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Complementary rare earth element patterns in unique achondrites, such as ALHA 77005 and shergottites, and in the earth

Abundances of major, minor, and trace elements are determined in the Antarctic achondrite Allan Hills (ALHA) 77005 via sequential instrumental and radiochemical neutron activation analysis. The rare earth element (REE) abundances of ALHA 77005 reveal a unique chondritic normalized pattern; that is, the REEs are nearly unfractionated from La to Pr at approximately 1.0X chondrites, monotonically increased from Pr to Gd at approximately 3.4X with no Eu anomaly, nearly unfractionated from Gd and Ho and monotonically decreased from Ho to Lu at approximately 2.2X. It is noted that this unique REE pattern of ALHA 77005 can be modeled by a melting process involving a continuous melting and progressive partial removal of melt from a light REE enriched source material. In a model of this type, ALHA 77005 could represent either a crystallized cumulate from such a melt or the residual source material. Calculations show that the parent liquids for the shergottites could also be derived from a light REE enriched source material similar to that for ALHA 77005.

Ma, M.-S.↗

Trace element concentrations in the isotopically unique Allende inclusion, EK 1-4-1

The bulk sample and mineral separates of the isotopically unique Allende inclusion, EK 1-4-1, are analyzed by instrumental neutron activation for the concentrations of REE, Sc, Fe, Co, Cr, Na, and Ir, and REE concentrations were also determined by mass spectrometric isotope dilution for two density separates. Results show that the inclusion is enriched in light REE compared to heavy REE with a positive Yb anomaly, and has a high Cr concentration, both of which indicate group II affinity, although EK 1-4-1 is a coarse-grained group I inclusion. On the other hand, high Ir, and Sc, and low FeO and Co concentrations were found in the bulk inclusion, and low Na concentrations were found in mineral separates, which indicate an affinity to group I. In addition, for melilite and pyroxene fractions REE, Sc, Co, and Fe were determined to have distributions that were substantially different from those observed for normal Allende type B inclusions.

Nagasawa, H.↗

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.↗

Phosphates in pallasite meteorites as probes of mantle processes in small planetary bodies

Trace element analyses of the phosphates minerals in stony-iron pallasite meteorites are used here to investigate the magmatic history of the silicate portions of pallasites. In Eagle Station and seven other pallasites, the phosphates have relatively low concentrations of REEs and are strongly enriched in heavy relative to light REE. These patterns are consistent with formation of phosphate by subsolidus reactions between metal and silicate, in which phosphate inherits the REE pattern of olivine. In Springwater and Santa Rosalia, calcium-rich phosphates have higher concentrations of REE, are enriched in light relative to heavy REE, and have negative europium anomalies. These patterns are consistent with crystallization of phosphate from a europium-depleted chondritic liquid. This is unlikely to have happened near the base of the differentiating parent-body mantle; it suggests that some pallasites may come from regions of their parent bodies much nearer the surface than the core-mantle boundary.

Davis, Andrew M.↗

The Mineralogical Record of Oxygen Fugacity Variation and Alteration in Northwest Africa 8159: Evidence for Interaction Between a Mantle Derived Martian Basalt and a Crustal Component(s)

A prominent geochemical feature of basaltic magmatism on Mars is the large range in initial Sr isotopic ratios (approx. 0.702 - 0.724) and initial epsilon-Nd values (approx. -10 to greater than +50). Within this range, the shergottites fall into three discreet subgroups. These subgroups have distinct bulk rock REE patterns, mineral chemistries (i.e. phosphate REE patterns, Ni, Co, V in olivine), oxygen fugacity of crystallization, and stable isotopes, such as O. In contrast, nakhlites and chassignites have depleted epsilon-Nd values (greater than or equal to +15), have REE patterns that are light REE enriched, and appear to have crystallized near the FMQ buffer. The characteristics of these various martian basalts have been linked to different reservoirs in the martian crust and mantle, and their interactions during the petrogenesis of these magmas. These observations pose interesting interpretive challenges to our understanding of the conditions of the martian mantle (e.g. oxygen fugacity) and the interaction of mantle derived magmas with the martian crust and surface. Martian meteorite NWA 8159 is a unique fine-grained augite basalt derived from a highly depleted mantle source as reflected in its initial epsilon-Nd value, contains a pronounced light REE depleted pattern, and crystallized presumably under very oxidizing conditions. Although considerably older than both shergottites and nahklites, it has been petrogenetically linked to both styles of martian magmatism. These unique characteristics of NWA 8159 may provide an additional perspective for deciphering the petrogenesis of martian basalts and the nature of the crust of Mars.

Shearer, Charles K.↗

Elemental abundances in meteoritic and terrestrial matter

Major and trace element analyses of over 180 individual chondrules from 12 carbonaceous chondrites are reported, including individual analyses of 60 chondrules from Pueblito de Allende. Siderophile elements in most chondrules are depleted, compared to the whole chondrite. Correlations of Al-Ir and Ir-Sc among chondrules high in Ca and Al were observed. A Cu-Mn correlation was also found for chondrules from some meteorites. No correlation was observed between Au and other siderophile elements (Fe, Ni, Co and Ir). It is suggested that these elemental associations were present in the material from which the chondrules formed. Compositionally, chondrules appear to be a multicomponent mixture of remelted dust. One component displaying an Al-Ir correlation is identified as Allende-type white aggregates. The other components are a material chemically similar to the present matrix and sulfides-plus-metal material. Abundances of the REE (rare earth elements) were measured in ordinary Allende chondrules and were 50% higher than REE abundances in Mokoia chondrules; REE abundances in Ca-Al rich chondrules were similar to REE abundances in Ca-rich white aggregates.

Schmitt, R. A.↗

Fractionation in the solar nebula - Condensation of yttrium and the rare earth elements

The condensation of Y and the rare earth elements (REE) from the solar nebula may be controlled by thermodynamic equilibrium between gas and condensed solids. Highly fractionated REE patterns may result if condensates are removed from the gas before condensation is complete. It is found that the fractionation is not a smooth function of REE ionic radius but varies in an extremely irregular pattern. Both Yb and Eu are predicted to be extremely depleted in the early condensate without the requirement of condensation in the divalent state. The model is discussed with respect to a highly fractionated pattern observed by Tanaka and Masuda (1973), in a pink Ca-Al-rich inclusion from the Allende meteorite and can account for the abundances of each REE determined. According to the model this inclusion represents a condensate from a previously fractionated gas rather than from a gas of solar composition. Before the condensation of this inclusion, an earlier condensate was formed and was removed from equilibrium with the gas.

Boynton, W. V.↗

Major and trace element chemistry of separated fragments from a hibonite-bearing Allende inclusion

The major and trace elements of separated fragments and a bulk sample from CG-11, a hibonite-bearing inclusion in the Allende meteorite, were analyzed. Major element abundances were used to determine the minerology of separated fragments. The high degree of correlation between Eu/Sm ratios and Lu/Yb ratios for the samples studied indicates that their rare earth element (REE) distributions are governed by two components. One, Lu-, Eu-rich, is probably hibonite; the other, depleted in these elements, seems to be associated with the secondary alteration phases, grossular, nepheline and anorthite. The REE distribution in CG-11 precludes melting events after formation of the secondary alteration phases, but a melting event involving the primary minerals cannot be excluded. The enrichment of Lu with respect to other measured REE in hibonite can be explained by present REE condensation models. Two Hf-bearing components, most likely hibonite and perovskite, are necessary to account for variations in Sc/Hf ratios in the fragments studied. The lithophile volatiles Na, Mn, Fe, Zn, and probably Cr increase in the same order as the amount of secondary alteration minerals; the volatile siderophile elements Co and Au, however, do not.

Davis, A. M.↗

The 'North American shale composite' - Its compilation, major and trace element characteristics

North American shale composite (NASC) major element composition and compilation are presented, together with rare earth element (REE) redeterminations obtained by high precision analytical methods. The major element composition of the NASC compares closely with other average shale compositions, and significant portions of the REE and some other trace elements are contained in minor phases. The uneven REE distribution in NASC powder appears to yield the heterogeneity in analyzed aliquants. REE distributions of detrital sediments may to some extent be dependent on their minor mineral assemblages and the sedimentological factors controlling these assemblages.

Gromet, L. P.↗

Ion probe determinations of the rare earth concentrations of individual meteoritic phosphate grains

A new ion probe method for quantitative measurements of the concentrations of all the REE down to the ppm level in 5-20 micron spots is presented. The first application of the method is the determination of REE abundances in meteoritic phosphates. Results are shown to be in good agreement with previous INAA and ion probe determinations. The merrillites in the St. Severin amphoterite are richer in REE than the apatites (the enrichment factors, for various REE, range from 2.3 to 14.2) in contradiction with the results of Ebihara and Honda (1983). Provided good standards for other mineral phases are found or implanted marker ion techniques are used, the method should find a wide range of applications for the study of both terrestrial and extraterrestrial crystals at the microscopic level.

Crozaz, G.↗

Rare earth and other elements in components of the Abee enstatite chondrite

Radiochemical and instrumental neutron activation analyses of REEs and other elements have been conducted for Abee clast samples, a matrix sample, a dark inclusion, magnetic and nonmagnetic samples, and bulk samples. Correlations of the REEs and oldhamite abundance for both the clasts and dark inclusions indicate that the REEs chiefly occur in oldhamite. The similar REE patterns for clasts and dark inclusions, and the similar mineral composition of oldhamite in clast and dark inclusions, suggest that the oldhamite in both the clasts and dark inclusions is of a common origin.

Frazier, R. M.↗

Chemistry of the older supracrustals of Archaean age around Sargur

In the Archaeans of the Karnataka craton two stratigraphically distinct volcano-sedimentary sequences occur, namely the older supracrustals of the Sargur type and the younger Dharwar greenstones. The dividing line between these is the 3 by old component of the Peninsular gneiss. The trace and rare earth element chemistry of the Sargur metasediments show, in general, marked similarity to the Archaean sediments. The significant departures are in the nickel and chromium abundances. The REE data of the Sargur pelites of the Terakanambi region represented by Silli-gt-bio-feldspar schists and paragneisses show LREE enrichment and flat to depleted HREE pattern. Banded iron formations have very low REE abundance. They show slightly enriched LREE and flat to depleted HREE pattern. REE abundance in the Mn-horizons is comparable to that of the Archaean sediments. Mn-horizons show enriched LREE and flat HREE with anamolous Eu. REE patterns of these bands is well evolved and has similarities with PAAS.

Janardhan, A. S.↗

Rare earth elements in minerals of the ALHA77005 shergottite and implications for its parent magma and crystallization history

Analyses of mineral REE and selected minor and trace elements were carried out on individual grains of pyroxenes, whitlockite, maskelynite, and olivine of the Antarctic shergottite ALHA77005, and the results are used to interpret its parent magma and crystallization history. The results of mineral compositions and textural observations suggest that ALHA77005 is a cumulate with about half cumulus material (olivine + chromite) and half postcumulus phases. Most of the REEs in ALHA77005 reside in whitlockite whose modal concentration is about 1 percent. Mineral REE data support previous suggestions that plagioclase and whitlockite crystallized late, and that low-Ca pyroxene initiated crystallization before high-Ca pyroxene. The REE patterns for the intercumulus liquid, calculated from distribution coefficients for ALHA77005 pyroxene, plagioclase, and whitlockite, are in very good agreement and are similar to that of Shergotty.

Lundberg, Laura L.↗

Generation of abnormal trace element abundances in Antarctic eucrites by weathering processes

Data were obtained on the trace- and major-element compositions of 16 Antarctic abnormal eucrites, many of which exhibiting positive (but sometimes negative) Ce anomalies, positive Eu anomalies, and low abundances of the remainder of the REEs. The results of data analysis suggest that the unusual REE patterns of abnormal Antarctic eucrites arise from weathering effects generated in or on the Antarctic ice. The suggested scenario involves the formation of melt water and its equilibration with the atmosphere, promoting the dissolution of REE-rich phosphates and the oxidation of Ce. As a result, tetravalent Ce is fractionated from the trivalent REE in solution.

Mittlefehldt, David W.↗

Compositional and phase relations among rare earth element minerals

A review is presented that mainly treats minerals in which the rare-earth elements are essential constituents, e.g., bastnaesite, monazite, xenotime, aeschynite, allanite. The chemical mechanisms and limits of REE substitution in some rock-forming minerals (zircon, apatite, titanite, garnet) are also derived. Vector representation of complex coupled substitutions in selected REE-bearing minerals is examined and some comments on REE-partitioning between minerals as related to acid-based tendencies and mineral stabilities are presented. As the same or analogous coupled substitutions involving the REE occur in a wide variety of mineral structures, they are discussed together.

Burt, D. M.↗

Searching for neuKREEP: An EMP study of Apollo 11 Group A basalts

The Apollo 11 and 17 landing sites are characterized by the presence of high-Ti basalts (TiO2 greater than 6 percent). The Group A basalts of Apollo 11 have elevated K compositions (greater than 2000 ppm); and are enriched in incompatible trace elements relative to the other types of high-Ti basalt found in the region. These unique basalts also are the youngest of all high-Ti basalts, with an age of 3.56 +/- 0.02 Ga. Recent modelling of the Apollo 11 Group A basalts by Jerde et al. has demonstrated that this unique variety of high-Ti basalt may have formed through fractionation of a liquid with the composition of the Apollo 11 orange glass, coupled with assimilation of evolved material (dubbed neuKREEP and having similarities to lunar quartz monzodiorite). Assimilation of this material would impart its REE signature on the liquid, resulting in the elevated REE abundances observed. Minerals such as whitlockite which contain a large portion of the REE budget can be expected to reflect the REE characteristics of the assimilant. To this end, an examination of the whitlockite present in the Apollo 11 Group A basalts was undertaken to search for evidence of the neuKREEP material assimilated.

Jerde, Eric A.↗

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.↗

Orthopyroxene as a recorder of lunar crust evolution: An ion microprobe investigations of Mg-suite norites

The lunar Mg suite, which includes dunites, troctolites, and norites, could make up 20-30% of the Moon's crust down to a depth of 60 km. The remainder is largely anorthositic. This report focuses on norites because we have found that the chemical characteristics of orthopyroxene are effective recorders of their parental melt compositions. Many of the samples representing the Mg suite are small and unrepresentative. In addition, they are cumulates and thus are difficult to study by whole-rock techniques. Therefore, we decided to study these rocks by SIMS techniques to analyze a suite of trace elements in orthopyroxene. The 12 norite samples were selected from a recent compilation by Warren who attempted to select the best candidate samples from the standpoint of their pristine character. Our present database includes greater than 300 superior Electromagnetic Pulse (EMP) analyses and greater than 50 scanning ion mass spectroscopy (SIMS) analyses for 8 Rare Earth Elements (REE), Zr, Y, and Sr. The Mg#s for the parental melts calculated from Mg#s in orthopyroxene show that most melts have Mg#s in the range of 0.36-0.60. This compares with a range of Mg#s for lunar volcanic picritic glass beads of 0.4-0.68. Therefore, although the cumulate whole-rock compositions of the Mg suite can be extremely magnesian, the calculated parental melts are not anomalously high in Mg. A chemical characteristic of the Mg-suite norites that is more difficult to explain is the high KREEP content of the calculated parental melts. The REE contents for the calculated norite parental melts have REE that match or exceed the high-K KREEP component of Warren. Therefore, mixing of a KREEP component and a picritic melt cannot, by itself, explain the high estimated REE contents of the melts parental to norites. Advanced crystallization following KREEP incorporation, especially of plagiclase, may also be required.

Papike, J. J.↗