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All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Apollo 14 mare basalt petrogenesis - Assimilation of KREEP-like components by a fractionating magma

Based on analysis of whole rock and mineral data from 22 samples, it is shown that the trace element characteristics of 14321 high-AL mare basalts exhibit variations that cannot be related to short-range mixing alone. It is suggested that the five groups defined for Apollo 14 high-Al basalts are due to sampling. It is found that the addition of new data results in a continuum of compositions. Detailed trace element modeling demonstrates that a primitive parental magma evolves by assimilation and fractional crystallization (AFC) with KREEP. The ratio of mass assimilated to mass crystallized is found to be 0.22. It is suggested that this AFC process occurs within the lunar crust and that the fractionating phases are effectively removed from the system.

Neal, Clive R.↗
NASA NTRS1992

Optical luminescence spectroscopy as a probe of the surface mineralogy of Mars

Optical luminescence (OpL) spectroscopy is an attractive use of a visible-near-IR spectrometer on a Mars lander because mineral products of atmosphere-surface interactions on Mars will probably have characteristic OpL spectra. Optical luminescence spectra would be taken at night, when a spectrometer might otherwise sit idle. Also needed would be a source of exciting radiation, which could be shared with other experiments. Optical luminescence is emission of nonthermal optical photons (near-UV through near-IR) as a response to energy input. On absorption of energy, an atom (or ion) will enter an excited state. The favored decay of many such excited states involving valence-band electrons is emission of an optical photon. Optical luminescence spectra can be useful in determining mineralogy and mineral composition. Optical luminescence in crystals can arise from essential elements (or ions), trace-element substituents (activators), or defects. Common activators in salts of alkali and alkaline earth elements include Mn(2+)(VI), other transition metals, the rare earths, and the actinides. Trace substituents of other species can enhance or quench OpL (e.g., Pb(2+) vs. Fe(3+)). Optical luminescence can also arise from defects in crystal structures, including those caused by radiation and shock.

Treiman, A. H.↗
NASA NTRS2003

Northwest Africa 773: Lunar Mare Breccia with a Shallow-formed Olivine-Cumulate Component, Very-Low-Ti Heritage, and a KREEP Connection

Northwest Africa 773 is one of the more unusual lunar meteorites found in recent years because it contains a prominent clast lithology, which appears to be an olivine-rich cumulate and because it is a very-low-Ti (VLT) mare breccia with relatively high incompatible-trace-element concentrations and LREE/HREE enrichment. A lunar origin was verified by Fagan and coworkers on the basis of noble-gas contents, oxygen isotopes, and mineral compositions. Fagan et al. described two lithologies: (1) heterolithic impact breccia with a regolith component and (2) cumulus olivine gabbronorite. Here, we refer to these as the breccia (Bx) lithology and the olivine-cumulate (OC) lithology. The impact breccia components are predominantly volcanic (basaltic), and, in this context, the occurrence of the cumulus lithology is especially significant: is it related to the volcanic components or does it represent a deep-seated rock entrained by the basaltic magma as it rose to the surface? Elevated incompatible-element concentrations with more or less KREEP-like inter-element ratios and very-low-Ti concentrations distinguish both lithologies of this meteorite from Apollo mare basalts. Here, we summarize key compositional information (bulk and mineral), especially related to the OC lithology, to show that it formed at shallow depth and comes from a VLT ultramafic precursor that mixed with a KREEP-like trace-element component deep in the crust or upper mantle.

Jolliff, B. L.↗
NASA NTRS1982

Anomalies within the system - Rochechouart target rock meteorite

Contaminated impact crater formations are pertinent to the study of meteoritic contamination at the Cretaceous-Tertiary boundary and other Ir-enriched layers. Target mixing considerations and volumetric estimates of Rochechouart breccias are presently combined with the geochemistry of both major and siderophile trace elements, to evaluate how the chemistry of the preserved target rock-projectile mixture evolved since deposition. Over 99 percent of the mass of extraterrestrial Ir and Os in preserved formations at Rochechouart is located in suevite-like breccias and impact melts. Hydrothermal alteration and/or weathering are the most likely processes to explain both major and trace element redistribution in Rochechouart formations.

Lambert, P.↗
NASA NTRS1981

Columbia River volcanism - The question of mantle heterogeneity or crustal contamination

It is found that, although crystal fractionation played an important role in producing the chemical characteristics of Columbia River Province basalts displaying a wide range of chemical and isotopic compositions, the isotopic variability calls for the involvement of at least two isotopically distinct components. The major and trace element characteristics of the main volume of the basalts are not consistent with a metasomatized mantle source region, and the presence of a primordial mantel component is not supported by the chemical data. Models of simple binary mixing between a primary magma and Precambrian sialic crustal materials, while satisfying the observed Nd and Sr isotopic variations, fail to account for major trace element abundances. The combination of crustal assimilation and fractional crystalization is found to give a superior fit to the compositional data.

Carlson, R. W.↗
NASA NTRS1977

Chemistry of Apollo 12 mare basalts - Magma types and fractionation processes

Major and trace element data for a large suite of petrographically diverse Apollo 12 mare basalts are presented, and magma types sampled at the Apollo 12 site are characterized. The data confirm earlier classifications of the basalts into olivine, pigeonite, ilmenite, and feldspathic basalts. The olivine and pigeonite basalts are shown to be comagnetic and related by olivine fractionation. The other types, which differ in trace element and isotopic characteristics, are derived from different sources within the lunar interior. The spatial relations between the main basalt types are discussed in terms of local cratering events, and it is suggested that the younger ilmenite basalts overlie the olivine-pigeonite basalts. The role of olivine-dominated near-surface crystal fractionation in causing chemical variation is examined, and a relation between inferred cooling rate and the position of a sample in the fractionation sequence is determined.

Rhodes, J. M.↗
NASA NTRS2009

Chemistry of Diogenites and Evolution of their Parent Asteroid

Diogenites are orthopyroxenite meteorites [1]. Most are breccias, but remnant textures indicate they were originally coarse-grained rocks, with grain sizes of order of cm. Their petrography, and major and trace element chemistry support an origin as crustal cumulates from a differentiated asteroid. Diogenites are genetically related to the basaltic and cumulate-gabbro eucrites, and the polymict breccias known as howardites, collectively, the HED suite. Spectroscopic observations, orbit data and dynamical arguments strongly support the hypothesis that asteroid 4 Vesta is the parent object for HED meteorites [2]. Here we discuss our new trace element data for a suite of diogenites and integrate these into the body of literature data. We use the combined data set to discuss the petrologic evolution of diogenites and 4 Vesta.

Mittlefehldt, D.W.↗
DOE OSTI2019

Multivariate Analysis Based on Geochemical, Isotopic, and Mineralogical Compositions of Uranium-Rich Samples

The chemical and isotopic (U, Pb, Sr) signatures for a suite (n = 23) of pristine (>80 wt. % UO 2 ) and altered uraninite samples (>70–80 wt. % UO 2 ) from various locations worldwide have been determined for the purpose of identifying potential fingerprints for nuclear forensic analysis. The characterization of the uraninite samples included determination of major, minor and trace element contents, Sr, Pb, and U isotopic compositions, and secondary mineral assemblages. Due to the multivariate approach adopted in this study, principal component analysis (PCA) has been employed to allow the direct comparison of multiple variable types. The PCA results indicate that the geological origin (sandstone, metamorphite, intrusive, granite and unconformity) of pristine uraninite can be readily identified utilizing various combinations of major and/or trace element concentrations with isotopic compositions.

58 GEOSCIENCES↗
DOE OSTI2021

Sectoral and growth rate control on elemental uptake by individual calcite crystals

Heterogeneous distribution of trace elements (impurities) within individual calcite crystals is a phenomenon commonly observed in natural and laboratory systems. Changes in thermodynamic intensive parameters (mostly chemical potential and temperature) cannot always explain the inhomogeneous impurity patterns in calcite crystals and it has been suggested that growth rate and crystallographic orientation may exert strong effects on elemental incorporation into calcite. In addition, there are a number of experimental studies on micro-scale element (E) distribution between non-equivalent pairs of calcite vicinal faces (known as sectoral zoning); however, the variability of partition coefficients (e.g., K E = (E/Ca) calcite /(E/Ca) fluid ) within individual crystals remains undetermined. In this study, we have extended the work on elemental distribution between crystal sectors to evaluation of partition coefficients of trace and minor elements (Li, B, Mg, and Sr) in calcite crystal faces (10–14) and (01-12), whose growth rates were assessed. Growth entrapment model (GEM) and lattice strain theory were applied to explain K E heterogeneity by varying near-surface diffusivity of Mg and Sr and by varying surface enrichment factor for Li, B, Mg, and Sr. Decoupling of sectoral and growth rate effects reveals that sectoral zoning plays a key role in elemental distribution. More specifically, K Li and K B vary by more than one order of magnitude and K Mg varies by a factor of two within individual crystal faces. Strontium sectoral distribution is different from those of Li, B, and Mg and K Sr varies by up to a factor of two. Finally, these behaviors likely reflect different mechanisms of incorporation of Li, B, Mg, and Sr into calcite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has a H-isotopic composition that is intermediate (δD of 1000-2000per mille) between an isotopically light mantle (Delta D is less than 275per mille [10]) and an isotopically heavy atmosphere (δD of 2500-6100per mille [11, 12]). Apatites in NWA 7034 occur in a number of lithologic domains, however apatites across all lithologic domains have been affected by a Pb-loss event at about 1.5 Ga before present [5], so they are unlikely to have retained a primary composition and are more likely to have equilibrated with fluids within the martian crust that may or may not have exchanged with the martian atmosphere. Equilibration of apatite with crustal fluids is further supported by the chlorine-rich compositions exhibited by apatites in NWA 7034 in comparison to apatites from other martian meteorites (Figure 1; [13]). Cl is more hydrophilic than F, which promotes formation of Cl-rich apatite compositions in fluid-rich systems [e.g., 14, 15-17].

McCubbin, F. M.↗
NASA NTRS2011

Towards a Regolith Maturity Index for Howardites

The Dawn spacecraft has just arrived at asteroid 4 Vesta, parent of the howardite, eucrite and diogenite (HED) meteorites [1], to begin a yearlong surface study from orbit [2]. As Dawn will view a debris-covered surface, understanding the formation and mixing processes for the debris layer will strongly aid surface data interpretations. Howardites are polymict breccias mainly composed of clasts derived from basaltic (eucritic) and orthopy-roxenitic (diogenitic) parent materials [3]. Some howardites are poorly reworked (fragmental howardites) whilst others have been extensively gardened in an active regolith (regolithic howardites) [4]. The latter may represent an ancient, well-mixed regolith, whilst the former may be from more recent ejecta deposits [4]. Due to environmental differences, regolith development on Vesta differs in detail from that on the Moon [4-6]. We have been developing petrological criteria to apply to howardite thin sections to determine their relative regolithic maturity, which we are fine-tuning with comparison to noble gas data [7, 8]. Whilst we previously emphasized the abundance of reworked clasts (fragmental and impact-melt breccia clasts), this is an imperfect criterion: one howardite with abundant re-worked clasts (EET 99408) shows no evidence of solar wind Ne (SW-Ne), yet, two of our alleged fragmental howardites have clear SW-Ne signatures (LEW 85313, MET 00423) [7, 8]. We are now investigating the diversity in minor and trace element contents of low-Ca pyroxene clasts in howardites as a measure of regolith grade, and will begin analyses of such grains within reworked clasts. Our hypothesis is that regolithic howardites (and the breccia clasts they contain) will show greater diversity because they sampled more diverse diogenitic plutons than fragmental howardites, which formed from ejecta from only a few impacts [e.g. 4]. Our initial LA-ICP-MS work showed ranges in trace element diversity in low-Ca pyroxenes (estimated from the standard error of the mean of analyses), where those howardites considered of medium to high regolithic grade showed greater diversity [9]. Our EMPA results (from a larger howardite suite) show an overall greater diversity in our putative medium to high regolithic grade howardites, though there are exceptions. The greatest diversity is found for paired howardites GRO 95574 and GRO 95581, which were not considered regolithic in our initial study. We will continue investigating avenues to determine regolith maturity in thin section, factoring in bulk rock compositional data, and will coordinate these studies with noble gas results.

Mittlefehldt, David W.↗
DOE OSTI2026

A case study on the use of carbon sticky tabs for microbeam uranium isotope measurement with an emphasis on understanding the influence of subtle variations in substrate composition

In this paper we integrate laser induced breakdown spectroscopy (LIBS), large geometry secondary ion mass spectrometry (LG-SIMS), laser ablation—multi collector—inductively coupled plasma—mass spectrometry (LA-MC-ICP-MS), and trace elemental compositions obtained by bulk digestion from a suite of commercially available carbon sticky tabs to determine if subtle variations in the tab’s composition can be tied to shifts in the observed uranium isotopic composition of the IRMM-2020 standard relative to its ‘true’ value. The results suggest that, although clear differences exist in the relative abundances of carbon and hydrogen across the various carbon sticky tabs examined, as well as differences in their trace elemental and total uranium concentrations, these differences do not appear to influence the LG-SIMS or LA-MC-ICP-MS uranium isotope ratio measurements, or the appearance of the uranium mass spectrum scans. Instead, the quality (i.e., precision and accuracy) of the LG-SIMS and LA-MC-ICP-MS results are directly proportional to the observed signal intensity at the time of analysis. For the LG-SIMS measurements, there does appear to be a direct correlation between 235U1H hydride formation rates and vacuum conditions within the instrument’s analytical chamber. Furthermore, none of the carbon sticky tabs examined by LG-SIMS displayed evidence of elevated background uranium content. While a preliminary correlation was observed between the uranium isotope background signal during LA-MC-ICP-MS and the total uranium concentrations determined by isotope dilution, none of the tabs displayed a high enough analytical background to affect the isotope ratio measurements.

Zirakparvar, Alex [ORNL] (ORCID:0000000337797730)↗
NASA NTRS1979

The mean age of mantle and crustal reservoirs

An analysis of two transport models for trace elements in mantle and crust evolution and related to the observed abundance patterns. In model I, continents are derived by melt extraction over the earth history from undepleted mantle, and the residue forms a depleted mantle which is the current source of mid-ocean ridge basalts. In model II, new additions to continents are derived from a mantle reservoir 2, which becomes more depleted by repeated extraction of melts. The isotopic composition and concentrations of trace elements are shown to reduce to simple mathematical expressions which permit calculations of basic evolutionary parameters. The mean age of the crust mass and isotopic data for the continental crust and the mantle are discussed, concluding with a consideration of their difference in compositions of newly derived crust.

Jacobsen, S. B.↗
DOE OSTI2018

Archaeological Arsenical Bronzes and Equilibrium in the As-Cu System

Understanding the effects of impurities, segregation, undercooling, and solidification velocity is necessary to reconstruct prehistoric As-Cu alloy manufacturing processes and practices. Moreover, these alloys often contain a wide variety of minor and trace elements such that the binary As-Cu equilibrium phase diagram does not adequately represent arsenical bronze artifacts as-cast in ancient molds. Furthermore, the variable cooling rates present in as-cast alloys of predominantly arsenic and copper, due to the thermal properties of differing mold materials, would have had profound effects on the formation of inversely segregated arsenic. Alloys with 1 to 15 wt pct arsenic were prepared and studied using differential thermal analysis, metallography, and scanning electron microscopy with energy-dispersive X-ray spectroscopy. Equilibrium diagrams were established and the potential influence of trace elements discussed. A new liquidus curve for the equilibrium diagram in this compositional range, measuring slightly higher in temperature, was established.

36 MATERIALS SCIENCE↗
NASA NTRS1978

Chemistry and petrology of Luna 24 lithic fragments and less than 250-micron soils - Constraints on the origin of VLT mare basalts

Results are reported on a combined INAA-petrologic study of 17 small (0.2-1.5 mg) Luna 24 lithic and mineral fragments and INAA study of 5 bulk soils and mineral separates from gabbro 24170. Lithic and mineral fragments are classified into VLT mare basalts (ferrobasalt and metabasalts), low-Ti, variolitic mare basalt, gabbros, melt rock and soil breccia. Data indicate 5 possible magma types, represented by: (1) VLT ferrobasalt and gabbro fragments, with low-TiO2 (about 1%), slightly bow-shaped REE pattern, and low REE concentrations (5-10X chondritic); (2) a ferrobasalt (Laul et al., 1978) and metabasalt fragments with major and trace element contents similar to (1), but positive Eu anomalies; (3) one gabbro fragment with distinctive pyroxene compositional trend (increasing Ti with nearly constant Fe/Fe + Mg) and highest REE contents of any Luna 24 mare basaltic sample, (4) a gabbro fragment with considerably less V and Cr2O3 than ferrobasalt and metabasalt fragments; and (5) variolitic basalt fragment with higher Ti2(2.3%) than other Luna 24 basalts and pyroxene that has increasing then decreasing Ti with increasing Fe/Fe + Mg. Trace element data place constraints on the nature of the source region and possible parent magmas for the Luna 24 VLT ferrobasalt.

Ma, M.-S.↗
NASA NTRS1975

Petrogenesis of KREEP

Solid/liquid distribution coefficients (weight basis) were experimentally determined for a number of trace elements for olivine, orthopyroxene, plagioclase and ilmenite. Values of distribution coefficients were measured at 1200 C and a f sub O2 of 10 to the -13.0 power for liquids similar in composition to the olivine-opx-plagioclase peritectic in the pseudoternary system (Fe,Mg)2SiO4-CaAl2Si2O8-SiO2. Values were also measured at 1140 C and a f sub O2 of 10 to the -12.8 power for liquids similar in composition to high-Ti mare basalts. Major and trace element partitioning and relevant phase equilibria were used to investigate possible parent-daughter relationships between a number of highland samples and highly evolved KREEP-rich materials. Out of about 80 highlands samples tested, 33 were found to be possible parents to the KREEP-rich materials. The average composition of these samples is very similar to that of the Low-K Fra Mauro basalt (LKFM). A model is proposed to explain the production of LKFM-type material and more evolved members of the KREEP suite.

Mckay, G. A.↗
NASA NTRS1977

Geochemical studies of the White Breccia Boulders at North Ray Crater, Descartes region of the lunar highlands

The samples of the White Breccia Boulders obtained during the Apollo 16 mission and investigated in the reported study include an anorthositic breccia (67415), a dark matrix breccia (67435), a light matrix breccia (67455), and a large clast of dark matrix breccia (67475) taken from the 67455 boulder. The chemical analyses of bulk samples of the samples are listed in a table. A graph shows the lithophile trace element abundances. Another graph indicates the variation of Sm with Al2O3 content for samples from the White Breccia Boulders. The North Ray Crater breccias are found to be in general slightly more aluminous than breccias from the other stations at the Apollo 16 site. Analyses of eight Apollo 16 breccias cited in the literature range from 25% to 35% Al2O3. However, the North Ray Crater breccias are more clearly distinct from the other Apollo 16 breccias in their contents of lithophile trace elements.

Lindstrom, M. M.↗
NASA NTRS2017

Determination of Trace and Volatile Element Abundance Systematics of Lunar Pyroclastic Glasses 74220 and 15426 Using LA-ICP-MS

Since their recognition as pyroclastic glasses generated by volcanic fire fountaining on the Moon, 74220 and 15426 have garnered significant scientific interest. Early studies recognized that the glasses were particularly enriched in volatile elements on their surfaces. More recently, detailed analyses of the interiors of the glasses, as well as of melt inclusions within olivine grains associated with the 74220 glass beads, have determined high H2O, F, Cl and S contents. Such elevated volatile contents seem at odds with evidence from moderately volatile elements (MVE), such as Zn and K, for a volatile- depleted Moon. In this study, we present initial results from an analytical campaign to study trace element abundances within the pyroclastic glass beads. We report trace element data determined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for 15426 and 74220.

McIntosh, E. Carrie↗