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DOE OSTI2020

Evaluation of the Change in Uranium Mobility in Sediments from the Hanford 300-FF-5 Stage B Polyphosphate Field Injection

The purpose of this study was to evaluate the change in uranium mobility in the periodically re-wetted zone (PRZ) and upper unconfined aquifer of the Hanford Site’s 300-FF-5 operable unit as a result of Stage B polyphosphate (PO 4 ) injections. These 300 Area sediments are beneath or near the former North Process Pond, which has previously been shown to contain metatorbernite [Cu(UO 2 ) 2 (PO 4 ) 2 •8H 2 O] and uranophane [Ca(UO 2 ) 2 (SiO 3 OH) 2 •5H 2 O], along with aqueous and adsorbed uranium (U), and small amounts of U in calcite as a result of acidic disposal with a significant number of co-contaminants. Previous laboratory-scale studies have identified multiple mechanisms that decrease uranium mobility with polyphosphate injection: (a) precipitation of a low-solubility uranium-phosphate mineral (autunite); (b) precipitation of a Ca-phosphate solid that incorporates U; (c) precipitation of Ca-phosphate mineral (apatite group minerals) that coats existing uranium phases (i.e., U in calcite, U in Fe-oxides), reducing uranium leaching; and (d) aqueous Ca-U-carbonate species adsorption onto apatite. Given the significant amount of apatite precipitation, other U phases such as carbonates could also coprecipitate with apatite. To quantify differences in solubility, leachability, and phases of uranium between pre- and post-PO 4 -treated sediments, different types of analyses were conducted, including analysis of uranium in (a) a carbonate solution extraction from sediment over 1000 h (41.67 days), (b) six sequential liquid extractions from sediment over approximately 1 week, (c) leaching of uranium from sediments in one dimensional (1-D) column experiments over 2 months, and (d) solid phase characterization of select sediments. An additional extraction and solid phase measurements were conducted to evaluate phosphate precipitate formation. Metals were also analyzed in sequential liquid extractions as indicators of (a) amendment injection delivery, (b) co-contaminant movement, and (c) changes in solid phases. Aqueous and solid phase carbonate measurements were also conducted to evaluate changes in carbonates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS2024

Variations in Apatite F, Cl, and OH Abundances in Primitive Achondrites: Evidence of Fractional Melting?

The apatite group minerals [Ca 5 (PO 4 ) 3 (F,Cl,OH)] are some of the primary mineralogical reservoirs for phosphorus on Earth and a common phosphate mineral within a broad range of extraterrestrial samples. Naturally occurring apatite hosts F, Cl, and OH as essential structural constituents, and all three make up the apatite endmembers fluorapatite, chlorapatite, and hydroxylapatite, respectively. Although apatite is one of the most common phosphate minerals in meteorites and rocks from Earth, it typically occurs at minor to trace abundances. Apatite has been widely used as a mineralogical tool to probe the interiors of both differentiated and undifferentiated parent bodies for information about volatiles; however, little work has been done on apatite F, Cl, and OH abundances of apatite from primitive achondrite meteorites. There are broad differences between apatite X -site chemistry in chondrite parent bodies (typically F-poor) compared to apatite from basaltic rocks from many achondrite parent bodies (Cl-poor, apart from Mars). These differences could indicate that planetary differentiation processes, namely melting, play an important role in the evolution of apatite X -site chemistry. In fact, some ordinary chondrite meteorites that exhibit evidence of minor impact melting have apatite with X -site compositions that are much more F-rich than typical chondrite apatite. McCubbin et al., hypothesized that the F-rich compositions of the apatite in ordinary chondrites affected by impact melting could be the result of apatite partially melting, driving the residual apatite to more F-rich compositions; however, they also indicated that degassing of the more volatile Cl and H may also contribute to the F-enrichment. To further test the partial melting hypothesis, we investigate the F, Cl, and OH (by difference) abundances of apatite from primitive achondrite parent bodies given that they are thought to come from partially differentiated parent bodies that represent residues after partial melting. Consequently, their apatites could provide valuable insights into the effects of melting on apatite X -site chemistry. In this study, we report F and Cl abundances of apatite from a broad array of primitive achondrite meteorites, and we develop a model for apatite fractional melting using known apatite-melt partitioning relationships. Together, we use these results to further elucidate the role of melting on apatite X -site compositions.

F M McCubbin↗

DOE OSTI2021

Phase Transitions in Natural Vanadinite at High Pressures

The structural stability of vanadinite, Pb 5 [VO 4 ] 3 Cl, is reported by high-pressure experiments using synchrotron radiation X-ray diffraction (XRD) and Raman spectroscopy. XRD experiments were performed up to 44.6 GPa and 700 K using an externally-heated diamond anvil cell (EHDAC), and Raman spectroscopy measurements were performed up to 26.8 GPa at room temperature. XRD experiments revealed a reversible phase transition of vanadinite at 23 GPa and 600 K, which is accompanied by a discontinuous volume reduction and color change of the mineral from transparent to reddish during compression. The high-pressure Raman spectra of vanadinite show apparent changes between 18.0 and 22.8 GPa and finally become amorphous at 26.8 GPa, suggesting structural transitions of this mineral upon compression. The structural changes can be distinguished by the emergence of a new vibrational mode that can be attributed to the distortion of [VO 4 ] and the larger distortion of the V–O bonds, respectively. The [VO 4 ] internal modes in vanadinite give isothermal mode Grüneisen parameters varying from 0.149 to 0.286, yielding an average VO 4 internal mode Grüneisen parameters of 0.202.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Thermodynamic characterization of synthetic lead-arsenate apatites with different halogen substitutions

Abstract Thermodynamic parameters have been measured for synthetic analogs of the mimetite-group minerals Pb5(AsO4)3X (X = OH, Cl, Br, I) belonging to the apatite supergroup. Phases precipitated from aqueous solutions under ambient conditions with well characterized structures and compositions were studied. For each phase, dissolution enthalpy was experimentally determined by oxide melt drop solution calorimetry in a molten solvent of sodium molybdate (3Na2O·4MoO3) at 976 K. The enthalpy of formation from the elements ΔHf,elo was calculated using thermochemical cycles and was −3030.6 ± 11.5, −3026.6 ± 15.8, −2967.6 ± 25.0, and −2993.1 ± 12.2 kJ/mol for Pb5.00(AsO4)3.00OH0.86(CO3)0.07, Pb5.00(AsO4)3.00Cl0.80(CO3)0.10, Pb5.00(AsO4)3.00Br0.80(CO3)0.10, and Pb5.00(AsO4)3.00I0.45OH0.35(CO3)0.10, respectively. These ΔHf,elo values exhibit typical trends for apatites: they increased (were less negative) with the increasing molar mass and ionic radius of X and decreased with the electronegativity and ionization energy of X. The compilation and comparison of data for Ca-, Pb-, P-, and As-apatites revealed correlations indicating that thermodynamic enthalpic stability is largely influenced by chemical factors (e.g., differences in electronegativities of the elements, ionization energy, or ionic characteristics of the bonds) and to a lesser extent by physical and geometric parameters in the crystal structure related to the mass and size of the X anion. Using the correlations, it was possible to estimate the value of hitherto unknown ΔHf,elo for Pb5(AsO4)3F, −3144.3 ± 66.5 kJ/mol. The observed relationships apply to the entire apatite supergroup and can be used to predict the values of ΔHf,elo for phases that have not been studied experimentally. The new data on environmentally significant phases will contribute to the modeling of mineral-water interactions, particularly for potential use in the remediation of soils and wastes contaminated with Pb and As and in the immobilization of radioactive waste containing I-129.

Geochemistry & Geophysics↗

NASA NTRS2017

Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (Xsite), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al., recently reported that the exchange coefficients vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

McCubbin, F. M.↗

DOE OSTI2024

Polymorphism of Pb 5 (PO 4 ) 3 OH δ within the LK-99 mixture

During the synthetic exploration targeting the polycrystalline compound LK-99, an unexpected phase, Pb 5 (PO 4 ) 3 OH δ , was identified as a byproduct. We elucidated the composition of this compound through single-crystal X-ray diffraction analysis. Subsequent synthesis of the target compounds was achieved via high-temperature solid-state pellet reactions. The newly identified Pb 5 (PO 4 ) 3 OH δ has an orthorhombic crystal structure with space group Pnma , representing a unique structure differing from the hexagonal apatite phases of Pb 10 (PO 4 ) 6 O and Pb 5 (PO 4 ) 3 OH. Comprehensive temperature- and magnetic-field-dependent magnetization studies unveiled a temperature-independent magnetic characteristic of Pb 5 (PO 4 ) 3 OH δ . Solid-state nuclear magnetic resonance spectroscopy was employed to decipher the origins of the phase stability and confirm the presence of hydrogen atoms in Pb 5 (PO 4 ) 3 OH δ . These investigations revealed the presence of protonated oxygen sites, in addition to the interstitial water molecules within the structure, which may play critical roles in stabilizing the orthorhombic phase.

Xu, Mingyu (ORCID:0000000171386009)↗

DOE OSTI2021

Binding mechanism and binding free energy of amino acids and citrate to hydroxyapatite surfaces as a function of crystallographic facet, pH, and electrolytes

Hydroxyapatite (HAP) is the major mineral phase in bone and teeth. The interaction of individual amino acids and citrate ions with different crystallographic HAP surfaces has remained uncertain for decades, creating a knowledge gap to rationally design interactions with peptides, proteins, and drugs. In this contribution, we quantify the binding mechanisms and binding free energies of the 20 end-capped natural amino acids and citrate ions on the basal (001) and prismatic (010)/(020) planes of hydroxyapatite at pH values of 7 and 5 for the first time at the molecular scale. We utilized over 1500 steered molecular dynamics simulations with highly accurate potentials that reproduce surface and hydration energies of (hkl) hydroxyapatite surfaces at different pH values. Charged residues demonstrate a much higher affinity to HAP than charge-neutral species due to the formation of superficial ion pairs and ease of penetration into layers of water molecules on the mineral surface. Binding free energies range from 0 to -60 kJ/mol and were determined with ~10% uncertainty. The highest affinity was found for citrate, followed by Asp(-) and Glu(-), and followed after a gap by Arg(+), Lys(+), as well as by His(+) at pH 5. The (hkl)-specific area density of calcium ions, the protonation state of phosphate ions, and subsurface directional order of the ions in HAP lead to surface-specific binding patterns. Amino acids without ionic side groups exhibit weak binding, between -3 and 0 kJ/mol, due to difficulties to penetrate the first layer of water molecules on the apatite surfaces. We explain recognition processes that remained elusive in experiments, in prior simulations, discuss agreement with available data, and reconcile conflicting interpretations. In conclusion, the findings can serve as useful input for the design of peptides, proteins, and drug molecules for the modification of bone and teeth-related materials, as well as control of apatite mineralization.

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.↗

NASA NTRS1982

The significance of Cl/P2O5 ratios from lunar samples

The Cl(r)/P2O5 ratios of lunar samples are reported to occur in three groups (Jovanovic and Reed, 1975; etc.). These data have been modeled as representative of three discrete volumes of differentiating magma and correlated with large convection cells and moon-wide heterogeneities. The assumptions inherent to their model are not valid. That the Cl(r)/P2O5 ratio of apatite or a rock is indicative of a magma system is unrealistic. A range of ratios can be generated during the fractionation of a magma. Apatite is not the major Cl- and P-bearing phase in most of the samples analyzed; rust, FeO(OH, Cl) and schreibersite, (FeNi)3P, occur in over 2/3 rds of the Apollo 16 rocks where they constitute 0.1-0.6 modal %, enough to account for most of the Cl(r) and P2O5 analyzed. Due to the complexities and presence of these minerals in soils and breccias, Cl(r)/P2O5 ratios have no real significance in non-igneous samples. However, basaltic rocks alone do not define any statistically significant Cl(r)P2O5 groupings.

Taylor, L. A.↗

DOE OSTI2020

Structural Assessment of Fluorine, Chlorine, Bromine, Iodine, and Hydroxide Substitutions in Lead Arsenate Apatites (Mimetites)–Pb 5 (AsO 4 ) 3 X

Five lead-arsenate apatites (mimetites)-Pb 5 (AsO 4 ) 3 X—where X denotes fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and hydroxide (OH)—were synthesized via precipitation from aqueous solutions. The crystal structures were determined through Rietveld refinement of powder synchrotron X-ray data. All the compounds crystallized in the hexagonal class symmetry (space group P6 3 /m). The Rietveld refinement indicated that mimetite-Cl, -Br, -I, and -OH had an anion deficiency at position X. Substitution of halogens in a mimetite structure brought about systematic changes in unit-cell parameters, interatomic distances, and metaprism twist angles φ, proportional to the substituted halogen’s ionic radius. Mimetite-OH did not follow the linear correlations determined within the series. Twist angle φ, a useful device for monitoring changes in apatite topology, ranged from 20.34° for mimetite-F to 11.42° for mimetite-I. The geometric method has been proposed for determining the diameter of hexagonal channels hosting halogens in apatites. A comparison of the results with halogenated pyromorphites showed similar systematic trends: the substitutions in mimetites have comparable effect on the interatomic distances as in their phosphorous analogues.

58 GEOSCIENCES↗

NASA NTRS2017

Petrology of Zircon-Bearing Diogenite Northwest Africa 10666

The howardite, eucrite, and diogenite (HED) meteorites are a group of achondrites thought to be derived from the asteroid 4 Vesta, though there is active debate as to whether all diogenites are part of the HED suite. Petrologic investigation of the HED meteorite group provides a means of understanding early planetary differentiation processes and early evolution of planets in our solar system. Diogenites are predominantly coarse grained ortho-pyroxenites with some samples containing appreciable amounts of clinopyroxene, olivine, chromite, and plagioclase. Accessory metal, troilite, and apatite are common. Many diogenites are brecciated, however, there are few poorly to unbrecciated samples. Diogenites are important because they may represent the lower crust of 4 Vesta. Although Mg isotope data indicates that the sources of diogenites are ancient, their crystallization ages are difficult to constrain due to their protracted thermal histories. The limited chronologic data for diogenites also limits the ability to test petrogenetic connections with eucrites and even parent body. A reliable and high closure-temperature isotope system, such as U-Pb in zircon, is needed to address the timing of diogenite igneous crystallization. Description of the textures and mineralogy of diogenites are essential to their classification and understanding their formation, in particular, whether all phases are petrogenetically related. Here, we present detailed petrographic data from a rare zircon-bearing feldspathic diogenite, Northwest Africa (NWA) 10666 and provide textural evidence for igneous crystallization of the zircon.

Tanner, T. B.↗

NASA NTRS2017

Volatiles in High-K Lunar Basalts

Chlorine is an unusual isotopic system, being essentially unfractionated ((delta)Cl-37 approximately 0 per mille ) between bulk terrestrial samples and chondritic meteorites and yet showing large variations in lunar (approximately -4 to +81 per mille), martian, and vestan (HED) samples. Among lunar samples, the volatile-bearing mineral apatite (Ca5(PO4)3[F,Cl,OH]) has been studied for volatiles in K-, REE-, and P (KREEP), very high potassium (VHK), low-Ti and high-Ti basalts, as well as samples from the lunar highlands. These studies revealed a positive correlation between in-situ (delta)Cl-37 measurements and bulk incompatible trace elements (ITEs) and ratios. Such trends were interpreted to originate from Cl isotopic fractionation during the degassing of metal chlorides during or shortly after the differentiation of the Moon via a magma ocean. In this study, we investigate the volatile inventories of a group of samples for which new-era volatile data have yet to be reported - the high-K (greater than 2000 ppm bulk K2O), high-Ti, trace element-rich mare basalts. We used isotope imaging on the Cameca NanoSIMS 50L at JSC to obtain the Cl isotopic composition [((Cl-37/(35)Clsample/C-37l/(35)Clstandard)-1)×1000, to get a value in per thousand (per mille)] which ranges from approximately -2.7 +/- 2 per mille to +16.1 +/- 2 per mille (2sigma), as well as volatile abundances (F & Cl) of apatite in samples 10017, 10024 & 10049. Simply following prior models, as lunar rocks with high bulk-rock abundances of ITEs we might expect the high-K, high-Ti basalts to contain apatite characterized by heavily fractionated (delta)Cl-37 values, i.e., Cl obtained from mixing between unfractionated mantle Cl (approximately 0 per mille) and the urKREEP reservoir (possibly fractionated to greater than +25 per mille.). However, the data obtained for the studied samples do not conform to either the early degassing or mixing models. Existing petrogentic models for the origin of the high-K, high-Ti basalts do not include urKREEP assimilation into their LMO cumulate sources. Therefore, Cl in these basalts either originated from source region heterogeneity or through assimilation or metasomatism by volatile and incompatible trace element rich materials. The new data presented here could provide evidence for the existence of region(s) in the lunar interior that are ITE-enriched and contain Cl that does not share isotopic affinities with lunar urKREEP, possibly representing the composition of the purported 'neuKREEP'.

Barnes, Jessica J.↗

NASA NTRS2019

Constraints on Martian Ancient Magmatic Processes Using Mineral Chemistry of Sedimentary Rocks in Gale Crater, Mars

If Mars has been assumed to be mostly basaltic for a long time, a series of recent discoveries have challenged this simplistic view. Orbital data indicated feldspar-rich rocks in Noachian terrains, likely supporting ancient evolved magmatism. The first indurated regolithic martian meteorite breccia NWA 7034, dated at 4.43 Gyr, contain several leucocratic felsic clasts identified as monzonitic and trachyandesitic, containing feldspars including K-spars and Na-rich plagioclases, pyroxenes, ilmenites and apatites. These clasts have been interpreted as the result of crystallization of a large impact pond. The Mars Science Laboratory rover (Curiosity), travelling within sedimentary bedrock on the floor of the Gale impact crater, discovered feldspar cumulates and a trachyandesite suggesting fractional crystallization of a basaltic melt. In addition, in the Bradbury group of fluvio-deltaic rocks (observed during the 1st 750 sols), sedimentary rocks are mostly comprised of secondary phases and detrital igneous minerals like feldspar, and pyroxene that are thought to come from Noachian-aged magmatic sources, although no definite origin and igneous processes have been inferred.

Payr, V.↗

NASA NTRS1973

Uranium concentration and distribution in six peridotite inclusions of probable mantle origin

Fission-track activation was used to investigate uranium concentration and distribution in peridotite inclusions in alkali basalt from six localities. Whole-rock uranium concentrations range from 24 to 82 ng/g. Most of the uranium is uniformly distributed in the major silicate phases - olivine, orthopyroxene, and clinopyroxene. Chromian spinels may be classified into two groups on the basis of their uranium content - those which have less than 10 ng/g and those which have 100 to 150 ng/g U. In one sample accessory hydrous phases, phlogopite and hornblende, contain 130 and 300 ng/g U, respectively. The contact between the inclusion and the host basalt is usually quite sharp. Glassy or microcrystalline veinlets found in some samples contain more than 1 microgram/g. Very little uranium is associated with microcrystals of apatite. These results agree with some earlier investigators, who have concluded that suboceanic peridotites contain too little uranium to account for normal oceanic heat flow by conduction alone.

Haines, E. L.↗

NASA NTRS1997

Mineral induction by immobilized phosphoproteins

Dentin phosphoproteins are thought to have a primary role in the deposition of mineral on the collagen of dentin. In this study we determined the type of binding between collagen and phosphoproteins necessary for mineral formation onto collagen fibrils and whether the phosphate esters are required. Bovine dentin phosphophoryn or phosvitin from egg yolk were immobilized on reconstituted skin type I collagen fibrils by adsorption or by covalent cross-linking. In some samples the ester phosphate was removed from the covalently cross-linked phosphoproteins by treatment with acid phosphatase. All samples were incubated at 37 degrees C in metastable solutions that do not spontaneously precipitate. Reconstituted collagen fibrils alone did not induce mineral formation. The phosphoproteins adsorbed to the collagen fibrils desorbed when the mineralization medium was added, and mineral was not induced. The mineral induced by the cross-linked phosphoproteins was apatite, and the crystals were confined to the surface of the collagen fibrils. With decreasing medium saturation the time required for mineral induction increased. The interfacial tensions calculated for apatite formation by either phosphoprotein cross-linked to collagen were about the same as that for phosphatidic acid liposomes and hydroxyapatite. This similarity in values indicates that the nucleation potential of these highly phosphorylated surfaces is about the same. It is concluded that phosphoproteins must be irreversibly bound to collagen fibrils for the mineralization of the collagen network in solutions that do not spontaneously precipitate. The phosphate esters of phosphoproteins are required for mineral induction, and the carboxylate groups are not sufficient.

Non-NASA Center↗

NASA NTRS2003

Purification, Crystallization, and Preliminary X-ray Analysis of Native Canavalin

The protein canavalin is a 7S vicilin, from the Jack Bean, Canavalis ensfomis. Canavalin is described as a seed storage protein, an energy source for a developing seed, as no other known activity or function has been found. The protein was first isolated and crystallized by Sumner and Howell (J. Biol. Chem. 113, 607-610, 1936). Canavalin spontaneously crystallizes after proteolytic cleavage at neutral pH, which removes residues 1-46, 224-245, and 325-330 and produces peptides of approximately 25, 13, and 12 kDa. Preliminary gel filtration experiments indicated the presence of nucleic acid with the uncleaved protein. We developed a dual column procedure, ion exchange followed by hydroxy apatite chromatography, that effectively removes the nucleic acid and yields an essentially pure uncut canavalin preparation with an OD 280/260 ratio of approximately 1.9-2.0. Standard crystallization screens using this material gave a number of positive results having a common requirement for alcohols and Mg(2+) ion, with crystals typically appearing within a day or less. Optimization experiments to date have shown that we can obtain crystals from pH 6.5 to pH 8.2, using MPD from 5 to 20% and 0.05 to 0.2M Mg(2+) (sulfate or acetate). The crystals are of space group P2(sub 1)2(sub 1)2(sub 1), unit cell dimensions, and a complete data set to 1.5 Angstroms, resolution has now been collected at a synchrotron source. Most importantly, the crystals are not twinned, a persistent problem with the most commonly obtained rhombohedral form of proteolytically cleaved canavalin.

Pusey, Marc↗

NASA NTRS2024

Revisiting the petrogenesis of pyroclastic glass bead deposits at the Apollo 15 and 17 sites

The Apollo 15 low-titanium and Apollo 17 high-titanium pyroclastic glass beads are amongst the most primitive magmatically derived samples obtained from the Moon. Two key samples, the low-Ti Apollo 15426 green glass clod and the high-Ti Apollo 74220 orange glass are morphologically distinct, where the Apollo 15 beads are larger (~ 107 μm along maximum axis) and more fractured, and the Apollo 17 are smaller (~42 μm) and less fractured. In this study, holohyaline beads as well as crystallized beads were examined from both samples. Crystallized beads show compositional variability in major, minor, and trace elements and enable examination of magmatic mineral fractionation processes during cooling of both deposits. The Apollo 15426 beads experienced variable olivine crystallization, whereas the Apollo 74220 beads experienced both olivine and ilmenite crystallization. Holohyaline beads from both deposits show more limited major, minor, and trace element variability than their crystallized counterparts. Trace element abundance data for individual holohyaline beads show that in Apollo 74220, they are tightly clustered at ~30 × Carbonaceous Ivuna chondrite [CI] with negative Eu anomalies and subchondritic Nb/Ta, and interpreted to reflect the presence of late-stage magma ocean cumulate overturned into an otherwise primitive mantle source. Incompatible trace element abundances for holohyaline beads in 15426 are supra-chondritic from ~8 × CI, to >80 × CI, with pronounced relative depletions in Sr and Eu for the most incompatible element enriched beads, which represent a distinct bead group within the deposit. Apollo 15426 beads have elevated Ni and Co abundances at the edges of the beads compared to their centers. These data are interpreted to reflect a more complex magmatic evolution of the 15426 deposit, beginning with: (i) initial magma generation, storage and assimilation within shallower low-Ca and high-Ca pyroxene bearing magma ocean cumulates (15B,C); (ii) mobilization of the earlier magmas by more recently generated primitive magmas (15A); (iii) eruption and crystallization of some beads (15D,E), and (iv) later jumbling of the deposit, possible impact contamination and addition of exotic bead components (J Group). In contrast, the 74220 data shows no discernable difference between Ni and Co abundances at the edges and centers supporting prior observations for limited melt fractionation and an absence of meteoritic components. It is further suggested that both deposits are likely to have been formed in the presence of a transient atmosphere. Using 74220 melt compositions from this study, post-entrapment crystallization abundances range from 266 to 1130 micrograms/g for H 2 O, 36 to 68 micrograms/g for F, 441 to 832 micrograms/g for S, and zero to 2.31 micrograms/g for Cl, consistent with prior studies and suggesting up to ~0.1 wt.% H 2 O in the melt, with considerably less in the source. The role that late-stage magma ocean cumulates rich in ilmenite, apatite and high-Ca pyroxene might play in modifying this volatile element estimate, however, casts remaining doubt on the volatile element abundance and evolution of the primitive Moon.

Moon↗

NASA NTRS2019

The Sariçiçek Howardite Fall in Turkey: Source Crater of HED Meteorites on Vesta and Impact Risk of Vestoids

The Sariçiçek howardite meteorite shower consisting of 343 documented stones occurred on September 2, 2015 in Turkey and is the first documented howardite fall. Cosmogenic isotopes show that Sariçiçek experienced a complex cosmic‐ray exposure history, exposed during ~12–14 Ma in a regolith near the surface of a parent asteroid, and that an ~1 m sized meteoroid was launched by an impact 22 ± 2 Ma ago to Earth (as did one‐third of all HED meteorites). SIMS dating of zircon and baddeleyite yielded 4550.4 ± 2.5 Ma and 4553 ± 8.8 Ma crystallization ages for the basaltic magma clasts. The apatite U‐Pb age of 4525 ± 17 Ma, K‐Ar age of ~3.9 Ga, and the U,Th‐He ages of 1.8 ± 0.7 and 2.6 ± 0.3 Ga are interpreted to represent thermal metamorphic and impact‐related resetting ages, respectively. Petrographic; geochemical; and O‐, Cr‐, and Ti‐isotopic studies confirm that Sariçiçek belongs to the normal clan of HED meteorites. Petrographic observations and analysis of organic material indicate a small portion of carbonaceous chondrite material in the Sariçiçek regolith and organic contamination of the meteorite after a few days on soil. Video observations of the fall show an atmospheric entry at 17.3 ± 0.8 km/s from NW; fragmentations at 37, 33, 31, and 27 km altitude; and provide a pre‐atmospheric orbit that is the first dynamical link between the normal HED meteorite clan and the inner Main Belt. Spectral data indicate the similarity of Sariçiçek with the Vesta asteroid family (V‐class) spectra, a group of asteroids stretching to delivery resonances, which includes (4) Vesta. Dynamical modeling of meteoroid delivery to Earth shows that the complete disruption of a ~1 km sized Vesta family asteroid or a ~10 km sized impact crater on Vesta is required to provide sufficient meteoroids ≤4 m in size to account for the influx of meteorites from this HED clan. The 16.7 km diameter Antionia impact crater on Vesta was formed on terrain of the same age as given by the 4He retention age of Sariçiçek. Lunar scaling for crater production to crater counts of its ejecta blanketshow it was formed ~22 Ma ago.

Unsalan, Ozan↗