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At least 73 records · Page 4

Mid-Infrared OPO for High Resolution Measurements of Trace Gases in the Mars Atmosphere

The Martian atmosphere is composed primarily (>95%) of CO2 and N2 gas, with CO, O2, CH4, and inert gases such as argon comprising most of the remainder. It is surprisingly dynamic with various processes driving changes in the distribution of CO2, dust, haze, clouds and water vapor on global scales in the meteorology of Mars atmosphere [I]. The trace gases and isotopic ratios in the atmosphere offer important but subtle clues as to the origins of the planet's atmosphere, hydrology, geology, and potential for biology. In the search for life on Mars, an important process is the ability of bacteria to metabolize inorganic substrates (H2, CO2 and rock) to derive energy and produce methane as a by-product of anaerobic metabolism. Trace gases have been measured in the Mars atmosphere from Earth, Mars orbit, and from the Mars surface. The concentration of water vapor and various carbon-based trace gases are observed in variable concentrations. Within the past decade multiple groups have reported detection of CH4, with concentrations in the 10's of ppb, using spectroscopic observations from Earth [2]. Passive spectrometers in the mid-infrared (MIR) are restricted to the sunlit side of the planet, generally in the mid latitudes, and have limited spectral and spatial resolution. To accurately map the global distribution and to locate areas of possibly higher concentrations of these gases such as plumes or vents requires an instrument with high sensitivity and fine spatial resolution that also has global coverage and can measure during both day and night. Our development goal is a new MIR lidar capable of measuring, on global scales, with sensitivity, resolution and precision needed to characterize the trace gases and isotopic ratios of the Martian atmosphere. An optical parametric oscillator operating in the MIR is well suited for this instrument. The sufficient wavelength tuning range of the OPO can extend the measurements to other organic molecules, CO2, atmospheric water vapor, clouds, temperature, dust, and aerosols, as well as possibly polar-cap properties. Our OPO-approach may allow a new capability for active remote sensing of the outer planets and moons, where the weaker sunlight further limit passive instruments. Here we report on the OPO development effort for this lidar instrument.

Yu, Anthony W.↗

Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

Kimura, Makoto↗

Tracer versus trace element diffusion - Diffusional decoupling of Sr concentration from Sr isotope composition

Chemical diffusivities for nonalkali major, minor, and selected trace elements have been measured at 10 kbar, 1300 C during interdiffusion of dacitic and rhyolitic melts. Sr tracer diffusivities were measured at the same conditions in melts of dacitic and rhyolitic composition and in a diffusion couple of these two melts undergoing simultaneous chemical diffusion. Chemical diffusivities of all elements studied are functions of the silica content of the melt, but at any one silica content the chemical diffusivities of all elements studied are within a factor of five of the Si and Al diffusivities. Si diffusivity varies from 2.8 x 10 to the -9th sq cm/s at 65 percent SiO2 to 5.1 x 10 to the -10th sq cm/s at 75 percent SiO2. The diffusivities of minor and trace elements are proposed to be controlled by the ability of the local melt structure to accommodate these elements while maintaining LTE. The measured Sr tracer diffusivities are an order of magnitude above Sr chemical diffusivities.

Baker, Don R.↗

Evidence for distillation in the formation of HAL and related hibonite inclusions

New Ca- and Ti-isotopic analyses of DH-H1, 7-404, and 7-971, and Mg-isotopic analyses on DH-H1 and 7-404 are reported. O-isotopic analyses of HAL, 7-404, 7-971, and a variety of other refractory inclusions from Murchison were made in order to establish the presence or absence of FUN O-isotopic systematics. A higonite-rich residue produced by the evaporation of kaersutite was analyzed for its trace-element and isotopic abundances to see if any of the characteristics of FUN hibonite inclusions can be produced by distillation in the laboratory. These data are then used to evaluate for all four inclusions the HAL-type formation models originally proposed by Allen et al. (1980) and Lee et al. (1980). The four inclusions were found to have very similar chemical and isotopic features. All are characterized by large Ce depletions and very low Mg, Ti, and V concentrations compared to other meteoritic hibonites. All four inclusions have delta(C-48) within error of -5 per mil. Ca-, Ti-, and O-isotopic compositions are fractionated with enrichments of the heavy isotopes, and the Ti-isotopic mass fractionation is inversely correlated with Ti concentration. It is concluded that the inclusions formed primarily as distillation residues in accord with the early conclusions.

Ireland, Trevor R.↗

Calcium Isotope Constraints on Recycled Carbonates in Subduction-related Magmas

Calcium isotope ratios are readily mass-fractionated by low-temperature depositional processes that can be recorded in sedimentary rocks and, therefore, have the potential to track distinct geochemical signatures of recycled materials in mantle-derived igneous rocks. In this study, I report calcium isotopic compositions for well-characterized lavas from the Central American volcanic arc that exhibit a range of trace element and radiogenic isotope signatures that have been used to indicate variable amounts of subducted marine carbonate and hemipelagic sedimentary rocks, fresh carbonatite lavas from Oldoinyo Lengai Volcano, Tanzania, and an intrusive carbonatite clast erupted 12.8 ka from the Laacher See Volcano, Germany. I observed no calcium isotope evidence for recycled sedimentary rocks in the Central American arc magmas or in the Oldoinyo Lengai carbonatite volcanic rocks. They all exhibit isotopic compositions similar to rocks dominated by a primitive, mantle-like, bulk silicate Earth (BSE) composition. The exception in this work is the calcium isotope composition measured in the intrusive Laacher See carbonatite that is resolvable from BSE (δ^44 Ca = 0.0). Although this calcium isotopic signature might be related to ancient carbonate recycling, the magnitude and relatively light calcium isotopic composition (δ^44 Ca = –0.4) of this carbonatite could also reflect an origin that involved partial melting of altered lithospheric mantle, from which isotopically heavy Ca-bearing fluids have been lost. The decoupled signatures between trace elements and their radiogenic isotopes and those recorded by calcium isotope data are important because they likely reflect different sources and processes, and demonstrate that sediment subduction is not a bulk mixing process.

Ca isotopes↗

Coordinated Isotopic and Mineral Characterization of Highly Fractionated 18O-Rich Silicates in the Queen Alexandra Range 99177 CR3 Chondrite

Carbonaceous chondrites contain a mixture of solar system condensates, pre-solar grains, and primitive organic matter. Each of these materials record conditions and processes in different regions of the solar nebula, on the meteorite parent body, and beyond the solar system. Oxygen isotopic studies of meteorite components can trace interactions of distinct oxygen isotopic reservoirs in the early solar system and secondary alteration processes. The O isotopic compositions of the earliest solar system condensates fall along a carbonaceous chondrite anhydrous mineral (CCAM) line of slope approximately 1 in a plot of delta 17O against delta 18O. This trend is attributed to mixing of material from 16O-poor and 16O-rich reservoirs. Secondary processing can induce mass-dependent fractionation of the O isotopes, shifting these compositions along a line of slope approximately 0.52. Substantial mass-dependent fractionation of O isotopes has been observed in secondary minerals in CAIs, calcite, and FUN inclusions. These fractionations were caused by significant thermal or aqueous alteration. We recently reported the identification of four silicate grains with extremely fractionated O isotopic ratios (delta 18O equals 37 - 55 per mille) in the minimally altered CR3 chondrite QUE 99177. TEM analysis of one grain indicates it is a nebular condensate that did not experience substantial alteration. The history of these grains is thus distinct from those of the aforementioned fractionated materials. To constrain the origin of the silicate grains, we conducted further Mg and Fe isotopic studies and TEM analyses of two grains.

Nguyen, A. N.↗

Reassessing the Evidence for the Earliest Traces of Life

The isotopic composition of graphite is commonly used as a biomarker in the oldest (>3.5 Gyr ago) highly metamorphosed terrestrial rocks. Earlier studies on isotopic characteristics of graphite occurring in rocks of the approximately 3.8-Gyr-old Isua supracrustal belt (ISB) in southern West Greenland have suggested the presence of a vast microbial ecosystem in the early Archean. This interpretation, however, has to be approached with extreme care. Here we show that graphite occurs abundantly in secondary carbonate veins in the ISB that are formed at depth in the crust by injection of hot fluids reacting with older crustal rocks (metasomatism). During these reactions, graphite forms from the disproportionation of Fe(II)-bearing carbonates at high temperature. These metasomatic rocks, which clearly lack biological relevance, were earlier thought to be of sedimentary origin and their graphite association provided the basis for inferences about early life. The new observations thus call for a reassessment of previously presented evidence for ancient traces of life in the highly metamorphosed Early Archaean rock record.

vanZullen, Mark A.↗

Rb-Sr, Sm-Nd, K-Ca, O, and H isotopic study of Cretaceous-Tertiary boundary sediments, Caravaca, Spain Evidence for an oceanic impact site

The results of isotopic and trace-element-abundance analyses of Ir-enriched Cretaceous-Tertiary-boundary clay sediments from Caravaca, Spain, and of adjacent carbonate and marl layers, are presented. Acetic-acid and HCl leachates and residues were analyzed by isotope dilution to determine K, Rb, Sr, Sm, and Nd concentrations and Sr-87/Sr-86 and Nd-143/Nd-144 ratios. The stable isotope ratios delta-D, delta-(C-13), and delta-(0-18) were also determined. The results are presented in tables and graphs and compared with published data on the Caravaca sediments and on samples from other locations. The boundary clay is found to be distinguished from the adjacent layers by its isotopic ratios and to be of mainly terrestrial, lithospheric (deeper than 3-km) origin. Although submarine-weathering effects are evident and difficult to quantify, the degree of variation in Ni, Ir, Sr, and REE concentrations is considered too large to be attributed to postdepositional processes alone. These findings are seen as evidence for the ocean impact of a large single asteroid producing a worldwide blanket of ejecta, a large injection of water vapor into the atmosphere, and perhaps a gigantic tsunami, at the end of the Cretaceous period.

Depaolo, D. J.↗

Rb, Sr and strontium isotopic composition, K/Ar age and large ion lithophile trace element abundances in rocks and glasses from the Wanapitei Lake impact structure

Shock metamorphosed rocks and shock-produced melt glasses from the Wanapitei Lake impact structure have been examined petrographically and by electron microprobe. Eleven clasts exhibiting varying degrees of shock metamorphism and eight impact-produced glasses have been analyzed for Rb, Sr and Sr isotopic composition. Five clasts and one glass have also been analyzed for large ion lithophile (LIL) trace element abundances including Li, Rb, Sr, and Ba and the REE's. The impact event forming the Wanapitei Lake structure occurred 37 m.y. ago based on K/Ar dating of glass and glassy whole-rock samples. Rb/Sr isotopic dating failed to provide a meaningful whole-rock or internal isochron. The isotopic composition of the glasses can be explained by impact-produced mixing and melting of metasediments.

Winzer, S. R.↗

Petrology and Physics of Magma Ocean Crystallization

Early Mars is thought to have been melted significantly by the conversion of kinetic energy to heat during accretion of planetesimals. The processes of solidification of a magma ocean determine initial planetary compositional differentiation and the stability of the resulting mantle density profile. The stability and compositional heterogeneity of the mantle have significance for magmatic source regions, convective instability, and magnetic field generation. Significant progress on the dynamical problem of magma ocean crystallization has been made by a number of workers. The work done under the 2003 MFRP grant further explored the implications of early physical processes on compositional heterogeneity in Mars. Our goals were to connect early physical processes in Mars evolution with the present planet's most ancient observable characteristics, including the early, strong magnetic field, the crustal dichotomy, and the compositional characteristics of the SNC meteorite's source regions as well as their formation as isotopically distinct compositions early in Mars's evolution. We had already established a possible relationship between the major element compositions of SNC meteorite sources and processes of Martian magma ocean crystallization and overturn, and under this grant extended the analysis to the crucial trace element and isotopic SNC signatures. This study then demonstrated the ability to create and end the magnetic field through magma ocean cumulate overturn and subsequent cooling, as well as the feasibility of creating a compositionally- and volumetrically-consistent crustal dichotomy through mode-1 overturn and simultaneous adiabatic melting.

Elkins-Tanton, Linda T.↗

Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

Makishima, J.↗

The evolution of complex type B Allende inclusion - An ion microprobe trace element study

Results are presented of a detailed trace-element and isotopic analyses of the constituent phases in each of the major textural parts (mantle, core, and islands) of a Type B refractory inclusion, the USNM 5241 inclusion from Allende, first described by El Goresy et al. (1985). The REE data on 5241 were found to be largely consistent with a model in which the mantle and the core of 5241 formed sequentially out of a single melt by fractional crystallization. The numerical models of REE evolution in the 5241 melt, especially that of Eu, require that a significant mass of spinel-free island material was assimilated into the evolving melt during the last half of the solidification history of 5241. The trace element results pbtained thus strongly support the interpretation of El Goresy et al. (1985) that the spinel-free islands in the 5241 are trapped xenoliths.

Macpherson, Glenn J.↗

Preliminary Report on U-Th-Pb Isotope Systematics of the Olivine-Phyric Shergottite Tissint

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions, and trace element abundances.. These correlations have been interpreted as indicating the presence of a reduced, incompatible-element- depleted reservoir and an oxidized, incompatible-element-rich reservoir. The former is clearly a depleted mantle source, but there has been a long debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former clearly requires the ancient martian crust to be the enriched source (crustal assimilation), whereas the latter requires a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and U-Th-Pb concentration analyses of the olivine-phyric shergottite Tissint because U-Th-Pb isotope systematics have been intensively used as a powerful radiogenic tracer to characterize old crust/sediment components in mantle- derived, terrestrial oceanic island basalts. The U-Th-Pb analyses are applied to sequential acid leaching fractions obtained from Tissint whole-rock powder in order to search for Pb isotopic source components in Tissint magma. Here we report preliminary results of the U-Th-Pb analyses of acid leachates and a residue, and propose the possibility that Tissint would have experienced minor assimilation of old martian crust.

Moriwaki, R.↗

A Complex History of Silicate Differentiation of Mars from Nd and Hf Isotopes in Crustal Breccia NWA 7034

Resolving the possible mantle and crustal sources for shergottite meteorites is crucial for understanding the formation and early differentiation of Mars. Orbiter and rover characterization of the martian surface reveal that the major element composition of most of its surface does not match the shergottites (McSween et al., 2009)leaving the relationship between them poorly understood. The identification of the meteorite NWA 7034 and its pairs as a Mars surface rock (Cartwright et al., 2014)provides access to a representative sample of Mars' crust (Agee et al., 2013;Humayun et al., 2013). Utilizing the short-lived Sm-146 - Nd-142, and long-lived Sm-142 - Nd-142 and Lu-176 - Hf-176 chronometers, which are sensitive to silicate differentiation, we analyzed three fragments of NWA 7034. The very negative mean isotopic compositions for this breccia, μNd-142(sub JNdi-1)=−45 +/-5(2SD), εNd-143(sub CHUR)=−16.7 +/-0.4(2SD) and εHf176(sub CHUR)=−61 +/-9(2SD) point to an ancient origin for this martian crust. However, modeling of the data shows that the crust sampled by NWA 7034 possesses a Hf/Nd ratio and coupled εNd-143 - μNd-142 model age that are incompatible with this crustal reservoir being an end-member that generated the shergottite source mixing array. In addition, this crust is not juvenile, despite its rare earth element profile, but has had a multistage formation history. Therefore, early crustal extraction alone was not responsible for the creation of the reservoirs that produced the shergottites. Instead mantle reservoirs formed via other early differentiation processes such as in a Mars magma ocean must be responsible for the trace element and isotopic signatures present in shergottites.

Rosalind M. G. Armytage↗

A FIB/TEM/Nanosims Study of a Wark-Lovering Rim on an Allende CAI

Ca- Al-rich inclusions (CAIs) are commonly surrounded by Wark-Lovering (WL) rims - thin (approx. 50 micrometers) multilayered sequences - whose mineralogy is dominated by high temperature minerals similar to those that occur in the cores of CAIs [1]. The origins of these WL rims involved high temperature events in the early nebula such as condensation, flashheating or reaction with a nebular reservoir, or combinations of these processes. These rims formed after CAI formation but prior to accretion into their parent bodies. We have undertaken a coordinated mineralogical and isotopic study of WL rims to determine the formation conditions of the individual layers and to constrain the isotopic reservoirs they interacted with during their history. We focus here on the spinel layer, the first-formed highest- temperature layer in the WL rim sequence. Results and Discussion: We have performed mineralogical, chemical and isotopic analyses of an unusual ultrarefractory inclusion from the Allende CV3 chondrite (SHAL) consisting of an approx. 500 micrometers long single crystal of hibonite and co-existing coarsegrained perovskite. SHAL is partially surrounded by WL rim. We previously reported on the mineralogy, isotopic compositions and trace elements in SHAL [2-4]. The spinel layer in the WL rim is present only on the hibonite and terminates abruptly at the contact with the coarse perovskite. This simple observation shows that the spinel layer is not a condensate in this case (otherwise spinel would have condensed on the perovskite as well). The spinel layer appears to have formed by gas-phase corrosion of the hibonite by Mg-rich vapors such that the spinel layer grew at the expense of the hibonite. We also found that the spinel layer has the same 16Orich composition as the hibonite. The spinel layer is polycrystalline and individual crystals do not show a crystallographic relationship with the hibonite. An Al-diopside layer overlies the spinel layer, and is present on both the hibonite and perovskite. While the spinel is 16O-rich, WL-rim perovskite and pyroxene are 16O-poor. This isotopic heterogeneity likely reflects O isotopic equilibration of WL-rim perovskite and pyroxene with a planetary O isotopic reservoir after the WL rim formation. The hibonite is zoned and contains wt.% levels of Ti, Mg and Fe in contact with the Fe-bearing spinel (Sp60Hc40) in the WL rim. The Fe enrichment in spinel is likely related to the Na-Fe metasomatism that is ubiquitous in Allende. Conclusions: The petrography and microstructure of the spinel layer in a WL rim sequence shows that it formed by gas phase reactions at high temperature in the nebula. The oxygen isotopic composition of the spinel indicates that this WL rim layer formed in the same (or similar) nebular gas reservoir as the host CAI.

Keller, L. P.↗

The supernova trigger for formation of the solar system

It is suggested that the explosion of a Type II supernova triggered the collapse of a nearby interstellar cloud and led to the formation of the solar system. Estimates of the abundances resulting from nuclear processing of the supernova ejecta are presented. It appears promising that nucleosynthesis in this single supernova event can account for most isotopic anomalies and traces of extinct radioactivities in solar-system material.

Cameron, A. G. W.↗

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.↗