. These data provide the first direct visual evidence from 3-D imaging describing the size, shape, orientation, and growth of mineral crystals in association with collagen of a normally mineralizing vertebrate tissue. They support concepts that c-axial crystal growth is unhindered by collage hole zone dimensions, that crystals are organized in the tendon in a series of generally parallel platelets, and that crystal growth in width across collagen fibrils may follow channels or grooves formed by adjacent hole zones in register.

Non-NASA Center↗

NASA NTRSDate not supplied

Testing Destruction of Clay Minerals By Silica-Poor Brines in Gale Crater, Mars Using Laboratory and Field Experiments

The Mars Science Laboratory (MSL) Curiosity rover landed in Gale crater to investigate the cause for mineralogical changes seen from orbit, including the clay-sulfate mineral transition observed on its central mound, Aeolis Mons. The lower strata show spectral signatures of clay minerals, hematite, and hydrated Mg sulfates, and the upper strata are dominated by hydrated Mg sulfate signatures. This significant transition has been observed in other locations on Mars, and therefore processes related to the clay mineral-sulfate transition are likely important broadly across Mars. The bulk mineralogy of ~3.7 Ga sedimentary rocks in Gale crater is a product of variations in sediment sources and depositional processes, with overprinting by episodes of early and late diagenetic alteration. Sedimentary analyses of the smectite clay minerals observed in the Glen Torridon (GT) region of Mount Sharp suggest formation in a lacustrine aqueous environment. Examination of the Vera Rubin ridge (VRR) strata indicate that it was formed at the same time as GT and later altered by extensive diagenesis. Recent work suggests that the observed mineral transition from smectites and talc-serpentinites in GT to iron oxides and oxyhydroxides and VRR may have resulted from extensive diagenetic alteration by density driven, silica-poor brines sourced from the overlying sulfur-bearing unit on Mount Sharp. This process of alteration by silica-poor brines is observed in limited locations on Earth. We are therefore working to demonstrate the impacts of silica poor brines on clay mineral alteration in laboratory column and terrestrial analog burial experiments. Column experiments allow the investigation of dissolution and precipitation under conditions that represent a closer analog to natural environments, while burial experiments allow examination of weathering reactions of a known starting material after a specific period of time in a natural field environment. Both methods are valuable for interpreting the water-rock interactions between clay minerals and brines. In preparation for these longer-term column and burial experiments, we are performing preliminary batch dissolution experiments on materials relevant to Glen Torridon: nontronite and serpentinite. We are using magnesium sulfate brine solutions relevant to those proposed on Mars. The results of this study can provide constraints on the characteristics of the diagenetic fluids that formed the altered minerals in Gale crater. They can also provide insights into the role of brine density-driven diagenesis in past aqueous environments on Mars, which have been proposed to be widespread.

J E Valdueza↗

NASA NTRS2021

An evolutionary system of mineralogy, Part IV: Planetesimal differentiation and impact mineralization (4566 to 4560 Ma)

The fourth installment of the evolutionary system of mineralogy considers two stages of planetesimal mineralogy that occurred early in the history of the solar nebula, commencing by 4.566 Ga and lasting for at least 5 million years: (1) primary igneous minerals derived from planetesimal melting and differentiation into core, mantle, and basaltic components and (2) impact mineralization resulting in shock-induced deformation, brecciation, melting, and high-pressure phase transformations. We tabulate 90 igneous differentiated asteroidal minerals, including the earliest known occurrences of minerals with Ba, Cl, Cu, F, and V as essential elements, as well as the first appearances of numerous phosphates, quartz, zircon, and amphibole group minerals. We also record 40 minerals formed through high-pressure impact alteration, commencing with the period of asteroid accretion and differentiation. These stages of mineral evolution thus mark the first time that high pressures, both static and dynamic, played a significant role in mineral paragenesis.

Shaunna M. Morrison↗

NASA NTRSDate not supplied

Anhydrous Primary Minerals in Ryugu, Ivuna, and Bennu

Samples returned from asteroid Ryugu are chemically and mineralogically similar to CI chondrites [e.g., 1–3]. Both are predominantly composed of low-temperature aqueously formed secondary minerals, whereas high-temperature anhydrous primary minerals, such as olivine, low-Ca pyroxene, spinel, and hibonite, are rarely present. Using secondary ion mass spectrometry (SIMS; Cameca ims-1280HR at Hokkaido University), we performed O [4] and Al–Mg [5] isotope measurements of anhydrous primary minerals in samples of Ryugu and the Ivuna CI chondrite to constrain their origin.Anhydrous primary minerals in our samples of Ryugu and Ivuna occur mostly as monomineralic isolated grains embedded in hydrated matrix. Their O-isotope compositions are distributed along the slope-1 line on the O three-isotope diagram and range from Δ17O ~ –23 to 0‰. Mg-Al spinel grains are 16O-rich (Δ17O ~ –23‰). Low-Ca pyroxene grains are 16O-poor (Δ17O ~ –5‰). Olivine grains show a bimodal distribution of O-isotope composition:10 of 34 grains measured are 16O-rich (Δ17O ~ –23‰) and 24 grains are 16O-poor (Δ17O ~ –7 to 0‰). We found refractory inclusions composed of Mg-Al spinel and hibonite, one from Ryugu and one from Ivuna. Also, in Ivuna, we found an amoeboid olivine aggregate ( AOA) composed of olivine, diopside, anorthite, and Mg-Al spinel and an inclusion composed of olivine and Mg-Al spinel. The minerals in all of these inclusions are 16O-rich (Δ17O ~ –24‰).The 16O-rich grains and inclusions are mineralogically and O-isotopically similar to calcium-aluminum–rich inclusions (CAIs) and AOAs reported in other carbonaceous chondrites [6, 7]. In addition, the initial 26Al/27Al ratios of the two spinel-hibonite inclusions are inferred as ~4.4 × 10–5, also similar to most CAIs in carbonaceous chondrites [6, 8]. The range of Δ17O values for the 16O-poor olivine and low-Ca pyroxene grains is consistent withthat of these minerals in chondrules in most carbonaceous chondrites [9]. Moreover, the most frequent Δ17O value (–6‰) for Mg-rich (Mg# > 97) olivine grains is identical to those for chondrules. Although CI chondrites and Ryugu samples are devoid of chondrules, the 16O-poor grains most likely represent fragments of chondrule-like objects. The presence of both 16O-poor chondrule-like and 16O-rich refractory inclusion–like minerals in Ryugu and Ivuna suggests that some of their building blocks are similar to those of other carbonaceous chondrite groups. They both probably formed in the inner solar protoplanetary disk and were subsequently transported outward.Preliminary data for petrography of asteroid Bennu samples and chemical and isotopic compositions of theiranhydrous primary minerals will also be presented in the meeting.

N Kawasaki↗

DOE OSTI2018

Experimental studies of reactivity and transformations of rocks and minerals in water-bearing supercritical CO2

Geologic storage of carbon dioxide is a promising strategy for reducing CO2 concentrations in the atmosphere. In this process, silicate minerals in the host rock can react to permanently trap CO2 as precipitated carbonates. In addition, expandable clays in caprocks can swell or shrink and impact the integrity of the caprock seal. While the reactivity of minerals in CO2-rich aqueous fluids has been well studied, much less is known about mineral transformations in supercritical CO2 (scCO2) containing dissolved water. This chapter focuses on experimental investigations of mineral reactivity and transformations in variably hydrated scCO2. We summarize research regarding reservoir rocks, including carbonates, sandstone, granite, basalt, and peridotite. We also cover studies on several mineral systems, including phyllosilicate (montmorillonite), olivine (forsterite), serpentine (antigorite), pyroxene (enstatite), and feldspars (albite, anorthite, and microcline). For expandable phyllosilicate clay minerals, it is shown that volume changes are induced by both H2O and CO2 intercalation. For metal silicate minerals, a common observation is the adsorption of ångstroms- to nanometers-thick H2O films, which facilitate mineral dissolution, ion transport, and nucleation of metal carbonate precipitates. Many silicates exhibit a threshold concentration of adsorbed H2O, before which carbonation is limited to possibly amorphous phase precipitation or surface complexation, but beyond which carbonation is continuous and crystalline carbonates can form.

Loring, John S.↗

NASA NTRS2020

Global earth mineral inventory: A data legacy

Minerals contain important clues to understanding the complex geologic history of Earth and other planetary bodies. Therefore, geologists have been collecting mineral samples and compiling data about these samples for centuries. These data have been used to better understand the movement of continental plates, the oxidation of Earth's atmosphere and the water regime of ancient martian landscapes. Datasets found at ‘RRUFF.info/Evolution’ and ‘mindat.org’ have documented a wealth of mineral occurrences around the world. One of the main goals in geoinformatics has been to facilitate discovery by creating and merging datasets from various scientific fields and using statistical methods and visualization tools to inspire and test hypotheses applicable to modelling Earth's past environments. To help achieve this goal, we have compiled physical, chemical and geological properties of minerals and linked them to the above-mentioned mineral occurrence datasets. As a part of the Deep Time Data Infrastructure, funded by the W.M. Keck Foundation, with significant support from the Deep Carbon Observatory (DCO) and the A.P. Sloan Foundation, GEMI (‘Global Earth Mineral Inventory’) was developed from the need of researchers to have all of the required mineral data visible in a single portal, connected by a robust, yet easy to understand schema. Our data legacy integrates these resources into a digestible format for exploration and analysis and has allowed researchers to gain valuable insights from mineralogical data. GEMI can be considered a network, with every node representing some feature of the datasets, for example, a node can represent geological parameters like colour, hardness or lustre. Exploring subnetworks gives the researcher a specific view of the data required for the task at hand. GEMI is accessible through the DCO Data Portal (https://dx.deepcarbon.net/11121/6200-6954-6634-8243-CC). We describe our efforts in compiling GEMI, the Data Policies for usage and sharing, and the evaluation metrics for this data legacy.

data legacy↗

DOE OSTI2018

Loss of PiT-2 results in abnormal bone development and decreased bone mineral density and length in mice

Highlights: • PiT-2 deficiency decreased mineral density in craniofacial and long bones in mice. • Bone length was reduced in long bones in PiT-2 deficient mice. • Trabecular and cortical bone mineral density were decreased in PiT-2 deficient mice. • Static bone morphometric parameters were altered in PiT-2 deficient mice. • PiT-2 deficiency altered craniofacial bone morphology. Normal bone mineralization requires phosphate oversaturation in bone matrix vesicles, as well as normal regulation of phosphate metabolism via the interplay among bone, intestine, and kidney. In turn, derangement of phosphate metabolism greatly affects bone function and structure. The type III sodium-dependent phosphate transporters, PiT-1 and PiT-2, are believed to be important in tissue phosphate metabolism and physiological bone formation, but their requirement and molecular roles in bone remain poorly investigated. In order to decipher the role of PiT-2 in bone, we examined normal bone development, growth, and mineralization in global PiT-2 homozygous knockout mice. PiT-2 deficiency resulted in reduced vertebral column, femur, and tibia length as well as mandibular dimensions. Micro-computed tomography analysis revealed that bone mineral density in the mandible, femur, and tibia were decreased, indicating that maintenance of bone function and structure is impaired in both craniofacial and long bones of PiT-2 deficient mice. Both cortical and trabecular thickness and mineral density were reduced in PiT-2 homozygous knockout mice compared with wild-type mice. These results suggest that PiT-2 is involved in normal bone development and growth and plays roles in cortical and trabecular bone metabolism feasibly by regulating local phosphate transport and mineralization processes in the bone. Further studies that evaluate bone cell-specific loss of PiT-2 are now warranted and may yield insight into complex mechanisms of bone development and growth, leading to identification of new therapeutic options for patients with bone diseases.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2019

Temperature sensitivity of mineral-enzyme interactions on the hydrolysis of cellobiose and indican by β-glucosidase

Extracellular enzymes are essentially responsible for depolymerizing soil organic matter (SOM) in terrestrial ecosystems, and soil minerals are known to affect enzyme activity. Yet, the mechanisms and the effects of mineral-enzyme interactions on enzymatic degradation of organic matter remain poorly understood. In this study, we examined the adsorption of fungal β-glucosidase enzyme on minerals and time-dependent changes of enzymatic reactivity, measured by the degradation of two organic substrates (i.e., cellobiose and indican) under both cold (4°C) and warm (20 and 30°C) conditions. Hematite, kaolinite, and montmorillonite were used, to represent three common soil minerals with distinctly different surface charges and characteristics. β-glucosidase was found to sorb more strongly onto hematite and kaolinite than montmorillonite. All three minerals inhibited enzyme degradation of cellobiose and indican, likely due to the inactivation or hindrance of enzyme active sites. The mineral-bound β-glucosidase retained its specificity for organic substrate degradation, and increasing temperature from 4 to 30°C enhanced the degradation rates by 2–4 fold for indican and 5–9 fold for cellobiose. These results suggest that enzyme adsorption, mineral type, temperature, and organic substrate specificity are important factors influencing enzymatic reactivity and thus have important implications in further understanding and modeling complex enzyme-facilitated SOM transformations in terrestrial ecosystems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗