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NASA NTRS2022

The Abundances of F, Cl, and H2O in 4Vesta from Eucrites

The abundance and distribution of magmatic volatiles (i.e., H, C, N, F, S, and Cl) within the silicate portion of a differentiated planetary body has important consequences on its thermochemical evolution. However, the abundances of magmatic volatiles within differentiated bodies are difficult to quantify, and they are often depleted by varying degrees relative to CI chondrites. The mechanisms of depletion are not well constrained and could relate to intrinsic volatile depletion of the building blocks that formed the bodies, high temperature processes that result from accretion, post-accretion loss through parent body geological processes and large-scale impacts, and/or redistribution within a parent body through processes like core formation [1–4]. In the present study, we aim to constrain the abundances of F, Cl, and H2O in eucrites to better understand the magnitude of volatile depletion on 4Vesta. To accomplish this objective, we report electron microprobe analyses of apatite from seven unbrecciated, non-cumulate eucrites (i.e., CMS 04049,GRA 98098, LEW 88010, MAC 02522, MAC 041169,QUE 94484, and QUE 97053) and two monomict, non-cumulate eucrites (i.e., Berthoud and Stannern). In combination with previously published data on eucrite-hosted apatite, we determine Cl/F and H2O/F ratios in bulk rock eucrites through the application of apatite-based melt hygrometry and chlorometry [e.g., 5–7].Additionally, we estimate the bulk rock abundances of F in six non-cumulate eucrites (i.e., GRA 98098, MAC041169, PCA 91078, QUE 97053, Stannern, and Berthoud), which we combine with previously published bulk rock F data on non-cumulate eucrites[8] to constrain the abundances of F, Cl, and H2O in 4Vesta using appropriately paired volatile/refractory element ratios for F, followed by Cl/F and H2O/F ratios for Cl and H2O, respectively.

F M McCubbin↗
NASA NTRS2022

The Zn, S, and Cl Isotope Compositions of Mare Basalts: Implications for the Effects of Eruption Style and Pressure on Volatile Element Stable Isotope Fractionation on the Moon

We compare the stable isotope compositions of Zn, S, and Cl for Apollo mare basalts to better constrain the sources and timescales of lunar volatile loss. Mare basalts have broadly elevated yet limited ranges in δ(66)Zn, δ(34)S, and δ(37)Cl_(SBC+WSC) values of 1.27 ± 0.71, 0.55 ± 0.18, and 4.1 ± 4.0‰, respectively, compared to the silicate Earth at 0.15, –1.28, and 0‰, respectively. We find that the Zn, S, and Cl isotope compositions are similar between the low- and high-Ti mare basalts, providing evidence of a geochemical signature in the mare basalt source region that is inherited from lunar formation and magma ocean crystallization. The uniformity of these compositions implies mixing following mantle overturn, as well as minimal changes associated with subsequent mare magmatism. Degassing of mare magmas and lavas did not contribute to the large variations in Zn, S, and Cl isotope compositions found in some lunar materials (i.e., 15‰ in δ(66)Zn, 60‰ in δ(34)S, and 30‰ in δ(37)Cl). This reflects magma sources that experienced minimal volatile loss due to high confining pressures that generally exceeded their equilibrium saturation pressures. Alternatively, these data indicate effective isotopic fractionation factors were near unity. Our observations of S isotope compositions in mare basalts contrast to those for picritic glasses (Saal and Hauri 2021), which vary widely in S isotope compositions from –14.0 to 1.3‰, explained by extensive degassing of picritic magmas under high-P/P_(Sat) values (>0.9) during pyroclastic eruptions. The difference in the isotope compositions of picritic glass beads and mare basalts may result from differences in effusive (mare) and explosive (picritic) eruption styles, wherein the high-gas contents necessary for magma fragmentation would result in large effective isotopic fractionation factors during degassing of picritic magmas. Additionally, in highly vesiculated basalts, the δ(34)S and δ(37)Cl values of apatite grains are higher and more variable than the corresponding bulk-rock values. The large isotopic range in the vesiculated samples is explained by late-stage low-pressure “vacuum” degassing (P/P-(Sat) ~ 0) of mare lavas wherein vesicle formation and apatite crystallization took place post-eruption. Bulk-rock mare basalts were seemingly unaffected by vacuum degassing. Degassing of mare lavas only became important in the final stages of crystallization recorded in apatite—potentially facilitated by cracks/fractures in the crystallizing flow. We conclude that samples with wide-ranging volatile element isotope compositions are likely explained by localized processes, which do not represent the bulk Moon.

Halogens↗
NASA NTRSDate not supplied

Volatile Abundance of Paired Lunar Troctolites and the Early Lunar Crust

Nominally anhydrous minerals (NAMs) such as plagioclase, pyroxene, and olivine can contain small amounts of water and other volatile elements, typically within crystal lattice defects. Given the volumetric abundance of NAMs, these minerals can contain a significant volatile reservoir despite their low abundances. At least one NAM is present in nearly all lunar rocks, unlike the more commonly studied volatile-bearing mineral apatite, making NAM-based hygrometry more widely applicable. NAMs are also not subject to enrichment in H due to self-fractionation of F, as is the case for apatite. Recent developments in secondary ion mass spectrometry (SIMS) techniques (e.g., the reduction of analytical background) have allowed the evaluation of volatiles in samples that were previously too low in abundance to measure. The ability to make volatile measurements in the sub-10 ppm range opens up a suite of samples where volatile-bearing phases, such as melt inclusions and apatite, are rare or entirely absent. In this study we measure the abundances of H, C, F, P, S, and Cl in plagioclase from two paired lunar troctolites to better understand the volatile inventory of the early lunar crust and its implications for the bulk Moon.

volatiles↗
NASA NTRSDate not supplied

Timing and Geochemical Evolution of Triassic and Jurassic Magmatism during the Break-up of Pangea along the Eastern North American Margin

While our understanding of continental break-up has seen dramatic advances over the past decades, the impact of syn-rift melt generation on the transition from mechanical stretching to seafloor spreading remains enigmatic. Early Mesozoic continental break-up along the U.S. Eastern North American Margin (ENAM) is characterized by protracted Triassic lithospheric stretching and syn-rift deposition interrupted by voluminous Central Atlantic Magmatic Province (CAMP) magmatism. This magmatic phase is followed by ~50 Myr of protracted rifting prior to steady-state seafloor spreading. Mesozoic magmatism recognized in outcrop and aeromagnetic datasets along the ENAM has been summarily attributed to CAMP, although extensive regional dikes preserved in the ENAM proximal rift domain remain largely undated. This study provides new constraints on the timing, duration, and geochemical evolution of syn-rift ENAM magmatism using in-situ apatite U-Pb geochronology and whole-rock geochemistry and integrates these data into a tectonic model. We present in-situ apatite U-Pb ages and whole-rock geochemical data for 16 diabase dikes and sills from NJ, PA, VA, NC, and SC. A Palisades Sill sample yielded an age of 201 ± 8 Ma and agrees with previous 40 Ar/39 Ar and U-Pb ages. Our new in-situ apatite U-Pb ages fall into three clusters and suggest three main pulses of magmatism along the ENAM, with an initial pulse of magmatism at ~205-195 Ma attributed to CAMP. Whole-rock geochemistry of this pulse shows silica (46-53 wt.%), total alkalis (2-4 wt.%), and enrichment of LREEs relative to HREEs, comparable to previously reported geochemical data for CAMP-related rocks along the ENAM. A second magmatic pulse occurred between ~181-175 Ma and shows slightly higher silica and total alkalis, compared to the older CAMP-age phase. The third pulse between ~166-145 Ma generally shows slightly higher silica and total alkalis. LOI and Sr/Yb values of the two younger pulses are similar to CAMP-age samples suggesting no post-crystallization alteration. These new data demonstrate long-lived syn-rift off-axis magmatism persisted ~50 Myr after the onset of CAMP. This post-CAMP off-axis magmatism is likely related to slow magma-limited spreading during the protracted transition to symmetric seafloor spreading along the ENAM.

Z. Foster-Baril↗
NASA NTRSDate not supplied

207Pb-206Pb Geochronology and Microstructures of Phosphates From Apollo 14 and 15 Soils

Phosphates (apatite and merrillite) are common accessory minerals in many Apollo basalt and regolith samples. Phosphates typically have lower closure temperatures than their companion accessory phase zircon for their U-Pb and (U-Th)/He geochronologic systems [e.g., 1, 2]. As such, the ages of phosphates in impact melt-bearing breccias have typically been used to constrain the ages of impact events [3]. Phosphates have also served as anchors for 207Pb-206Pb isochrons allowing for precise ages of basaltic samples to be determined [4]. Apatite is also a reservoir for volatile species (e.g., F, Cl, OH, S) [e.g., 5, 6] which are important for investigating the formation and evolution of the lunar interior [7-11]. Recent work by [11] and [12] has shown that deformation and exposure to high temperatures, especially those in impact environments, can influence both apatite chronology and chemistry. Here we present the first chronology and microstructure results of a large consortium study aimed at unraveling the impact and endogenous volatile record of phosphates extracted from lunar soils. These soils potentially sample a larger range of lithologies than the rocks returned by Apollo astronauts, and should, therefore, represent a more global phosphate record. For more information on low temperature (U-Th)/He thermochronology, please see the companion abstract [13].

C A Crow↗
NASA NTRS1972

Electron microscopy of some experimentally shocked counterparts of lunar minerals.

Particulate samples of experimentally shocked olivine, enstatite, and apatite and their unshocked equivalents were thinned by ion bombardment and examined by transmission methods in a conventional (100 kV) electron microscope. Enstatite shock-loaded at a peak pressure of 250 kb was partly transformed to relatively dense inverse defect spinel. Magnesian olivine shocked at a peak pressure of 200 kb shows intense lattice deformation. Magnesian olivine shock-loaded at a peak pressure of 400 kb was recrystallized to very fine polycrystalline aggregates. Apatite shock-loaded at a peak pressure of 250 kb shows planar deformation elements and shock-induced imperfections.

Sclar, C. B.↗
NASA NTRS1974

Effects of ultrasonic fields in the phosphoric acid process

A process of apatite decomposition with sulfuric acid was studied under the influence of ultrasound in the phosphoric acid production process. The studies were carried out with and without ultrasonic fields in the reaction mixture, which resembled the mixing ratio used in technical production processes. Ultrasound with a frequency of 20 kHz and an intensity of 1 W/sq cm was used in the studies. A very favorable ultrasonic effect upon the degree of apatite decomposition was observed. The ultrasonic field affects the shape of byproduct gypsum crystals. In the H3PO4 production process without ultrasound, the byproduct gypsum crystallizes as long, thin needles which cause problems in filtration. In the trials involving the application of wound, gypsum crystallized in the form of small platelets possessing a favorable ratio of length to width.

Kowalska, E.↗
NASA NTRS1981

Halogen and phosphorus storage in the earth

Chemical analyses of surface reservoirs, coupled with compositions for interior zones inferred from geophysical and geochemical data have been used to obtain a range of estimates of the bulk composition of the earth. It is suggested that (1) apatite with 3 wt% Fe, up to 1 wt% Cl, and 0.003 wt% Br is the principal mineral reservoir for halogens, and mica is a subsidiary reservoir; (2) apatite with 18 wt% P is the principal store of P in the upper mantle and perhaps lower mantle, but accounts for only one-twentieth of P in the earth; and (3) the remaining P is in a reservoir inaccessible to magmatism, and may amount to a maximum of 0.7 wt% in the core.

Smith, J. V.↗
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.↗
NASA NTRS1984

Trace element abundances in megacrysts and their host basalts - Constraints on partition coefficients and megacryst genesis

Rare earth and other trace element abundances are determined in megacrysts of clinopyroxene, orthopyroxene, amphibole, mica, anorthoclase, apatite and zircon, as well as their host basalts, in an effort to gather data on mineral/melt trace element partitioning during the high pressure petrogenesis of basic rocks. Phase equilibria, major element partitioning and isotopic ratio considerations indicate that while most of the pyroxene and amphibole megacrysts may have been in equilibrium with their host magmas at high pressures, mica, anorthoclase, apatite, and zircon megacrysts are unlikely to have formed in equilibrium with their host basalts. It is instead concluded that they were precipitated from more evolved magmas, and have been mixed into their present hosts.

Irving, A. J.↗
NASA NTRS1984

Magnesian anorthosites and associated troctolites and dunite in Apollo 14 breccias

Magnesian anorthosite, a new type of pristine lunar highlands rock, has been found in Apollo 14 breccias. It has primitive (high Ca and Mg) silicate mineral compositions, and high and variable REE concentrations. Variations in REE contents can be accounted for by variations in modal abundance of REE-rich apatite. Magnesian anorthosites are associated with troctolites and a dunite with very similar mineral compositions and it is suggested that all crystallized from a differentiated troctolitic intrusion. The origin of the REE-rich apatite is enigmatic. It is unlikely to have crystallized from an igneous liquid in equilibrium with the major minerals in the anorthosite. Possible origins are assimilation of urKREEP or metasomatism by REE-rich fluids. REE-rich alkali anorthosites and gabbronorites are also found and are likely to be related to KREEP basalt magmas. Lunar compositional associations are distributed in a regional rather than global manner.

Lindstrom, M. M.↗
NASA NTRS1985

Evolution of basin and range structure in the Ruby Mountains and vicinity, Nevada

Results from various age dating techniques, seismic reflection profiling hydrocarbon maturation studies, and structural analysis were used to evaluate the Cenozoic deformation in the Ruby Mountains and adjoining ranges (pinyon Range and Cortez Range) in Elko and Eureka Counties, Nevada. Age dating techniques used include potassium-argon ages of biotites from granites published by Kistler et al. (1981) and fission track ages from apatite and zircon. Fission track ages from apatite reflect a closing temperature of 100 plus or minus 20 deg C. Zircon fission track ages reflect a closing temperature of 175 plus or minus 25 deg C and potassium-argon ages from brotite reflect a closing temperature of 250 plus or minus 30 deg C. Thus these results allow a reasonably precise tracking of the evolution of the ranges during the Cenozoic. Seismic reflection data are available from Huntington Valley. Access to seismic reflection data directly to the west of the Harrison Pass Pluton in the central Ruby Mountains was obtained. In addition results are available from several deep exploration holes in Huntington Valley.

Blackwell, D. D.↗
NASA NTRS1985

Thermal history of a metamorphic core complex

Fission track (FT) thermochronology studies of lower plate rocks of the Ruby Mountains-East Humbolt Range metamorphic core complex provide important constraints on the timing an nature of major middle Tertiary extension of northeast Nevada. Rocks analyzed include several varieties of mylonitic orthogneiss as well as amphibolitic orthognesses from the non-mylonitic infrastructural core. Oligocene-age porphyritic biotite granodiorite of the Harrison Pass pluton was also studied. The minerals dated include apatite, zircon, and sphene and were obtained from the same rocks that have been previously studied. FT ages are concordant and range in age from 26.4 Ma to 23.8 Ma, with all showing overlap at 1 sigma between 25.4 to 23.4 Ma. Concordancy of all FT ages from all structural levels indicates that the lower plate cooled rapidly from temperatures above approx. 285 C (assumed sphene closure temperature (2)) to below approx. 150 C (assumed apatite closure temperature) near the beginning of the Miocene. This suggests that the lower plate cooled at a rate of at least approx. 36 deg C/Ma during this event. Rapid cooling of the region is considered to reflect large-scale tectonic denudation (intracrustal thinning), the vertical complement to intense crustal extension. FT data firmly establish the upper limit on the timing of mylonitization during detachment faulting and also coincide with the age of extensive landscape disruption.

Dokka, R. K.↗
NASA NTRS1987

Rare earth patterns in shergottite phosphates and residues

Leaching experiments with 1M HCl on ALHA 77005 powder show that rare earth elements (REE) are concentrated in accessory phosphate phases (whitlockite, apatite) that govern the REE patterns of bulk shergottites. The REE patterns of whitlockite are typically light REE-depleted with a negative Eu anomaly and show a hump at the heavy REE side, while the REE pattern of apatite (in Shergotty) is light REE-enriched. Parent magmas are calculated from the modal compositions of residues of ALHA 77005, Shergotty, and EETA 79001. The parent magmas lack a Eu anomaly, indicating that plagioclase was a late-stage crystallizing phase and that it probably crystallized before the phosphates. The parent magmas of ALHA 77005 and Shergotty have similar REE patterns, with a subchondritic Nd/Sm ratio. However, the Sm/Nd isotopoics require a light REE-depleted source for ALHA 77005 (if the crystallization age is less than 600 Myr) and a light REE-enriched source for Shergotty. Distant Nd and Sr isotopic signatures may suggest different source regions for shergottites.

Laul, J. C.↗
NASA NTRS1988

Rare earth element carriers in the Shergotty meteorite and implications for its chronology

This paper reports on the results of ion-probe measurements of REE concentrations in individual grains of the Shergotty meteorite. The phases analyzed included whitlockite, apatite, baddeleyite, augite, pigeonite, maskelynite, and K-rich glass; the whitlockite and apatite phases were also analyzed for U. Results indicate that whitlockite contains the bulk of the REE in Shergotty, with no evidence for distinct light-REE patterns in texturally different whitlockites. The results on the evolution of the REE abundances in the Shergotty late-stage interstitial melt, inferred from the analysis of whitlockite, are consistent with closed system crystallization. No metasomatic alteration is required to explain the REE data. It is concluded that there is no compelling reason to attribute chronological significance to the Sm-Nd array, as was done by Jagoutz and Waenke (1986).

Lundberg, Laura L.↗
NASA NTRS1993

A Monazite-bearing clast in Apollo 17 melt breccia

A phosphate-rich clast in a pigeonite-plagioclase mineral assemblage occurs in Apollo 17 impact-melt breccia 76503,7025. The clast, measuring 0.9 x 0.4 mm in thin section, contains 3.3 percent (volume) apatite (Ca5P3O12(F,Cl)), 0.8 percent whitlockite (Ca16(Mg,Fe)2REE2P14O56), and trace monazite ((LREE)PO4). Major minerals include 26 percent pigeonite, En53-57FS34-35W08-13, and 69 percent plagioclase, An84-92Ab7-15Oro.6-1.1. Troilite, ilmenite, and other accessory minerals constitute less than 1 percent of the assemblage and Fe-metal occurs along fractures. Also present in the melt breccia as a separate clast is a fragment of felsite. Based on the association of these clasts and their assemblages, a parent lithology of alkali-anorthositic monzogabbro is postulated. Monazite occurs in the phosphate-bearing clast as two less than 10 micron grains intergrown with whitlockite. The concentration of combined REE oxides in monazite is 63.5 percent and the chondrite-normalized REE pattern is strongly enriched in LREE, similar to lunar monazite in 10047,68 and terrestrial monazite. Thorium concentration was not measured in monazite, but based on oxide analyses of approximately 100 percent (including interpolated values for REE not measured), substantial Th concentration is not indicated, similar to monazite in 10047,68. Measured monazite/whitlockite REE ratios are La: 11, Ce: 8, Sm: 3.6, Y: 0.9, and Yb: 0.5. Compositions of monazite and coexisting whitlockite and apatite are given.

Jolliff, Bradley L.↗
NASA NTRS1994

ALH84001, a cumulate orthopyroxenite member of the Martian meteorite clan

ALH84001, originally classified as a diogenite, is a coarse-grained, cataclastic, orthopyroxenite meteorite related to the martian (SNC) meteorites. The orthopyroxene is relatively uniform in composition, with a mean composition of Wo3.3En69.4Fs27.3. Minor phases are euhedral to subhedral chromite and interstitial maskelynite, An31.1Ab63.2Or5.7, with accessory augite, Wo42.2En45.1Fs12.7, apatite, pyrite and carbonates, Cc11.5Mg58.0Sd29.4Rd1.1. The pyroxenes and chromites in ALH84001 are similar in composition to these phases in EETA79001 lithology a megacrysts but are more homogeneous. Maskelynite is similar in composition to feldspars in the nakhlites and Chassigny. Two generations of carbonates are present, early (pre-shock) strongly zoned carbonates and late (post-shock) carbonates. The high Ca content of both types of carbonates indicates that they were formed at moderately high temperature, possibly approximately 700 C. ALH84001 has a slightly LREE-depleted pattern with La 0.67x and Lu 1.85x CI abundances and with a negative Eu anomaly (Eu/Sm 0.56x CI). The uniform pyroxene composition is unusual for martian meteorites, and suggests that ALH84001 cooled more slowly than did the shergottites, nakhlites of Chassigny. The nearly monomineralic composition, coarse-grain size, homogeneous orthopyroxene and chromite compositions, the interstitial maskelynite and apatite, and the REE pattern suggest that ALH84001 is a cumulate orthopyroxenite containing minor trapped, intercumulus material.

Mittlefehldt, David W.↗
NASA NTRS1994

Geochemical evidence for mixing of three components in martian orthopyroxenite ALH 84001

ALH 84001, a ferroan martian orthopyroxenite, originally consisted of three petrographically defined components: a cumulus assemblage of orthopyroxene + chromite, a trapped melt assemblage of orthopyroxene(?) + chromite + maskelynite + apatite + augite +/- pyrite, and a metasomatic assemblage of carbonate +/- pyrite. We present the results of Instrumental Neutron Activation Analysis (INAA) study of five bulk samples of ALH 84001, combined with Scanning Ion Mass Spectrometer (SIMS) data on the orthopyroxene, in order to attempt to set limits on the geochemical characteristics of the latter two components, and therefore on the petrogenesis of ALH 84001. The INAA data support the petrographic observations, suggesting that there are at least three components in ALH 84001. We will assume that each of the three geochemically required components can be equated with one of the petrographically observed components. Both trapped melt and metasomatic components in ALH 84001 have higher Na than orthopyroxene based on compositions of maskelynite, apatite, and carbonate. For the metasomatic component, we will assume its Na content is that of carbonate, while for a trapped melt component, we will use a typical Na content inferred for martian meteorite parent melts, approximately 1 wt% Na2O. Under these assumptions, we can set limits on the Light Rare Earth Elements/Heavy Rare Earth Elements (LREE/HREE) ratios of the components, and use this information to compare the petrogenesis of ALH 84001 with other martian meteorites. The above calculations assume that the bulk samples are representative of different portions of ALH 84001. We will also evaluate the possible heterogeneous distribution of mineral phases in the bulk samples as the cause of compositional heterogeneity in our samples.

Mittlefehldt, D. W.↗