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At least 19 records

Crystal-chemistry and partitioning of REE in whitlockite

Partitioning of Rare Earth Elements (REE) in whitlockite is complicated by the fact that two or more charge-balancing substitutions are involved and by the fact that concentrations of REE in natural whitlockites are sufficiently high such that simple partition coefficients are not expected to be constant even if mixing in the system is completely ideal. The present study combines preexisting REE partitioning data in whitlockites with new experiments in the same compositional system and at the same temperature (approximately 1030 C) to place additional constraints on the complex variations of REE partition coefficients and to test theoretical models for how REE partitioning should vary with REE concentration and other compositional variables. With this data set, and by combining crystallographic and thermochemical constraints with a SAS simultaneous-equation best-fitting routine, it is possible to infer answers to the following questions: what is the speciation on the individual sites Ca(B), Mg, and Ca(IIA) (where the ideal structural formula is Ca(B)18 Mg2Ca(IIA)2P14O56); how are REE's charge-balanced in the crystal; and is mixing of REE in whitlockite ideal or non-ideal. This understanding is necessary in order to extrapolate derived partition coefficients to other compositional systems and provides a broadened understanding of the crystal chemistry of whitlockite.

Colson, R. O.↗

REE Partitioning in Lunar Minerals

Rare earth elements (REE) are an extremely useful tool in modeling lunar magmatic processes. Here we present the first experimentally derived plagioclase/melt partition coefficients in lunar compositions covering the entire suite of REE. Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. These features are taken as evidence of a large-scale differentiation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were subsequently derived. However, the extent of the Eu anomaly in lunar rocks is variable. Fagan and Neal [1] reported highly anorthitic plagioclase grains in lunar impact melt rock 60635,19 that displayed negative Eu anomalies as well as the more usual positive anomalies. Indeed some grains in the sample are reported to display both positive and negative anomalies. Judging from cathodoluminescence images, these anomalies do not appear to be associated with crystal overgrowths or zones.

Rapp, J. F.↗

Clinopyroxene REE distribution coefficients for shergottites The REE content of the Shergotty melt

Rare-earth element (REE) distribution coefficients were measured between synthetic pyroxenes and melts similar in composition to the Shergotty intercumulus fluid. REE-doped synthetic glass samples were analyzed by means of an automated microbeam electron microprobe. The coefficients were found to exhibit a strong positive correlation with pyroxene wollastonite content. Using distribution coefficients measured for the natural phase compositions, REE abundances for the Shergotty intercumulus melt were computed.

Mckay, G.↗

Cerium Stable Isotope Analysis of Synthetic and Terrestrial Rock Reference Materials by MC-ICPMS

Cerium is the most abundant rare earth element (REE) in the solar photosphere, CI chondrites, and the Earth. It has four main stable isotopes (masses: 136,138,140, and 142), with 138Ce being the most studied species, used in geochronology and petrogenesis. In addition, more abundant 140Ce and 142Ce are suggested to be potentially applicable in geochemical investigations. In this work, we developed a modified four-step ion chromatography procedure for Ce chemical separation. Using a MC-ICPMS, we designed a cup configuration to measure 142Ce/140Ce ratio of the samples with an optimized Nd correction equation. A 0.03‰ (2SD) reproducibility was obtained for Ce Ames metal standard. We analyzed ten different igneous and one sedimentary geochemical reference materials. Mean δ142Ce range from −0.07 to 0.32‰. Most of the samples show a heavier Ce isotopic composition than the Ce Ames standard. The majority of rocks have a homogenous δ142Ce. The δ142Ce does not show any correlation with rock chemical composition including their Ce content or rock types. A carbonatite (SARM 40) has a mean δ142Ce of −0.07 ± 0.13‰ (2SD), lower than the other rocks, suggesting the possibility of a pronounced isotopic fractionation. Our work demonstrates the applicability of the developed methodology and the potential of Ce stable isotopes for future geochemical studies. Production of a larger database of δ142Ce values is required to obtain a clearer view on the similarities and differences between different geological material and explaining Ce stable isotope dynamics.

Cerium↗

Anomalous REE patterns in unequilibrated enstatite chondrites: Evidence and implications

We present here a study of Rare Earth Element (REE) microdistributions in unequilibrated enstatite chondrites (EOC's). Although the whole rock REE contents are similar in both unequilibrated and equilibrated chondrites, the host minerals of these refractory elements are different. In the least equilibrated ordinary chondrites (UOC's), the REE reside mainly in glass whereas, in their more equilibrated counterparts, the bulk of the REE is in calcium phosphate, a metamorphic mineral that formed by oxidation of phosphorous originally contained in metal. In the smaller group of enstatite (E) chondrites, calcium phosphate is absent and the phase that contains the highest REE concentrations is a minor mineral, CaS (oldhamite), which contains approximately 50 percent of the total Ca present. In E chondrites, elements typically considered to be lithophiles (such as Ca and Mn) occur in sulfides rather than silicates. This indicates formation under extremely reducing conditions, thus in a region of the solar nebula distinct from those that supplied the more abundant ordinary and carbonaceous chondrites. Previously, we observed a variety of REE patterns in the oldhamite of UEC's; they range from almost flat to some with pronounced positive Eu and Yb anomalies. Here, we searched for complementary REE patterns in other minerals from E chondrites and found them in the major mineral, enstatite. Whenever Eu and Yb anomalies are present in this mineral, they are always negative.

Crozaz, Ghislaine↗

Partition coefficients for REE between garnets and liquids - Implications of non-Henry's Law behaviour for models of basalt origin and evolution

An experimental investigation of Ce, Sm and Tm rare earth element (REE) partition coefficients between coexisting garnets (both natural and synthetic) and hydrous liquids shows that Henry's Law may not be obeyed over a range of REE concentrations of geological relevance. Systematic differences between the three REE and the two garnet compositions may be explained in terms of the differences between REE ionic radii and those of the dodecahedral site into which they substitute, substantiating the Harrison and Wood (1980) model of altervalent substitution. Model calculations demonstrate that significant variation can occur in the rare earth contents of melts produced from a garnet lherzolite, if Henry's Law partition coefficients do not apply for the garnet phase.

Harrison, W. J.↗

Origin and history of the adcumulate eucrite, Moama as inferred from REE abundances, Sm-Nd and U-Pb systematics

The abundances of Sm-Nd and U-Pb isotopes and of rare earth elements (REE) in Moama cumulate eucrite were investigated. The Sm-Nd data plotted on a Nd-143/Nd-144 vs Sm-147/Nd-144 evolution diagram define a line with a slope corresponding to an age of 4.58 plus or minus 0.05 billion years and an initial Nd-143/Nd-144 ratio of about 0.50684. Moama was found to contain the lowest overall trivalent REE abundances, the most light REE-depleted abundance pattern, and largest positive Eu anomaly of any eucrite yet studied. The REE data indicate that Moama could have been derived by about 1 to 5% fractional crystallization from a liquid with REE contents similar to Juvinas, or about 20 to 30% fractional crystallization from a Sioux County-like liquid. The data are consistent with the hypothesis that the Moama, Serra de Mage, and Moore county cumulate meteorites could have been derived from the same parent liquid. Results of the U-Th-Pb study indicate that the majority of the Pb in Moama is of terrestrial origin, and suggest that the meteorite has undergone a minor thermal event causing re-equilibration of the U-Pb system.

Hamet, J.↗

Rare earth element abundances in rocks and minerals from the Fiskenaesset Complex, West Greenland

The paper reports activation-analysis determinations of rare-earth-element (REE) and other trace-element concentrations in selected rocks, plagioclase, and mafic separates from the Fiskenaesset Complex. The REE abundances are found to be very low and atypical in comparison with other terrestrial anorthosites. The plagioclases are shown to be characterized by a deficiency in heavy RE elements relative to light ones and a positive Eu anomaly, while the mafic separates are enriched in heavy rare earths and have no Eu anomaly, except in one sample. It is found that the bulk and trace-element abundances of the plagioclases are similar to those observed in some lunar anorthosites, but the degree of Eu anomaly is less in the plagioclases. The data are taken as confirmation of the idea that fractionation processes were involved in the origin of the Complex, and it is concluded that the Complex may have been produced from a magma generated by partial melting of a garnet-bearing source.

Henderson, P.↗

Crystal/liquid partitioning of REE in basaltic systems Extreme fractionation of REE in olivine

The calculation of partial coefficients for Nd, Sm, Gd, and Yb between olivine and synthetic basaltic melts using the percent level doping technique and microprobe analytical techniques is examined. The experimental and analytical procedures are described. The relationship between rare earth elements (REEs) concentrations and crystal margins caused by Rees X-rays from surrounding glass is discussed. Average olivine/liquid distribution coefficients for Nd, Sm, Gd, and Yb for mare and highlands basaltic melts are presented. The data reveal that the distribution coefficients for light REEs are lower than those obtained in previous studies, and the slope of the olivine/liquid distribution coefficient pattern is steeper; potential sources of error in the previous and present studies which could explain the differences in distribution coefficients and slope are investigated.

Mckay, G. A.↗

Isotopic and REE studies of lunar basalt 12038 - Implications for petrogenesis of aluminous mare basalts

Sr, Nd, and Sm isotopic studies of lunar basalt 12038, one of the so-called aluminous mare basalts, are reported. The evolution of the Sr and Nd isotopic compositions and the rare earth element (REE) abundances is successfully modeled within the framework of the model developed by Nyquist et al. (1977, 1979) for Apollo 12 olivine-pigeonite and ilmenite basalts. It is pointed out that the isotopic and trace element features of 12038 can by modeled as produced by partial melting of a cumulate mantle source which crystallized from a lunar magma ocean with a chondrite-normalized REE pattern of constant negative slope. Chondrite-normalized La/Yb is equal to 2.2 for this hypothetical magma ocean pattern.

Nyquist, L. E.↗

Al-26, Pu-244, Ti-50, REE, and trace element abundances in hibonite grains from CM and CV meteorites

Hibonites from the CM meteorites Murchison, Murray, and Cold Bokkeveld, and hibonites and Ti-rich pyroxene from the CV chondrite Allende are studied. Electron microprobe measurements of major element concentrations and track and ion probe measurements of Mg and Ti isotopic ratios, rare earth elements (REEs), and trace element abundances are analyzed. Correlations between isotopic anomalies in Ti, Al-26, Pu-244, and Mg-26(asterisk) are examined. Ti isotopic anomalies are compared with REE and trace element abundance patterns. Reasons for the lack of Al-26 in the hibonites are investigated and discussed. It is observed that there is no correlation between the Ti isotopic compositions, and the presence of Mg-26(asterisk), Pu-244, and REE and trace element patterns in individual hibonite samples. The data reveal that hibonites are not interstellar dust grains but formed on a short time scale and in localized regions of the early solar system.

Fahey, A. J.↗

Magnetism of Carbonados

Carbonados are porous polycrystalline (with crystal sizes up to 100 micrometer) diamonds. Carbonado is found only in alluvial deposits in Bahia, Brazil and in the Central African Republic (CAR). Alluvial deposit host is 1.5 Ga while the carbonados are between 2.6 - 3.8 Ga. The process of fusing the carbonado microcrystals together is not fully understood, partly due to fact that the origin of these carbonado, is not known. Several modes of origins are proposed for carbonado. First, a crustal origin. Carbonados have a light carbon and helium isotopic signature. They contain an enrichment of the rare-earth elements (REE). Carbonados have tightly trapped atmospheric noble gases and contain an evidence of high He content despite the carbonado expected depletion of He at mantle temperatures. Carbonados have high porosity incompatible with high pressure mantle conditions. Second, a mantle origin is proposed based on similar REE pattern to kimberlites. The presence of nitrogen platelet (by IR spectra) indicates high temperature origin and syngenetic inclusions of rutile, ilmenite, and magnetite indicates high pressure and high temperature conditions consistent with mantle origin as well. Third, it is proposed that carbonado diamonds are a result of early impacts into crustal rocks. This is indicated by the rare and controversial occurrence of high pressure diamond polymorph, londsdaleite, frequently found in diamonds from meteorite impact sites, and by observation of planar deformation features, possibly indicating shock events. Finally, it is suggested that carbonados have an extraterrestrial origin, as indicated by a long term annealing based on observation of a zero-phonon line, attributed to paired nitrogen atoms in association with a vacancy.

Kletetschka, G.↗

The Pasamonte unequilibrated eucrite: Pyroxene REE systematic and major-, minor-, and trace-element zoning

We are evaluating the trace-element concentrations in the pyroxenes of Pasamonte. Pasamonte is a characteristic member of the main group eucrites, and has recently been redescribed as a polymict eucrite. Our Pasamonte sample contained eucritic clasts with textures ranging from subophitic to moderately coarse-grained. This study concentrates on pyroxenes from an unequilibrated, coarse-grained eucrite clast. Major-, minor-, and trace-element analyses were measured for zoned pyroxenes in the eucritic clast of Pasamonte. The major- and minor-element zoning traverses were measured using the JEOL 733 electron probe with an Oxford-Link imaging/analysis system. Complemenatry trace elements were then measured for the core and rim of each of the grains by SIMS. The trace elements analyzed consisted of eight REE, Sr, Y, and Zr. These analyses were performed on a Cameca 4f ion probe. The results of the CI chondrite normalized (average CI trace-element analyses for several grains and the major- and minor-element zoning patterns from a single pyroxene grain are given. The Eu abundance in the cores of the pyroxenes represents the detection limit and therefore the (-Eu) anomaly is a minimum. Major- and minor-element patterns are typical for igneous zoning. Pyroxene cores are Mg enriched, whereas the rims are enriched in Fe and Ca. Also, Ti and Mn are found to increase, while Cr and Al generally decrease in core-to-rim traverses. The cores of the pyroxenes are more depleted in the Rare Earth Elements (REE) than the rims. Using the minor- and trace-element concentrations of bulk Pasamonte and the minor- and trace-element concentrations from the cores of the pyroxenes in Pasamonte measured in this study, we calculated partition coefficients between pyroxene and melt. This calculation assumes that bulk Pasamonte is representative of a melt composition.

Pun, A.↗

The Parent Magmas of the Cumulate Eucrites: A Mass Balance Approach

The cumulate eucrite meteorites are gabbros that are related to the eucrite basalt meteorites. The eucrite basalts are relatively primitive (nearly flat REE patterns with La approx. 8-30 x CI), but the parent magmas of the cumulate eucrites have been inferred as extremely evolved (La to greater than 100 x CI). This inference has been based on mineral/magma partitioning, and on mass balance considering the cumulate eucrites as adcumulates of plagioclase + pigeonite only; both approaches have been criticized as inappropriate. Here, mass balance including magma + equilibrium pigeonite + equilibrium plagiociase is used to test a simple model for the cumulate eucrites: that they formed from known eucritic magma types, that they consisted only of magma + crystals in chemical equilibrium with the magma, and that they were closed to chemical exchange after the accumulation of crystals. This model is tested for major and Rare Earth Elements (REE). The cumulate eucrites Serra de Mage and Moore County are consistent, in both REE and major elements, with formation by this simple model from a eucrite magma with a composition similar to the Nuevo Laredo meteorite: Serra de Mage as 14% magma, 47.5% pigeonite, and 38.5% plagioclase; Moore County as 35% magma, 37.5% pigeonite, and 27.5% plagioclase. These results are insensitive to the choice of mineral/magma partition coefficients. Results for the Moama cumulate eucrite are strongly dependent on choice of partition coefficients; for one reasonable choice, Moama's composition can be modeled as 4% Nuevo Laredo magma, 60% pigeonite, and 36% plagioclase. Selection of parent magma composition relies heavily on major elements; the REE cannot uniquely indicate a parent magma among the eucrite basalts. The major element composition of Y-791195 can be fit adequately as a simple cumulate from any basaltic eucrite composition. However, Y-791195 has LREE abundances and La/Lu too low to be accommodated within the model using any basaltic eucrite composition and any reasonable partition coefficients. Postcumulus loss of incompatible elements seems possible. It is intriguing that Serra de Mage, Moore County, and Moama are consistent with the same parental magma; could they be from the same igneous body on the eucrite parent asteroid (4 Vesta)?

Treiman, Allan H.↗

Expanding the REE Partitioning Database for Lunar Materials

Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. This is taken as evidence of a large-scale differentation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were later derived. However, the extent of the Eu anomaly in lunar rocks is variable. Some plagioclase grains in a lunar impact rock (60635) have been reported to display a negative Eu anomaly, or in some cases single grains display both positive and neagtive anomalies. Cathodoluminescence images reveal that some crystals have a negative anomaly in the core and positive at the rim, or vice versa, and the negative anomalies are not associated with crystal overgrowths. Oxygen fugacity is known to affect Eu partitioning into plagioclase, as under low fO2 conditions Eu can be divalent, and has an ionic radius similar to Ca2+ - significant in lunar samples where plagioclase compositions are predominantly anorthitic. However, there are very few experimental studies of rare earth element (REE) partitioning in plagioclase relevant to lunar magmatism, with only two plagioclase DEu measurements from experiments using lunar materials, and little data in low fO2 conditions relevant to the Moon. We report on REE partitioning experiments on lunar compositions. We investigate two lunar basaltic compositions, high-alumina basalt 14072 and impact melt breccia 60635. These samples span a large range of lunar surface bulk compositions. The experiments are carried out at variable fO2 in 1 bar gas mixing furnaces, and REE are analysed by and LA-ICP-MS. Our results not only greatly expand the existing plagioclase DREE database for lunar compositions, but also investigate the significance of fO2 in Eu partitioning, and in the interpretation of Eu anomalies in lunar materials.

Rapp, Jennifer F.↗

Thermal Analysis, Compressibility, and Decomposition of Synthetic Bastnäsite-(La) to Lanthanum Oxyfluoride

Understanding basic material properties of rare earth element (REE) bearing minerals such as their phase stability and equations of state can assist in understanding how economically viable deposits might form. Bastnäsite is the most commonly mined REE bearing mineral. We synthesized the lanthanum-fluoride end member, bastnäsite-(La) (LaCO3F), and investigated its thermal behavior and decomposition products from 298 K to 1173 K under ambient pressure conditions through thermogravimetric analysis, differential scanning calorimetry, evolved gas analysis, and high temperature powder X-ray diffraction. We also investigated the compressibility of bastnäsite-(La) via single crystal X-ray diffraction in diamond anvil cells at an ambient temperature up to 11.3 GPa and from 4.9 GPa to 7.7 GPa up to 673 K. At ambient pressure, bastnäsite-(La) was stable up to 598 K in air, where it decomposed into CO2 and tetragonal γ-LaOF. Above 948 K, cubic α-LaOF is stable. High temperature X-ray diffraction data were used to fit the Fei thermal equation of state and the thermal expansion coefficient α(sub 298) for all three materials. Bastnäsite-(La) was fit from 298 K to 723 K with V(sub 0) = 439.82 Å(exp 3), α(sub 298) = 4.32 × 10(exp -5) K(exp -1), a(sub 0) = −1.68 × 10(exp -5) K(exp -1), a(sub 1) = 8.34 × 10(exp -8) K(exp -1), and a(sub 2) = 3.126 K(exp -1). Tetragonal γ-LaOF was fit from 723 K to 948 K with V(sub 0) = 96.51 Å(exp 3), α(sub 298) = 2.95×10(exp -4) K(exp -1), a(sub 0) = −2.41×10(exp -5) K(exp -1), a(sub 1) = 2.42×10(exp -7) K(exp -1), and a(sub 2) = 41.147 K(exp -1). Cubic α-LaOF was fit from 973 K to 1123 K with V(sub 0) = 190.71 Å(exp 3), α(sub 298) = −1.12×10(exp -5) K(exp -1), a(sub 0) = 2.36×10(exp -4) K(exp -1), a(sub 1) = −1.73 × 10(exp -7) K(exp -1), and a(sub 2) = −17.362 K(exp -1). An ambient temperature third order Birch–Murnaghan equation of state was fit with V(sub 0) = 439.82 Å(exp 3), K(sub 0) = 105 GPa, and K’ = 5.58.

Bastnäsite↗

Rare earths, other trace elements and iron in Luna 20 samples.

The results of the analysis by neutron activation of six samples from the Luna 20 mission and one sample of less than 1 mm fines from Apollo 16 are reported. The concentrations of the rare-earth elements (REE) in the samples of fines from Luna 20 and Apollo 16 are less than those found for corresponding materials from the mare areas but a negative Eu anomaly is still present. The concentrations of the REE in fines from Luna 20 are only about two-thirds as great as in the sample of Apollo 16 fines, but the concentration of Co, Sc and Cr are greater by factors ranging from 1.5 to 2.3.

Helmke, P. A.↗

Major and trace elements in igneous rocks from Apollo 15.

The concentrations of major and trace elements have been determined in igneous rocks from Apollo 15. All materials analyzed have typical depletions of Eu except for minerals separated from sample 15085. Four samples have concentrations of trace elements that are similar to those of KREEP. The samples of mare basalt from Apollo 15 have higher concentrations of FeO, MgO, Mn, and Cr and lower concentrations of CaO, Na2O, K2O, and rare-earth elements (REE) as compared to the samples of mare basalt from Apollos 11, 12, and 14. The samples can be divided into two groups on the basis of their normative compositions. One group is quartz normative and has low concentrations of FeO while the other is olivine normative and has high concentrations of FeO. The trace element data indicate that the samples of olivine normative basalt could be from different portions of a single lava flow.

Helmke, P. A.↗