Rare earths and other trace elements in Apollo 11 lunar samples
Rare earth and trace element abundances for Apollo 11 lunar samples by neutron activation, comparing with Bruderheim chondrite and submarine basalts
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Rare earth and trace element abundances for Apollo 11 lunar samples by neutron activation, comparing with Bruderheim chondrite and submarine basalts
Concentrations of ten volatile/mobile trace elements and of nonvolatile Co in the Karoonda (C4) meteorite were determined, and the atomic abundances relative to C1 are compared with values for the Murchison (C2) and Allende (C3) meteorites. Empirical Bi, In, and Tl data for Karoonda and heated Allende and Murchison are compared with theoretical curves for condensation from a gas of cosmic composition at low pressures. It is suggested that Karoonda might derive from low-temperature open-system metamorphism of pristine C3-like material.
The origin of the incompatible trace element (ITE) enriched compositions of shergottites has been a point of contention for decades [1-2]. Two scenarios have been proposed, the first is that enriched shergottite compositions reflect an ITE-enriched mantle source, whereas in the second, the ITE enrichment reflects crustal contamination of mantle-derived parent magmas. Evidence supporting the first scenario is that the ITE-enriched shergottite compositions are consistent with the outcomes of magma ocean crystallization [3], and that Os-Nd isotope relationships for shergottites cannot be explained by realistic crustal contamination models [4]. In contrast, Cl and S isotopes are consistent with shergottite magmas interacting with Mars crust [5,6], and ITE-enriched olivine-hosted melt inclusions and interstitial glass are found in depleted shergottite Yamato 980459 [7]. These findings indicate that some level of crustal interaction occurred but the question of whether ITE-enrichments in some bulk shergottites reflect crustal contamination remains open. Recently, a Mars crustal breccia meteorite has been found, NWA 7034 and its paired stones, that is our best analogue to an average of Mars ancient crust [8-10]. This allows for better constraints on crustal contamination of shergottite magmas. We modeled magma-crust mixing and assimilation-fractional crystallization (AFC) using ITE-depleted shergottite compositions and bulk NWA 7034 and its clasts as end-members. The results of these models indicate that crustal contamination can only explain the ITE-enriched compositions of some bulk shergottites under unusual circumstances. It is thus likely that the shergottite range of compositions reflects primarily mantle sources.
This paper presents a systematic thermodynamic analysis of the effects of temperature and composition on olivine/melt and low-Ca pyroxene/melt partitioning. Experiments were conducted in several synthetic basalts with a wide range of Fe/Mg, determining partition coefficients for Eu, Ca, Mn, Fe, Ni, Sm, Cd, Y, Yb, Sc, Al, Zr, and Ti and modeling accurately the changes in free energy for trace element exchange between crystal and melt as functions of the trace element size and charge. On the basis of this model, partition coefficients for olivine/melt and low-Ca pyroxene/melt can be predicted for a wide range of elements over a variety of basaltic bulk compositions and temperatures. Moreover, variations in partition coeffeicients during crystallization or melting can be modeled on the basis of changes in temperature and major element chemistry.
Beginning in 1971 a cooperative program has been carried on by the City of Cleveland Division of Air Pollution Control and NASA Lewis Research Center to study the trace element and compound concentrations in the ambient suspended particulate matter in Cleveland Ohio as a function of source, monitoring location and meteorological conditions. The major objectives were to determine the ambient concentration levels at representative urban sites and to develop a technique using trace element and compound data in conjunction with meteorological conditions to identify specific pollution sources which could be developed into a practical system that could be readily utilized by an enforcement agency.
The isotopic and chemical properties of Ca-Al-rich inclusions (CAI) provide important clues to the early solar nebula environment. While the abundances of refractory major and trace elements are similar to those expected for high temperature condensates, the variety of textural, chemical, and isotopic signatures indicate most CAI experienced complex, multi-stage histories involving repeated episodes of condensation, evaporation, and metamorphism. Evidence of multiple processes is especially apparent in an unusual refractory inclusion from Essebi (URIE) described by El Goresy et al. The melilite (mel)-rich core of URIE contains polygonal framboids of spinel (sp) and hibonite (hb) or sp and fassaite (fas) and is surrounded by a rim sequence consisting of five layers. In contrast to rims on Allende, the mineralogy of the URIE rim layers becomes increasingly refractory from the core outwards, ending in a layer of spinel-Al2O3 solid solution + Sc-rich fassaite. The chemical and mineralogical features of URIE are inconsistent with crystallization from a homogeneous melt, and El Goresy et al. proposed a multi-step history involving condensation of sp + hb and aggregation into framboids, capture of framboids by a refractory silicate melt droplet, condensation of rim layers, and alteration of mel to calcite and feldspathoid. The PANURGE ion probe was used to investigate the isotopic and trace element characteristics of URIE to develop a more complete picture of the multiple processes leading to formation and metamorphism.
Charge-balancing substitution mechanisms are determined for the incorporation of the trivalent cations Al and Sc in low-Ca pyroxene and Al, Sc, Yb, and Cr in olivine. In low-Ca pyroxene, the substitution mechanism is determined by evaluating covariations of trivalent trace cations with Si, Mg, Fe, and Ca. In olivine, substitution mechanisms are determined by comparing the observed compositional dependence of partitioning to the compositional dependence theoretically expected for each substitution reaction. A realistic equilibrium constant is formulated for trace element exchanges between olivines, low-Ca pyroxenes, and melt, making possible improved modeling of the variations of trace element partitioning with temperature and phase composition.
The concentrations of Ni, Cu, Zn, Ga, Ge, and Se in five chondrule rims in the CO3 chondrite ALH A77307 (3.0) using the synchrotron x-ray fluorescence (SXRF) microprobe at Brookhaven National Laboratory were determined. The data show that the trace element chemistry of rims on different chondrules is remarkably similar, consistent with data obtained for the major elements by electron microprobe. These results support the idea that rims are not genetically related to individual chondrules, but all sampled the same reservoir of homogeneously mixed dust. Of the trace elements analyzed Zn and Ga show depletions relative to CI chondrite values, but in comparison with bulk CO chondrites all the elements are enriched by approximately 1.5 to 3.5 x CO. The high concentrations of the highly volatile elements Se and Ga and moderately volatile Zn (1.5 to 2 x CO) in rims show that matrix is the major reservoir of volatile elements in ALH A77307.
A number of trace element interrelationships support the concept of a laterally inhomogeneous moon based originally on Clr/P2O5 ratios. The correspondence between Clr/P2O3 and Rb/Sr ratios in basalts are of special interest since the isotropic evolution of the latter pair of elements relates to the earliest history of the moon. This implies the times when the Clr/P2O5 relationships were established. The early magma ocean is conjectured to have been made up of non-intermixing seas resulting either from large convection cells or large body accretion. These mutually exclusive regions could be lunar geological provinces. It is proposed that the diversity of basalts from the Apollo 17 site is related to the lateral inhomogeneity of the moon. Ca/Na ratios in basalts show a trend which parallels that of Ru/Os and in a corresponding fashion may serve as a depth indicator.
Data are reported for volatile/mobile Ag, As, Au, Bi, Cd, Co, Cs, Cu, Ga, In, Rb, Sb, Se, Te, T1 and Zn in exterior and/or interior samples of four Antarctic meteorites: 77005 (unique achondrite); 77257 (unreilite); 77278 (L3); 77299 (H3). Exterior samples reflect contamination and/or leaching by weathering but trace element (ppm-ppt) contents in interior samples seem reasonable for representatives of these rare meteoritic types. The 77005 achondrite seems related to shergottites; other samples extend compositional ranges previously known for their types. With suitable precautions, Antarctic meteorite finds yield trace element data as reliable as those obtained from previously known falls.
Eucrite, howardite, and diogenite members of the achondrites are considered, by many, to be genetically related. Therefore, each provide a piece of the puzzle for reconstructing magmatic processes on the eucrite parent body (EPB). The relationship between eucrites and diogenites can be viewed within the context of two distinctly different models: (1) fractional crystallization; and (2) partial melting. In fractional crystallization models, eucrites and diogenites represent a complementary continuum of planetary fractional crystallization products in which the diogenites represent crystal accumulations during the crystallization of eucritic magmas at shallow to deep levels in the EPB. Alternatively, experimental studies may be interpreted as indicating eucrites represent peritectic partial melts of a primitive, chondritic EPB mantle. Within this type of model, the diogenites are also generally considered to be cumulates; however, their petrogenetic relationship to the eucrites is less clear. Sack et al. proposed that the olivine diogenites represent residua from the partial melting events that produced eucritic liquids. Initial trace element studies of orthopyroxene (OPX) are consistent with this model. However, this trace element modeling of the olivine diogenites is nonunique. As a further test of these models, we did the following three things: (1) analyzed OPX from cumulate diogenites to compare with the olibine diogenite data; (2) improved ion microprobe analytical techniques for the analysis of elements critical to our interpretations; and (3) selected more relevant Kd's for OPX-eucritic melt.
The reduced nature of Mercury, enstatite chondrites, and the aubrite parent bodies (APB) have raised many questions regarding the geochemical behavior of typically lithophile, heat-producing, and rare-earth elements (REE) in magmas at low oxygen fugacity (fO2). Due to decreasing O availability at these low fO2, and an abundance of S(sup 2(-)), sulfur (S) acts as an important anion that changes the partitioning behavior of many elements and modifies the physical properties of silicate melts. Preliminary observations suggest that major and minor elements exhibit different geochemical affinities in highly reduced, S-rich systems compared to terrestrial rocks. The speciation and bonding environment of S, dictated by P/T/fO2 conditions, may strongly influence the degree to which S affects partitioning behavior. Here we investigate the partitioning behavior of major, minor, and trace elements between silicate melt, sulfide melt, and metal as well as the coordination chemistry of S in highly reduced silicate melts. Our work is focused on investigating solely the entropy-dependent temperature effect on partitioning of elements for which we currently have MESSENGER data (K, Na, Th, U, Si, Mg, Fe, Ti, Ca, Al, Cr, Mn, S, Cl) as well as a host of geochemically relevant trace elements such as REEs (P, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb). Previous studies in which temperature, pressure, and fO2 were co-varied found that as fO2 decreases, heat-producing elements U and Th become more chalcophile, while K becomes less chalcophile. Concurrently, nominally lithophile elements Mg and Ca become more chalcophile and were observed as minor elements in exsolved sulfides and bonded with S species in silicate melt. These studies, however, could not disentangle entropic effects from changes in the fO2. New temperature-dependent partitioning data from our work will be used to determine which elements are most likely to retain their lithophile character and hence be incorporated into silicates, and which elements are likely contained within the sulfide (chalcophile) and metal core (siderophile), setting the stage for the thermal and magmatic evolution of reduced planetary bodies.
Trace elements in sporulation of bacteria and germination of bacterial spores
Lithium, K, Rb, Sr, Ba, rare-earth, Zr, and Hf abundances have been determined by mass-spectrometric isotope-dilution for Apollo 16 soils, anorthosite 61016, and 'basalt' 68415 whole-rock and separated pyroxene and plagioclase. Our sample of 61016 is similar to some other lunar anorthosites in lithophile trace-element concentrations but at a slightly lower level. It was probably accumulated from a little differentiated basalt. Basalt 68415 might be a homogeneous mixture of KREEP and anorthosite material; it appears to have crystallized under conditions as reducing as those holding for mare-basalts. The soil fines cover only a limited compositional range. No obvious chemical differences were noted between the Descartes and Cayley formations. Most of the compositional variation of the soils can be accounted for in terms of the addition of plagioclase. The existence of very high alumina basalt as an independent magma-type appears debatable in view of its KREEP-like lithophile trace-element relative concentrations and the observed lunar radioactivity distribution.
Sediments spanning a 5 meter section across the Cretaceous-Tertiary boundary at ODP holes 689B and 690D, Maud Rise, Wedell Sea and hole 527, Walvis Ridge, are being analyzed for shock deformation, PGE's and other trace elements (including REE's). Mineral separates from each sample were studied with optical microscopy to determine the distribution and microstructural state of quartz and feldspar present in the sediments. Samples from Maud Rise were taken of the K/T transition and at about 50 cm intervals above and below it. These samples consist of carbonate-rich sediments, with the K/T transition marked by a change from white Maastrichtian oozes to a greenish ooze with higher concentrations of altered volcanic clay and vitric ash. The Walvis Ridge site is characterized by more clay-rich sediments with average carbonate content about 60 to 70 percent. Initial results from RNAA studies indicate that iridium is present in all the Maud Rise samples in concentrations equal to or greater than 0.01 ppb (whole-rock basis). Preliminary results from optical microscopy indicate the occurrence of shock mosaicism in quartz and feldspar in all of the samples studied. The pervasiveness of shock mosaicism and presence of planar features to 2 meters from the K/T boundary indicates that a single impact or volcanic explosion 66 ma may be ruled out as responsible for the K/T event. A similar conclusion may be drawn independently from the distribution of iridium and other trace elements. Regardless of the source of the shock waves and sediment contamination, multiple events are required over a ca.0.5 my timespan; currently we favor endogenous sources.
Trace elements detected in sporulation of bacteria and germination of bacterial spores
Data is examined for volatile/mobile Ag, As, Au, Bi, Cd, Co, Cs, Cu, Ga, In, Rb, Sb, Se, Te, Tl and Zn in exterior and/or interior samples of four Antarctic meteorites from the Allan Hills (ALH): A77005 (unique achondrite); A77257 (ureilite); A77278 (L3); A77299 (H3). Exterior samples reflect contamination and/or leaching by weathering but trace element (ppm-ppt) contents in interior samples seem reasonable for representatives of these rare meteoritic types. The A77005 achondrite is shown to be related to shergottites; other samples extend compositional ranges previously known for their groups or types. With suitable precautions, Antarctic meteorite finds yield trace element data as reliable as those obtained from previously known falls.
Today the major elemental composition of interplanetary dust particles (IDPs) is routinely determined in many laboratories. These and mineralogical studies have revealed the presence of at least two major types of IDPs, chondritic and refractory. Preliminary results of a successful attempt to determine abundances of a large suite of trace elements from both chondritic and refractory IDPs are reported. The analytical procedure can be used in the grain-by-grain analysis of returned cometary samples. Chondritic and refractory IDPs are characterized by standard scanning electron microscopy and energy dispersive x ray spectroscopy (SEM-EDX) techniques. With this system, detection limits for many elements are well below picogram levels, and some approach femtogram levels. This technique is non-destructive, although some sample handling is required, so particles can be analyzed by other techniques after instrument neutron activation analysis (INAA) is completed. Data is presently being reduced from the analyses of 7 IDPs. These are U2015E10, U2015F1, W7029-A2, W7029-A3, W7013A8, LACl (all chondritic) and 705 (refractory). So far, 17 different major and trace elements were detected and measured in these particles, including rare earths and some very volatile elements (Br and Zn).