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NASA NTRS1973

Minor and trace elements in some meteoritic minerals.

Despite the information available (Mason, 1971) on trace elements in different types of meteorites, relatively little is known about the distribution of these elements among the individual mineral phases. The mineral phases including olivine, orthopyroxene, clinipyroxene, troilite, nickel-iron, plagioclase, chromite, and the phosphates were separated from several meteorites. The purified minerals were analyzed for trace and minor elements by spark source mass spectrometry and instrumental neutron activation analysis. The elements are classified as siderophile, lithophile, and chalcophile.

Allen, R. O., Jr.↗

NASA NTRS2016

Northwest Africa 8535 and Northwest Africa 10463: New Insights into the Angrite Parent Body

The angrite meteorites are valuable samples of igneous rocks formed early in Solar System history (approx.4.56 Ga, summarized in [1]). This small meteorite group (approx.24 individually named specimens) consists of rocks with somewhat exotic mineral compositions (e.g., high Ca olivine, Al-Ti-bearing diopside-hedenbergite, calcium silico-phosphates), resulting in exotic bulk rock compositions. These mineral assemblages remain fairly consistent among angrite samples, which suggests they formed due to similar processes from a single mantle source. There is still debate over the formation process for these rocks (see summary in [1]), and analysis of additional angrite samples may help to address this debate. Toward this end, we have begun to study two new angrites, Northwest Africa 8535, a dunite, and Northwest Africa 10463, a basaltic angrite.

Santos, A. R.↗

NASA NTRS1993

A study of carbonates, sulfates, and phosphates using thermal emission spectroscopy

Thermal emission spectroscopy is useful for identifying mineralogies including carbonates, sulfates, and phosphates. Each of these groups of minerals has a distinct emissivity profile that allows for general identification (e.g., carbonate). Laboratory data are being collected that suggest the potential for determining specific composition of these minerals (e.g., calcite, magnesite). Previous studies of Mars suggest that the above groups of minerals should be present. On Mars fine-grained mineralogies are likely to be intimately mixed due to aeolian activity. Mixtures of calcite with palagonite will be studied to determine the volume percent requirement for salt identification and to understand the complexities of fine-grained mixtures observed by thermal emission. Further work with mixtures will include sulfate and phosphate mineralogies.

Wenrich, M. L.↗

DOE OSTI2024

Unraveling iron oxides as abiotic catalysts of organic phosphorus recycling in soil and sediment matrices

In biogeochemical phosphorus cycling, iron oxide minerals are acknowledged as strong adsorbents of inorganic and organic phosphorus. Dephosphorylation of organic phosphorus is attributed only to biological processes, but iron oxides could also catalyze this reaction. Evidence of this abiotic catalysis has relied on monitoring products in solution, thereby ignoring iron oxides as both catalysts and adsorbents. Here we apply high-resolution mass spectrometry and X-ray absorption spectroscopy to characterize dissolved and particulate phosphorus species, respectively. In soil and sediment samples reacted with ribonucleotides, we uncover the abiotic production of particulate inorganic phosphate associated specifically with iron oxides. Reactions of various organic phosphorus compounds with the different minerals identified in the environmental samples reveal up to twenty-fold greater catalytic reactivities with iron oxides than with silicate and aluminosilicate minerals. Importantly, accounting for inorganic phosphate both in solution and mineral-bound, the dephosphorylation rates of iron oxides were within reported enzymatic rates in soils. Our findings thus imply a missing abiotic axiom for organic phosphorus mineralization in phosphorus cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1992

Geochemistry and petrology of primitive achondrite meteorites LEW 88280, MAC 88177, ALHA 81187, EET 84302, and LEW 88663

Primitive achondrites are meteorites that have mineral and bulk chemical compositions similar to the most primitive meteorites (chondrites) but have textures similar to more evolved meteorites (achondrites). The unique geochemistry and texture of the primitive achondrites suggest these meteorites may be genetic intermediates between chondrites and achondrites and may preserve evidence of processes occurring in the early solar system. Five primitive achondrites LEW 88280, MAC 88177, ALHA 81187, EET 84302, and LEW 88663 were examined in this study in order to classify the meteorites and to determine processes that have affected them. Bulk chemical analyses of Nap, K2O, CaO, FeO, Cr, Co, Ni, Sc, Ir, Au, As, Sb, Se, Br, Cs, Ba, La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu were determined for each meteorite by Instrumental Neutron Activation Analysis (INAA). Concentrations of Hf, U, and Th were determined for some meteorites. Polished thin sections of the five meteorites were examined in transmitted and reflected light microscopy to identify minerals and examine petrographic relationships. Minerals found in the meteorites include olivine, orthopyroxene, clinopyroxene, plagioclase, Cr-spinel, phosphates, troilite, kamecite, and taenite along with other minor phases. Mineral compositions were determined with an electron microprobe. The initial study suggests that the meteorites have been altered by metamorphic processes although igneous processes may also have played a role in the evolution of these rocks. Further studies of isotope and bulk chemistry are planned for these meteorites.

Field, Stephen W.↗

NASA NTRS2007

A Rb-Sr and Sm-Nd Isotope Geochronology and Trace Element Study of Lunar Meteorite LaPaz Icefield 02205

Rubidium-strontium and samarium-neodymium isotopes of lunar meteorite LaPaz Icefield (LAP) 02205 are consistent with derivation of the parent magma from a source region similar to that which produced the Apollo 12 low-Ti olivine basalts followed by mixing of the magma with small amounts (1 to 2 wt%) of trace element-enriched material similar to lunar KREEP-rich sample SaU 169. The crystallization age of LAP 02205 is most precisely dated by an internal Rb-Sr isochron of 2991+/-14 Ma, with an initial Sr-87/Sr-88 at the time of crystallization of 0.699836+/-0.000010. Leachable REE-rich phosphate phases of LAP 02205 do not plot on a Sm-Nd mineral isochron, indicating contamination or open system behavior of the phosphates. Excluding anomalous phases from the calculation of a Sm-Nd isochron yields a crystallization age of 2992+/-85 (initial Epsilon Nd-143 = +2.9+/-0.8) that is within error of the Rb-Sr age, and in agreement with other independent age determinations for LAP 02205 from Ar-Ar and U-Pb methods. The calculated Sm-147/Nd-144 source ratios for LAP 02205, various Apollo 12 and 15 basalts, and samples with strong affinities to KREEP (SaU 169, NWA 773, 15386) are uncorrelated with their crystallization ages. This finding does not support the involvement of a common KREEP component as a heat source for lunar melting events that occurred after crystallization of the lunar magma ocean.

Rankenburg, K.↗

NASA NTRS1999

Mineral induced formation of pentose-2,4-bisphosphates

Formation of rac.-pentose-2,4-bisphosphates is demonstrated, starting from glycolaldehyde phosphate and glyceraldehyde-2-phosphate, and induced by mixed valence double layer metal hydroxide minerals. The reactions proceed from dilute aqueous reactant solutions (1.5 mM) at near neutral pH. Conditions have been established, where ribose-2,4-bisphosphate is the major product (approximately 48%) among the pentose-2,4-bisphosphates, which are formed with up to 25% yield.

Non-NASA Center↗

DOE OSTI2022

Probing elemental speciation in hydrochar produced from hydrothermal liquefaction of anaerobic digestates using quantitative X-ray diffraction

Valorization of hydrochar, a solid byproduct from hydrothermal liquefaction (HTL) of anaerobically-digested agriculture wastes (digestates), requires fundamental knowledge of elemental speciation. This study investigated the effects of reaction temperatures (320–360 °C), digestate pH (3.5–8), and digestate cellulose-to-lignin ratios (0.2–1.8) on the speciation (chemical form) and composition of organics and inorganics in hydrochars produced during hydrothermal treatment. Quantitative X-ray diffraction (XRD) method was the primary technique used to characterize hydrochars. The comprehensive XRD pattern processing including the Rietveld refinement protocols demonstrated that the organic phase was comprised of mostly crystalline monocyclic, heterocyclic, and polycyclic aromatics with diverse aliphatic and aromatic substituents, while the inorganic mineral phase consisted of calcium-phosphates, magnesium-phosphates, calcium-carbonates, and magnesium-carbonates. Further, XRD results were validated by the elemental yields of products and the distribution of chemical functionalities measured using solid-state nuclear magnetic resonance (NMR) spectroscopy. The characterization data were used to evaluate proposed mechanistic pathways using compositional analysis of biocrude and aqueous-phase coproducts. Mechanistic pathways developed in the study suggested that benzoic acids, phenols, benzaldehydes, phenolic aldehydes, α-dicarbonyls, and α-hydroxycarbonyls were responsible for the precipitation of organics through various reactions depending on operating conditions. Meanwhile, the formation of inorganic compounds appeared to be consistently represented by reactions including dehydration, hydrolysis, endergonic reduction, and structure rearrangement of native minerals in the digestates. This study provides basic knowledge needed to create and assess potential elemental speciation pathways. In addition, the results of the study facilitate the specification of process conditions to optimize targeted utilization routes of hydrochar for more economically-feasible and sustainable HTL processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2012

U-Pb Dating of Zircons and Phosphates in Lunar Meteorites, Acapulcoites and Angrites

Zircon U-Pb geochronology has made a great contribution to the timing of magmatism in the early Solar System [1-3]. Ca phosphates are another group of common accessory minerals in meteorites with great potential for U-Pb geochronology. Compared to zircons, the lower closure temperatures of the U-Pb system for apatite and merrillite (the most common phosphates in achondrites) makes them susceptible to resetting during thermal metamorphism. The different closure temperatures of the U-Pb system for zircon and apatite provide us an opportunity to discover the evolutionary history of meteoritic parent bodies, such as the crystallization ages of magmatism, as well as later impact events and thermal metamorphism. We have developed techniques using the Cameca IMS-1280 ion microprobe to date both zircon and phosphate grains in meteorites. Here we report U-Pb dating results for zircons and phosphates from lunar meteorites Dhofar 1442 and SaU 169. To test and verify the reliability of the newly developed phosphate dating technique, two additional meteorites, Acapulco, obtained from Acapulco consortium, and angrite NWA 4590 were also selected for this study as both have precisely known phosphate U-Pb ages by TIMS [4,5]. Both meteorites are from very fast cooled parent bodies with no sign of resetting [4,5], satisfying a necessity for precise dating.

Zhou, Q.↗

DOE OSTI2025

Unraveling Anion-Specific Inhibition and Structural Modulation of Gibbsite Crystallization: Implications for Aluminum Mobility in Natural and Engineered Systems

Gibbsite (α-Al(OH) 3 , sometimes designated as γ-Al(OH) 3 ) plays a crucial role in the chemistry of aluminum in the environment and industry, yet its crystallization behavior under multianionic conditions is not well understood. Here, in this study, we investigate how six common anions─fluoride (F – ), chloride (Cl – ), bromide (Br – ), nitrate (NO 3 – ), sulfate (SO 4 2– ), and phosphate (PO 4 3– )─influence the mineralization, structure, and morphology of gibbsite at room temperature. The results show that PO 4 3– , SO 4 2– , and F – strongly inhibit gibbsite formation, stabilizing amorphous or alternative crystalline phases such as nordstrandite and cryolite. On the contrary, Cl – , Br – , and NO 3 – allow partial to complete crystallization of gibbsite without significant morphological changes. Solid-state 27 Al magic angle spinning nuclear magnetic resonance provides crucial insight into aluminum coordination environments in both crystalline and amorphous phases, distinguishing between octahedral, pentahedral, and tetrahedral Al species. The density functional theory calculations reveal a direct correlation between the Al–X bond strength and the inhibition of crystallization, following the order: PO 4 3– > SO 4 2– > F – > NO 3 – > Cl – > Br – . These findings offer molecular-scale insights into anion-specific effects on aluminum hydroxide nucleation and transformation, improving the understanding of gibbsite formation and aluminum cycling in soils, phosphate retention, contaminant immobilization, and waste treatment strategies in nuclear and industrial settings. These insights can also guide the controlled synthesis of aluminum hydroxide materials with tailored crystallinity and morphology via liquid-assisted methods.

Anions effect↗

DOE OSTI2023

Mineralogy and petrology of fine‐grained samples recovered from the asteroid (162173) Ryugu

Abstract Samples returned from the carbonaceous asteroid (162173) Ryugu by the Hayabusa2 mission revealed that Ryugu is composed of materials consistent with CI chondrites and some types of space weathering. We report detailed mineralogy of the fine‐grained Ryugu samples allocated to our “Sand” team and report additional space weathering features found on the grains. The dominant mineralogy is composed of a fine‐grained mixture of Mg‐rich saponite and serpentine, magnetite, pyrrhotite, pentlandite, dolomite, and Fe‐bearing magnesite. These grains have mineralogy comparable to that of CI chondrites, showing severe aqueous alteration but lacking ferrihydrite and sulfate. These results are similar to previous works on large Ryugu grains. In addition to the major minerals, we also find many minerals that are rare or have not been reported among CI chondrites. Accessory minerals identified are hydroxyapatite, Mg‐Na phosphate, olivine, low‐Ca pyroxene, Mg‐Al spinel, chromite, manganochromite, eskolaite, ilmenite, cubanite, polydymite, transjordanite, schreibersite, calcite, moissanite, and poorly crystalline phyllosilicate. We also show scanning transmission electron microscope and scanning electron microscope compositional maps and images of some space‐weathered grains and severely heated and melted grains. Although our mineralogical results are consistent with that of millimeter‐sized grains, the fine‐grained fraction is best suited to investigate impact‐induced space weathering.

Geochemistry & Geophysics↗

NASA NTRS1999

The age of the carbonates in martian meteorite ALH84001

The age of secondary carbonate mineralization in the martian meteorite ALH84001 was determined to be 3.90 +/- 0.04 billion years by rubidium-strontium (Rb-Sr) dating and 4.04 +/- 0.10 billion years by lead-lead (Pb-Pb) dating. The Rb-Sr and Pb-Pb isochrons are defined by leachates of a mixture of high-graded carbonate (visually estimated as approximately 5 percent), whitlockite (trace), and orthopyroxene (approximately 95 percent). The carbonate formation age is contemporaneous with a period in martian history when the surface is thought to have had flowing water, but also was undergoing heavy bombardment by meteorites. Therefore, this age does not distinguish between aqueous and impact origins for the carbonates.

Carbonates/analysis↗

NASA NTRS2017

Constraints on Mechanisms of Chondrule Formation from Chondrule Precursors and Chronology of Transient Heating Events in the Protoplanetary Disk

The mineralogy, petrography, and oxygen-isotope compositions of porphyritic chondrules—dominant chondrule type in most chondrite groups—suggest formation by incomplete melting of isotopically diverse precursors during localized transient heating events in dust-rich regions of the protoplanetary disk characterized by 16O-poor compositions (D17Odust+gas~ –7‰ to +4‰) relative to the inferred Sun’s value (D17O ~ –28 ± 2‰). The chondrule precursors included Ca,Al-rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), chondrules of earlier generations, fine-grained matrix-like material, and possibly fragments of pre-existing planetesimals. Like porphyritic chondrules, igneous CAIs formed by melting of isotopically diverse precursors during transient heating events, but in an isotopically distinct, solar-like reservoir of the protoplanetary disk (D17O dust + gas ~ –24‰), probably near the proto Sun. Based on a narrow range of the initial 26Al/27Alratios inferred from the internal Al-Mg isochrons in igneous CAIs, their melting started at the very beginning of Solar System formation (t0), defined by the CV CAIs with U-corrected Pb-Pb age of 4567.3 ± 0.16 Ma and the canonical 26Al/27Al ratio of (5.25 ± 0.02) ¥ 10–5, and lasted at least 0.3 Ma. The U-corrected Pb-Pb absolute and 26Al-26Mg relative ages of porphyritic chondrules from type 3 ordinary, CO, CV, and CR carbonaceous chondrites (assuming uniform distribution of 26Al in the disk at the canonical level) suggest chondrule formation started at t0 and lasted for about 4 Ma. These observations may preclude formation of the majority of porphyritic chondrules by splashing of differentiated planetesimals and by collisions between planetesimals; instead, they are consistent with melting of dust balls by bow shocks or magnetized turbulence in the disk. Some porphyritic chondrules in equilibrated (petrologic type 4–6) ordinary chondrites contain relict fragments of coarse-grained chromite, ilmenite, phosphates, and albitic plagioclase. The similar mineral assemblage is commonly observed in type 4–6 ordinary chondrites, but is absent in type 3 chondrites, suggesting these chondrules formed by incomplete melting of thermally metamorphosed ordinary chondrite material, possibly by impacts. The CB metal-rich carbonaceous chondrites contain exclusively magnesian non-porphyritic chondrules crystallized from complete melts. These chondrules formed in a gas-melt plume generated by a hypervelocity (≥20 km/s) collision between planetesimals ~4.8 Ma after t0 in a transition or a debris disk. One of the colliding bodies was probably differentiated. The CH metal-rich carbonaceous chondrites contain chondrules formed by different mechanisms. The magnesian non-porphyritic chondrules formed in the CB impact plume ~4.8 Ma after t0. The chemically diverse (magnesian, ferroan, and Al-rich) porphyritic chondrules formed by incomplete melting of isotopically diverse precursors in the protoplanetary disk, most likely prior the CB impact plume event. We conclude that there are multiple mechanisms of chondrule formation that operated over the entire life-time of the disk.

Chondrules↗

NASA NTRS1974

Prevention of bone mineral changes induced by bed rest: Modification by static compression simulating weight bearing, combined supplementation of oral calcium and phosphate, calcitonin injections, oscillating compression, the oral diophosphonatedisodium etidronate, and lower body negative pressure

The phenomenon of calcium loss during bed rest was found to be analogous to the loss of bone material which occurs in the hypogravic environment of space flight. Ways of preventing this occurrence are investigated. A group of healthy adult males underwent 24-30 weeks of continuous bed rest. Some of them were given an exercise program designed to resemble normal ambulatory activity; another subgroup was fed supplemental potassium phosphate. The results from a 12-week period of treatment were compared with those untreated bed rest periods. The potassium phosphate supplements prevented the hypercalciuria of bed rest, but fecal calcium tended to increase. The exercise program did not diminish the negative calcium balance. Neither treatment affected the heavy loss of mineral from the calcaneus. Several additional studies are developed to examine the problem further.

Schneider, V. S.↗

DOE OSTI2020

Controls on Iron Reduction and Biomineralization over Broad Environmental Conditions as Suggested by the Firmicutes Orenia metallireducens Strain Z6

Microbial iron reduction is a ubiquitous biogeochemical process driven by diverse microorganisms in a variety of environments. However, it is often difficult to separate the biological from the geochemical controls on bioreduction of Fe(III) oxides. In this study, we investigated the primary driving factor(s) that mediate secondary iron mineral formation over a broad range of environmental conditions using a single dissimilatory iron reducer, Orenia metallireducens strain Z6. A total of 17 distinct geochemical conditions were tested with differing pH (6.5–8.5), temperature (22–50 °C), salinity (2–20% NaCl), anions (phosphate and sulfate), electron shuttle (anthraquinone-2,6-disulfonate), and Fe(III) oxide mineralogy (ferrihydrite, lepidocrocite, goethite, hematite, and magnetite). The observed rates and extent of iron reduction differed significantly with k int between 0.186 and 1.702 mmol L –1 day –1 and Fe(II) production ranging from 6.3% to 83.7% of the initial Fe(III). Using X-ray absorption and scattering techniques (EXAFS and XRD), we identified and assessed the relationship between secondary minerals and the specific environmental conditions. It was inferred that the observed bifurcation of the mineralization pathways may be mediated by differing extents of Fe(II) sorption on the remaining Fe(III) minerals. These results expand our understanding of the controls on biomineralization during microbial iron reduction and aid the development of practical applications.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1999

The Thermal Emission Imaging System (THEMIS) Instrument for the Mars 2001 Orbiter

The primary objective of the Thermal Emission Imaging System (THEMIS) on the Mars Surveyor '01 Orbiter is to study the composition of the Martian surface at high spatial resolution. THEMIS will map the surface mineralogy using multi-spectral thermal infrared images in 8 spectral bands from 6.5 to 14.5 microns. In addition, a band centered at 15 microns will be used to map atmospheric temperatures and provide an important aid in separating the surface and atmospheric components. The entire planet will be mapped at 100 m resolution within the available data volume using a multi-spectral, rather than hyperspectral, imaging approach. THEMIS will also acquire 20 m resolution visible images in up to 5 spectral bands using a replica of the Mars 98 Orbiter (MARCI) and Lander (MARDI) cameras. Over 15,000 panchromatic (3,000 5-color), 20 x 20 km images will be acquired for morphology studies and landing site selection. The thermal-infrared spectral region contains the fundamental vibrational absorption bands of most minerals which provide diagnostic information on mineral composition. All geologic materials, including carbonates, hydrothermal silica, sulfates, phosphates, hydroxides, silicates, and oxides have strong absorptions in the 6.5-14.5 micron region. Silica and carbonates, which are key diagnostic minerals in thermal spring deposits, are readily identified using thermal-IR spectra. In addition, the ability to identify all minerals allows the presence of aqueous minerals to be interpreted in the proper geologic context. An extensive suite of studies over the past 35 years has demonstrated the utility of vibrational spectroscopy for the quantitative determination of mineralogy and petrology. The fundamental vibrations within different anion groups, such as C03, S04, P04, and SiO4, produce unique, well separated spectral bands that allow carbonates, sulfates, phosphates, silicates, oxides, and hydroxides to be readily identified. Additional stretching and bending modes involving major cations, such as Mg, Fe, Ca, and Na, allow Further mineral identification, such as the excellent discriminability of minerals within the silicate and carbonate groups.

Christensen, P. R.↗

NASA NTRS1992

FT-IR microscopic mappings of early mineralization in chick limb bud mesenchymal cell cultures

Chick limb bud mesenchymal cells differentiate into chondrocytes and form a cartilaginous matrix in culture. In this study, the mineral formed in different areas within cultures supplemented with 4 mM inorganic phosphate, or 2.5, 5.0, and 10 mM beta-glycerophosphate (beta GP), was characterized by Fourier-transform infrared (FT-IR) microscopy. The relative mineral-to-matrix ratios, and distribution of crystal sizes at specific locations throughout the matrix were measured from day 14 to day 30. The only mineral phase detected was a poorly crystalline apatite. Cultures receiving 4 mM inorganic phosphate had smaller crystals which were less randomly distributed around the cartilage nodules than those in the beta GP-treated cultures. beta GP-induced mineral consisted of larger, more perfect apatite crystals. In cultures receiving 5 or 10 mM beta GP, the relative mineral-to-matrix ratios (calculated from the integrated intensities of the phosphate and amide I bands, respectively) were higher than in the cultures with 4 mM inorganic phosphate or in the in vivo calcified chick cartilage.

NASA Discipline Musculoskeletal↗

DOE OSTI2024

Interactions between phosphate and arsenic in iron/biochar-treated groundwater: Corrosion control insights from column experiments

An increasing number of studies have reported the coexistence of arsenic (As) and phosphorus at high concentrations in groundwater, which threatens human health and increases the complexity of groundwater remediation. However, limited work has been done regarding As interception in the presence of phosphate in flowing systems. In this study, a series of experiments were conducted to evaluate the interactions between phosphate and As during As removal by iron (Fe)-based biochar (FeBC). The addition of phosphate promoted As removal by FeBC in the batch and column experiments. X-ray absorption near edge structure (XANES) analysis provided evidence of simultaneous oxidation and reduction of trivalent arsenic in the FeBC column experiment, accompanied by corrosive Fe oxidation. However, the addition of phosphate enhanced As stabilization, attributed to the As-incorporated Fe-Ca-phosphates precipitates. The involvement of phosphate decelerated the Fe corrosion and the formation of secondary minerals in the column, mediating the risk of passivation and clogging. The As retained by Fe-Ca-phosphate precipitates was more readily oxidized, resulting in higher proportions of pentavalent arsenic. In conclusion, the results of this work identify the corrosion control and sustained-release roles of phosphate in FeBC application, informing the perspective of FeBC in As-contaminated groundwater remediation and providing new insights into the interactions between phosphate and As.

54 ENVIRONMENTAL SCIENCES↗