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All sources NASA NTRS DOE OSTI

DOE OSTI2016

Tin(II)apatite: Synthesis, Characterization, and Challenge with Pertechnetate - 16194

We will report on the synthesis of stannous apatite and the subsequent reductive capacity attained, using a cerium (IV) titration method. Also reported will be the distribution coefficients derived using a Hanford tank supernatant simulant of 7.8 M sodium with chrome (VI) as a contaminant of concern, as a potential non-isotopic oxy-anion and technetium surrogate for reductive capacity determinations. Pertechnetate will be subjected to reduction using hydroxylamine, glucose and threose. The purpose is to take the first step in laboratory analyses to determine the amount of non-pertechnetate species in Hanford tank waste. A proposed sequestration mechanism will be presented as to why the reacted tin(II)apatite does not release technetium once reacted. SEM and EDS spectra will be presented on the crystalline apatite. Areas of incorporation of the tin(II)apatite will be presented for the Hanford tank waste process. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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↗

DOE OSTI2015

Probing the limit of magnesium uptake by β-tricalcium phosphate in biphasic mixtures formed from calcium deficient apatites

A series of magnesium doped non-stoichiometric calcium deficient apatites were synthesized through an aqueous precipitation route. The resultant structural changes during heat treatment were investigated by X-ray diffraction, Raman and FT-IR spectroscopy and Rietveld refinement. The results confirmed the formation of biphasic mixtures comprising Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} and β-Ca{sub 3}(PO{sub 4}){sub 2} after heat treatment at 1000 °C with the preferential occupancy of Mg{sup 2+} at the crystal lattice of β-Ca{sub 3}(PO{sub 4}){sub 2}. The concentration of Mg{sup 2+} uptake in β-Ca{sub 3}(PO{sub 4}){sub 2} is limited till reaching the stoichiometric ratio of (Ca+Mg)/P=1.67 and beyond this stoichiometric value [(Ca+Mg)/P>1.67], Mg{sup 2+} precipitates as Mg(OH){sub 2} and thereafter gets converted to MgO during heat treatment. Any kind of Mg{sup 2+} uptake in the crystal lattice of Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} is discarded from the investigation. - Highlights: • Aqueous co-precipitation of calcium deficient apatites with excess magnesium (Mg{sup 2+}) additions. • Heat treatments beyond 800 °C results in the formation of biphasic apatite mixtures. • Mg{sup 2+} gets accommodated at the β-Ca{sub 3}(PO{sub 4}){sub 2} lattice of biphasic mixtures. • Mg{sup 2+} additions exceeding stoichiometric value (Ca/P>1.67) results in its formation as MgO. • Mg{sup 2+} occupancy at β-Ca{sub 3}(PO{sub 4}){sub 2} lattice delays its allotropic conversion α-Ca{sub 3}(PO{sub 4}){sub 2} till 1350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Synthesis of apatite phosphates containing Cs{sup +}, Sr{sup 2+} and RE{sup 3+} ions and chemical durability studies

Graphical abstract: New chemically durable hydroxy and fluoro apatite phosphate wasteforms CsLa{sub 0.8}Nd{sub 0.1}Sm{sub 0.1}Sr{sub 3}(PO{sub 4}){sub 3}OH and CsLa{sub 0.7}Nd{sub 0.1}Sm{sub 0.1}Eu{sub 0.1}Sr{sub 3}(PO{sub 4}){sub 3}F are fabricated. Display Omitted Highlights: ► Novel apatite phosphates CsLaSr{sub 3}P{sub 3}(PO{sub 4}){sub 3}OH and CsLaSr{sub 3}(PO{sub 4}){sub 3}F are reported. ► New hydroxyapatite wasteform CsLa{sub 0.8}Nd{sub 0.1}Sm{sub 0.1}Sr{sub 3}P{sub 3}O{sub 12}OH is fabricated. ► Fluoro analogue CsLa{sub 0.7}Nd{sub 0.1}Sm{sub 0.1}Eu{sub 0.1}Sr{sub 3}P{sub 3}O{sub 12}F incorporates ‘Eu{sup 3+}’. ► Negligible leachability of Cs and rare earth ions demonstrated. -- Abstract: Crystallization of Cs, Sr and selected rare earth ions in apatite phosphate structure was investigated. Compounds of the formula CsLaSr{sub 3}(PO{sub 4}){sub 3}OH (CSOH), CsLaSr{sub 3}(PO{sub 4}){sub 3}F (CSF) and the simulated waste forms of the compositions CsLa{sub 0.8}Nd{sub 0.1}Sm{sub 0.1}Sr{sub 3}(PO{sub 4}){sub 3}OH (CNSOH) and CsLa{sub 0.7}Nd{sub 0.1}Sm{sub 0.1}Eu{sub 0.1}Sr{sub 3}(PO{sub 4}){sub 3}F (CNSEF) were synthesized and characterized by powder XRD, TGA and SEM techniques. The leachability behaviour of the single phases was studied for a period of one month by MCC-5 test using powder specimen. The leachability of Cs and other rare earth ions was found to be negligible. The leach rates (LR{sub i}) of Sr and P were observed as follows: CSOH – LR{sub Sr} = 10{sup −3}–10{sup −4} g/m{sup 2}/d, LR{sub P} = 10{sup −4} g/m{sup 2}/d; CSF – LR{sub Sr} = 10{sup −3}–10{sup −5} g/m{sup 2}/d, LR{sub P} = 10{sup −4}–10{sup −5} g/m{sup 2}/d; CNSOH and CNSEF – LR{sub Sr} = 10{sup −3}–10{sup −4} g/m{sup 2}/d, LR{sub P} = 10{sup −4}–10{sup −5} g/m{sup 2}/d.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Thermal expansion of solid solutions in apatite binary systems

Graphical abstract: Thermal dependencies of volume thermal expansion parameter for with thermal expansion diagrams for Pb{sub 5}(PO{sub 4}){sub 3}F{sub x}Cl{sub 1−x}. - Highlights: • Solid solutions in three apatitic binary systems were investigated via HT-XRD. • Thermal expansion coefficients of solid solutions in the systems were calculated. • Features of the thermal deformation of the apatites were described. • Termoroentgenography is a sensitive method for the investigation of isomorphism. - Abstract: High-temperature insitu X-ray diffraction was used to investigate isomorphism and the thermal expansion of apatite-structured compounds in three binary systems in the entire temperature range of the existence of its hexagonal modifications. Most of the studied compounds are highly expandable (α{sub l} > 8 × 10{sup 6} (K{sup −1})). In Pb{sub 5}(PO{sub 4}){sub 3}F–Pb{sub 5}(PO{sub 4}){sub 3}Cl system, volume thermal expansion coefficient is independence from the composition at 573 K. In Pb{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(VO{sub 4}){sub 3}Cl, the compound with equimolar ratio of substituted atoms has constant volume thermal expansion coefficient in temperature range 298–973 K. Ca{sub 5}(PO{sub 4}){sub 3}Cl–Pb{sub 5}(PO{sub 4}){sub 3}Cl system is characterized by the most thermal sensitive composition, in which there is an equal ratio of isomorphic substituted atoms.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Identifying Rare Earth Elements and Thorium and Uranium in Iron Oxide–Apatite Deposit of Gazestan Bafgh, Southeast of Iran

The Gazestan magnetite-apatite deposit is one of Kiruna-type deposits located 78 km from Bafgh in the province of Yazd, in the Bafgh Posht-e-Badam district, southeast of Iran. In the mining region of Bafgh, volcanic rocks and Precambrian volcano-sedimentary are the main host of iron-apatite deposits. Iron deposits are essentially located in Bafgh region inside the green acidic metamorphic rocks. Volcanic rocks are basically rhyolite and rhyodacitic and the sedimentary units are mostly made of dolomite. Rock units of the region belong to the Rizzo series. The Bafgh apatite compounds are fluoride-type and seen in the monazite mineral. The similarity of the rare earth elements pattern in all samples indicates the magma source. The most amount of rare earth elements in the Gazestan deposit include 7766.25 ppm and the most amount of Th is equal to 65.1 ppm and U is equal to 8.33 ppm. The most amount of P2O5 s equal to 26.5 wt% and Fe is equal to 61.3 wt%. Also, it can be concluded that due to their high correlation with rare earth elements, the deposit is of Uranium Thorium-bearing type.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS2021

Thermal Expansion Coefficients of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 Apatite-type Silicates

High temperature X-ray diffraction (XRD) scans of Y2Si2O7 and Yb2Si2O7 reactions with calcium-magnesium-aluminosilicates (CMAS) were utilized to determine thermal expansion coefficients (CTEs) of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 apatite materials. In order to validate these measurements, the CTEs of Y2Si2O7, Yb2Si2O7 and SiO2 were also determined from the same scans. The directional CTEs for γ-Y2Si2O7 were determined to be αa=5.84×10-6/K, αb=6.81×10-6/K and αc=0.81×10-6/K, and β-Yb2Si2O7 was determined to have values of αa=6.89×10-6/K, αb=4.81×10-6/K and αc=2.78×10-6/K. The average CTEs of γ-Y2Si2O7 and β-Yb2Si2O7 were determined to be 4.5×10-6/K and 4.7×10-6/K, respectively, which agreed with previous analyses. Ca2Y8(SiO4)6O2 exhibited directional CTEs of αa=9.36×10-6/K and αc=7.95×10-6/K (averaged between two sets of data), whereas Ca2Yb8(SiO4)6O2 had values that were very similar (αa=9.63×10-6/K, αc=7.45×10-6/K). Both results for the Ca2RE8(SiO4)6O2 apatites correlated well with the limited data on apatite-type silicates available in literature.

rare earth↗

DOE OSTI2012

Reduction And Stabilization (Immobilization) Of Pertechnetate To An Immobile Reduced Technetium Species Using Tin(II) Apatite

Synthetic tin(II)apatite reduces pertechnetate from the mobile +7 to a non-mobile oxidation state and sequesters the technetium, preventing re-oxidization to mobile +7 state under acidic or oxygenated conditions. Previous work indicated technetium reacted Sn(II)apatite can achieve an ANSI leachability index of 12.8 in Cast Stone. An effect by pH is observed on the distribution coefficient, the highest distribution coefficient being l70,900 observed at pH levels of 2.5 to 10.2. The tin apatite was resistant to releasing technetium under test conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Selenite sorption by carbonate substituted apatite

The sorption of selenite, SeO 3 2– , by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m 2 /g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, K d , determined for the carbonated apatite in this work ranged from approximately 4200 to over 14,000 L/kg. A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. Furthermore, the results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.

36 MATERIALS SCIENCE↗

DOE OSTI2018

X-ray Linear Dichroism in Apatite

The recent observation in parrotfish teeth of X-ray linear dichroism motivated an in-depth investigation into this spectroscopic effect in various apatite crystals, including geologic hydroxyapatite (Ca 5 (PO 4 ) 3 OH), fluorapatite (Ca 5 (PO 4 ) 3 F), and their biogenic counterparts in human bone, mouse enamel, and in parrotfish bone, dentin, and enameloid, the equivalent of dental enamel in certain fish. These data are important because they now enable visualization of the nano- to microscale structure of apatite crystals in teeth and bone. Polarization-dependent imaging contrast (PIC) maps of lamellar bone, obtained with a new method that minimizes space-charge and charging effects, show the expected rotating apatite crystal orientations. PIC maps of mouse enamel reveal a complex arrangement of hydroxyapatite crystals perpendicular to the dentin-enamel junction, with rods arranged in a decussation pattern in inner enamel and nearly parallel to one another in outer enamel. In both inner and outer enamel crystal c-axes are not always aligned with the rod elongation direction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

DOE OSTI2021

X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal

Bone-like materials comprise carbonated-hydroxyapatite nanocrystals (c-Ap) embedding a fibrillar collagen matrix. The mineral particles stiffen the nanocomposite by tight attachment to the protein fibrils creating a high strength and toughness material. The nanometer dimensions of c-Ap crystals make it very challenging to measure their mechanical properties. Mineral in bony tissues such as dentine contains 2~6 wt.% carbonate with possibly different elastic properties as compared with crystalline hydroxyapatite. Here we determine strain in biogenic apatite nanocrystals by directly measuring atomic deformation in pig dentine before and after removing carbonate. Transmission electron microscopy revealed the platy 3D morphology while atom probe tomography revealed carbon inside the calcium rich domains. High-energy X-ray diffraction in combination with in situ hydrostatic pressurization quantified reversible c-Ap deformations. Additionally, crystal strains differed between annealed and ashed (decarbonated) samples, following 1 or 10 h heating at 250 °C or 550 °C respectively. Measured bulk moduli (K) and a-/c-lattice deformation ratios (η) were used to generate synthetic K syn and ηsyn identifying the most likely elastic constants C 33 and C 13 for c-Ap. These were then used to calculate the nanoparticle elastic moduli. For ashed samples, we find an average E 11 =107 GPa and E 33 =128 GPa corresponding to ~5% and ~17% stiffening of the a-/c-axes of the nanocrystals as compared with the biogenic nanocrystals in annealed samples. Ashed samples exhibit ~10% lower Poisson's ratios as compared with the 0.25~0.36 range of carbonated apatite. Carbonate in c-Ap may therefore serve for tuning local deformability within bony tissues.

36 MATERIALS SCIENCE↗

DOE OSTI2014

The interaction between cations and anionic groups inducing SHG enhancement in a series of apatite-like crystals: A first-principles study

It is an interesting topic to reveal the origin of the SHG intensity enhancement after substitution from alkali and alkali-earth metal atoms to cadmium in a series of apatite-like borates KSr{sub 4}(BO{sub 3}){sub 3}, Ca{sub 5}(BO{sub 3}){sub 3}F, Cd{sub 5}(BO{sub 3}){sub 3}F. Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the electronic structure, the optical properties and the contribution of respective ion and ion groups have been investigated. Second harmonic generation (SHG) responses are mainly attributed to BO{sub 3} groups with π conjugated configuration and their alignment framework. The contributions of A site are more important in CaBOF and CdBOF compounds than in KSrBO. It is also demonstrated that the strong covalent interactions between the boron–oxygen groups and the cadmium atoms contribute the enhancement of SHG responses after substitution from alkali and alkali-earth metal atoms. - graphical abstract: Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the enhancement of SHG response are attributed to the interaction between cadmium and BO{sub 3} groups. - Highlights: • SHG response on a series of apatite-like borates was studied by a SHG-density method. • SHG responses are mainly attributed to BO{sub 3} groups and their alignment framework. • The contributions of A site are more important in CaBOF and CdBOF than in KSrBO. • Covalent interaction between BO and Cd is responsible for SHG of CdBOF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Lead apatites: structural variations among Pb 5 ( B O 4 ) 3 Cl with B = P (pyromorphite), As (mimetite) and V (vanadinite)

The crystal structure of four Pb apatite samples, Pb 5 ( B O 4 ) 3 Cl, was refined with synchrotron high-resolution powder X-ray diffraction data, Rietveld refinements, space group P 6 3 / m and Z = 2. For this isotypic series, B = P 5+ is pyromorphite, B = As 5+ is mimetite and B = V 5+ is vanadinite. The ionic radius for As 5+ (0.355 Å) is similar to that of V 5+ (0.335 Å), and this is twice as large as that for P 5+ (0.170 Å). However, the c unit-cell parameter for mimetite is surprisingly different from that of vanadinite, although their unit-cell volumes, V , are almost equal to each other. No explanation was available for this peculiar c -axis value for mimetite. Structural parameters such as average $\langle$ B —O$\rangle$ [4], $\langle$Pb1—O 9 $\rangle$ [9] and $\langle$Pb2—O 6 Cl 2 $\rangle$ [8] distances increase linearly with V (the coordination numbers for the cations are given in square brackets). Mimetite has a short Pb2—O1 distance, so the O1 oxygen atom interacts with the 6 s 2 lone-pair electrons of the Pb 2+ cation that causes the Cl—Cl distance (= c /2) to increase to the largest value in the series because of repulsion, which causes the c -axis to increase anomalously. Although Pb apatite minerals occur naturally in ore deposits, they are also formed as scaly deposits in lead water pipes that give rise to lead in tap water, as was found recently in Flint, Michigan, USA. It is important to identify Pb-containing phases in water-pipe deposits.

chemistry↗

DOE OSTI2025

Exploration of a Combined LIBS and LA-ICP-MS Approach for Apatite Characterisation

A combined laser‐induced breakdown spectroscopy (LIBS) and laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) method is demonstrated for comprehensive apatite analysis. These measurements provide elemental imaging that can be used as a screening technique for chemical selection of grains for subsequent analysis (e.g., U‐Pb geochronology) or can be used to understand elemental distributions within a single grain that would have direct textural‐chemical implications (e.g., zoning patterns). Adding LIBS as a simultaneous measurement, to LA‐ICP‐MS U‐Pb geochronology, allowed for the direct determination of F (H and O show promise for future applications) in addition to major and trace elements of interest. Here, the quantitative measurements were validated against a series of apatites with known values and used to characterise a wide range of samples. Fluorine detection limits were determined to be as low as 70 μg g ‐1 F (broadband CMOS detector) and 4.2 μg g ‐1 F (ICCD detector). U‐Pb age dating was simultaneously collected by LA‐ICP‐MS with the quantitative elemental data from LIBS, providing a comprehensive method for geochronology.

Apatite↗

DOE OSTI2017

Apatite and sodalite based glass-bonded waste forms for immobilization of 129I and mixed halide radioactive wastes

The goal of the project was to utilize the knowledge accumulated by the team, in working with minerals for chloride wastes and biological apatites, toward the development of advanced waste forms for immobilizing 129I and mixed-halide wastes. Based on our knowledge, experience, and thorough literature review, we had selected two minerals with different crystal structures and potential for high chemical durability, sodalite and CaP/PbV-apatite, to form the basis of this project. The focus of the proposed effort was towards: (i) low temperature synthesis of proposed minerals (iodine containing sodalite and apatite) leading to the development of monolithic waste forms, (ii) development of a fundamental understanding of the atomic-scale to meso-scale mechanisms of radionuclide incorporation in them, and (iii) understanding of the mechanism of their chemical corrosion, alteration mechanism, and rates. The proposed work was divided into four broad sections. deliverables. 1. Synthesis of materials 2. Materials structural and thermal characterization 3. Design of glass compositions and synthesis glass-bonded minerals, and 4. Chemical durability testing of materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS2018

Chlorine Isotopic Compositions of Apatite in Apollo 14 Rocks: Evidence for Widespread Vapor-Phase Metasomatism on the Lunar Nearside ~4 Billion Years Ago

Compared to most other planetary materials in the Solar System, some lunar rocks display high delta (sup 37) Cl signatures. Loss of Cl in a H<<Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with delta (sup 37) Cl values ranging from +14.6 ± 1.6 per mille to +40.0 ± 2.9 per mille. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and delta (sup 37) Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of delta (sup 37) Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ~4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

apatit↗

DOE OSTI2017

Complex F,Cl Apatite Solid Solution Investigated Using Multinuclear Solid-State NMR Methods

In this paper, a series of synthetic F,Cl apatites with low hydroxyl content was investigated using 31 P, 19 F, and 35 Cl solid-state magic angle spinning (MAS) NMR spectroscopic methods. 31 P single-pulse (SP) NMR spectra show that for each composition the phosphate 31 P chemical shift depends on occupancy of the nearest anion site for each composition. Overall the average chemical shift deviates from linear across the F/Cl series. For intermediate compositions 19 F SP NMR spectra reveal complex, broadened spectral profiles that are not correlated to composition. 19 F{ 35 Cl} TRAPDOR results indicate that the spectral profiles do not reflect occupancy of F and Cl in adjacent column anion sites. We propose that the complex 19 F lineshapes are principally due to broad distributions of 19 F–Ca distances arising from displacement of F along the anion channel. Finally, approximate fluorine atomic positions are estimated based on 19 F chemical shifts of alkaline earth fluoride salts, and the results are in good accord with those proposed for intermediate composition F,Cl apatites from XRD data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗