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244 records · Page 14

Microstructural Evolution of the Civet Cat Norite (72255)

The ‘Civet Cat Norite’ is a ~ 2.5 cm clast within the Apollo impact melt breccia sample 72255 collected during Apollo 17 EVA 2 at Boulder 1. The norite is primarily composed of plagioclase and orthopyroxene with fine-scale exsolution lamellae of augite. The plagioclase and orthopyroxene (OPX) coexist with minor quartz and augitic clinopyroxene (CPX), and accessory apatite, baddeleyite, chromite, ilmenite, loveringite, merrillite, rutile and zircon. The major minerals range from 1 to 4 mm in size and show a cataclastic texture indicated by banding of the light and dark phases]. The chemical composition of the orthopyroxene, augitic exsolution lamellae, and exsolved oxides suggest the norite crystallized in the lower crust of the Moon (10 – 70 km depth) and was subsequently excavated by impact(s). Shock pressure estimates for the norite range from 15 – 35 GPa based on maskeleynite formation within the plagioclase, kink banding in pyroxenes, and granular recrystallization in the accessory phosphates. Previous Rb-Sr and 40 Ar/ 39 Ar analyses recalculated with modern decay constants yield relatively young ages of 4.16 ± 0.05 Ga and 3.99 ± 0.03 Ga, respectively. However, recent U-Pb analyses of some zircon grains from within the Civet Cat yield an age of 4.45 ± 0.03 Ga. While this is the oldest age for any rock recovered from the Moon, the full age spread of zircon from the Civet Cat range from ca. 4.46 to 4.02 Ga, indicating variable Pb-loss and complicating interpretation of the primary age. Recent atom probe analyses indicate minimal Pb mobilization within the oldest zircon grain from Civet Cat, supporting the interpretation that these ancient zircon ages reflect the age of the norite, rather than an apparent antiquity caused by reverse discordance. To investigate the potential antiquity and deep crustal origin of the Civet Cat norite, we have undertaken high resolution microstructural analyses of the major, minor, and accessory minerals to characterize the primary igneous textures and secondary overprinting by impact and metamorphism. The employed analytical techniques include scanning electron microscope-based electron backscatter diffraction (EBSD) analyses, electron probe microanalyzer (EPMA) chemical analyses, and transmission electron microscopy (TEM) of pyroxene, plagioclase, quartz, zircon, and phosphates.

T M Erickson↗

The Isotopic Composition of Molecular Water Formed by Hydrogen Reduction of Iron Oxides: A Proxy for Endogenous Water Formed From Solar Wind Implantation

Many workers have successfully utilized a variety of lunar materials to infer the sources and processing history of volatiles on the Moon. In situ techniques via NanoSIMS have enabled a plethora of hydrogen isotope measurements of isolated grains in regolith and apatite within igneous rocks, revealing an extraordinarily large range of δD values from ~ -900 to +1000‰. The lowest of these δD values are related to the incorporation of solar wind hydrogen, which is pure 1 H. Exposure to solar wind results in structural damage to crystalline phases, forming ubiquitous tens-to-hundreds of nanometer thick amorphous rims on mature regolith grains. Solar wind implantation of H + is also is also thought to result in the formation of nanophase Fe 0 (npFe), a quantitative metric of surface exposure time (e.g., Is/FeO). The formation of npFe can be generally described via the reaction: Fe 2+ O + H 2 = Fe 0 + H 2 O, resulting in the formation of endogenous molecular water reservoirs.

lunar water↗

Petrologic Comparison of High- and Low-Titanium Basalt Clasts Derived From ANGSA Core 73001

Volatile elements and compounds significantly influence the properties and behavior of magma, including ascent and eruptive processes. Basalts record a complicated history of the volatile species inherent to their parental magma, and the processes, such as degassing, that change these volatile inventories. On the Moon, outstanding questions remain concerning the behavior of magmatic volatiles and their roles in the evolution of lunar magmas and the formation of mare basalts. As part of the Apollo Next Generation Sample Analysis (ANGSA) program, we are investigating the petrogenesis of two basalt clasts collected from the recently processed Apollo 17 drive tube, 73001. Our team is studying the petrology of the two basalt clasts in 2D and 3D. Recent work has highlighted the utility of coupling traditional 2D methods with 3D measurements to better understand the crystallization and degassing histories of lunar lava flows. We are also investigating the volatile inventory of the samples through in situ studies of volatile-bearing phases, like apatite, to understand the eruptive signatures and degassing histories of low-titanium and high-titanium lunar basalts. At the upcoming conference, we will present the first detailed study of the 2D and 3D mineralogy, textures, 3D vesiculation, and chemistry of these basalt clasts to shed light on their magmatic, volcanic, and post-eruptive histories.

Basalt↗

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↗

Effect of temperature curing on properties and hydration of wollastonite blended magnesium potassium phosphate cements

K-struvite, the main hydrate of magnesium potassium phosphate (MKP) cements, dehydrates at ~50 °C, thus elevated temperatures at service conditions could affect cement properties and durability. In this study, properties and hydration of MKP cement without and with wollastonite were investigated at 20 and 50 °C. In hydrated pure MKP cement K-struvite decomposes progressively over time to MgKPO{sub 4}·H{sub 2}O at 50 °C, which leads to a strong reduction of solid volume and severe strength loss. The presence of wollastonite significantly slows down the decomposition rate of K-struvite, which is still observed after 393 days at 50 °C. K-struvite together with amorphous hydroxyapatite, M-(C)-S-H and CaK{sub 3}H(PO{sub 4}){sub 2} from the wollastonite reaction result in a cement with good short and long-term strength at both 20 and 50 °C.

36 MATERIALS SCIENCE↗

A high-efficiency self-healing cementitious material based on supramolecular hydrogels impregnated with phosphate and ammonium

High-efficiency self-healing cementitious materials using hydroxyapatites as healing product were described. Supramolecular hydrogels impregnated with phosphate and ammonium ions were designed. Morphology of the supramolecular hydrogel and its capability to release phosphate in solution, the structure of healing products and the self-healing efficiency were characterized with a range of analytical techniques. Cracks in the cementitious materials with width up to 1 mm are closed and completely healed. The healing product in the cracks without ammonium ions was brushite with a sponge-like morphology. Released ammonium ions reacted with calcium hydroxide in the cement matrix, increasing the concentration of soluble calcium ions up to 300 times that in reference pore solution. Ammonium ions facilitated the formation and aggregation of healing products which were converted into hydroxyapatites, improving the maximum healable crack width.

36 MATERIALS SCIENCE↗

Multiple Slater Determinants and Strong Spin-Fluctuations as Key Ingredients of the Electronic Structure of Electron- and Hole-Doped Pb 10− x Cu x (PO 4 ) 6 O

LK-99, with chemical formula Pb 10−x Cu x (PO 4 ) 6 O, was recently reported to be a room-temperature superconductor. While this claim has met with little support in a flurry of ensuing work, a variety of calculations (mostly based on density-functional theory) have demonstrated that the system possesses some unusual characteristics in the electronic structure, in particular flat bands. We have established previously that within DFT, the system is insulating with many characteristics resembling the classic cuprates, provided the structure is not constrained to the P3(143) symmetry nominally assigned to it. Here we describe the basic electronic structure of LK-99 within self-consistent many-body perturbative approach, quasiparticle self-consistent GW (QSGW) approximation and their diagrammatic extensions. QSGW predicts that pristine LK-99 is indeed a Mott/charge transfer insulator, with a bandgap gap in excess of 3 eV, whether or not constrained to the P3(143) symmetry. When Pb 9 Cu(PO 4 ) 6 O is hole-doped, the valence bands modify only slightly, and a hole pocket appears. However, two solutions emerge: a high-moment solution with the Cu local moment aligned parallel to neighbors, and a low-moment solution with Cu aligned antiparallel to its environment. In the electron-doped case the conduction band structure changes significantly: states of mostly Pb character merge with the formerly dispersionless Cu d state, and high-spin and low spin solutions once again appear. Thus we conclude that with suitable doping, the ground state of the system is not adequately described by a band picture, and that strong correlations are likely. Irrespective of whether this system class hosts superconductivity or not, the transition of Pb 10 (PO 4 ) 6 O from being a band insulator to Pb 9 Cu(PO 4 ) 6 O, a Mott insulator, and multi-determinantal nature of doped Mott physics make this an extremely interesting case-study for strongly correlated many-body physics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solubility Product of Vanadinite Pb 5 (VO 4 ) 3 Cl at 25 °C—A Comprehensive Approach to Incongruent Dissolution Modeling

Although vanadinite (Pb 5 (VO 4 ) 3 Cl occurs in abundance in various terrestrial geochemical systems of natural and anthropogenic origin and is seriously considered as a potential nuclear waste sequestering agent, its actual application is severely limited by a lack of understanding of its basic thermodynamic parameters. In this regard, the greatest challenge is posed by its incongruent dissolution, which is a pivotal hurdle for effective geochemical modeling. Our paper presents an universal approach for geochemical computing of systems undergoing incongruent dissolution which, along with unique, long-term experiments on vanadinites’ stability, allowed us to determine the mineral solubility constant. The dissolution experiments were carried out at pH = 3.5 for 12 years. Vanadinite has dissolved incongruently, continuously re-precipitating into chervetite (Pb 2 V 2 O 7 ) with the two minerals remaining in mutual equilibrium until termination of the experiments. The empirically derived solubility constant K sp,V,298 = 10 –91.89 ± 0.05 of vanadinite was determined for the first time. The proposed modeling method is versatile and can be adopted to other mineral systems undergoing incongruent dissolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Biosorption of Uranium by Bone Meal

The treatment of aqueous solution waste containing organic compounds and radionuclides has always been a great concern since the processes available are usually expensive and unfeasible for the low volume of radioactive liquid waste recovered. In view of a more efficient and low cost treatment, biosorption-based technologies for the removal of this hazardous radionuclides, heavy metals, and organic substances from contaminated matrices have been studied as an alternative process. In this context, bone meal is the material of choice, and contains calcium phosphate in the form of hydroxyapatite. Previous studies with hydroxyapatite showed that this material is efficient in removing heavy metals from polluted soils due to its adsorbing ability. In this context, uranium biosorption capacity by using bone meal was evaluated by different experimental conditions. This study aims at analyzing the capacity of bone meal to remove uranium from aqueous solution through biosorption process, considering that this nuclide is radiotoxic and may cause serious environmental problems and risks to human life if not correctly disposed. The biosorption capacity of U by bone meal was evaluated under different experimental conditions. The results suggested that adsorption with this material can be applied in the treatment of aqueous solutions as a low-cost and highly efficient alternative to remove U. Therefore, we believe that our results are useful for other investigators dealing with similar problems. Further work is required to evaluate this material as a potential adsorbent concerning the treatment of liquid organic radioactive waste containing uranium. Next studies are crucial to ascertain the biosorption efficiency, by analyzing other variables, such as adsorbent dosage, pH and temperature.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗