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Ni and Co variations in primary martian magmas exhibit anomalous incompatible behavior, which has remained an unexplained conundrum. Because martian magmas are S-rich, and some trace metals are reported to have enhanced solubility in S-bearing magmas, we have carried out a series of experiments to evaluate the effect of high-S melts on the olivine/melt partitioning of Ni, Co, Mn, V, and Cr. Near-liquidus experiments on a synthetic primary martian mantle melt (Yamato-980459 [Y98]) were completed in a piston-cylinder apparatus at 0.75 GPa. Previous studies in S-free systems illustrate that the partition coefficients for these elements are dependent chiefly on DMg(Ol/melt) (the partition coefficient defined as wt% Mg in olivine/wt% Mg in melt, a proxy for temperature), and were used to calibrate a predictive expression that includes the effects of temperature [i.e., DMg(Ol/melt)], melt composition, and oxygen fugacity. These predictive expressions are then used to isolate any effect in DM olivine/melt due to dissolved sulfur. The results show that S might have a small effect for Co, but not enough to change Co partitioning from compatible to incompatible in our experiments. The addition of a sulfur term to the DCo predictive expressions shows that nearly 8000 ppm of sulfur would be required in the melt (at liquidus temperature of Y98) for DCo to become

The life and work of Robert Charles Sheppard (1932-2019), Bob Sheppard informally among friends, is outlined. He was a leading pioneer of solid phase peptide synthesis and made the most significant and fundamental European contribution to the art of peptide synthesis since Emil Fischer.

Universal screening is the first mechanism by which students are identified as at risk of failure in the context of multitiered systems of supports. This study examined the validity and diagnostic accuracy of a reading computer-adaptive test as a screener to identify state achievement test performance for third through fifth graders ( N = 1,696). Single time points and slopes within year and longitudinally were examined. Validity results for single points were moderate (.60–.79, p < .002). Validity for slopes and the state test were weak or not significant. Diagnostic accuracy cut scores that maximized sensitivity and specificity yielded high accuracy for single points whereas sensitivity was inadequate for slopes. Practical implications and future directions are presented.

International audience

This research was supported by the Remote, In Situ, and Synchrotron Studies for Science and Exploration (RIS4 E) node of the NASA SSERVI program and NASA grants NNX16AR18G and NNX17AL07G. XANES spectroscopy data were collected at GeoSoilEnviroCARS (Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation, Earth Sciences (EAR-1128799) and Department of Energy, Geosciences (DE-FG02-94ER14466). Use of the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. King was supported by an Australian Research Council Future Fellowship (FT130101524).

Multitiered systems of support depend on screening technology to identify students at risk. The purpose of this study was to examine the use of a computer-adaptive test and latent class growth anal...

The application of Martian meteorite U–Th–Pb isotope systematics to track the geochemical evolution of the Martian mantle has had limited success because of the difficulty in discriminating an indigenous magmatic Pb component from secondary near-surface components that have additionally been overprinted by terrestrial contamination. To mitigate this challenge, a successive acid-leaching experiment was conducted on the Tissint meteorite, the freshest, witnessed fall of a primitive, olivine-bearing Martian basalt. Trace element concentration analyses of acid leachates and residues indicate that secondary terrestrial contaminants were effectively removed by the early steps in the leaching experiments and that the acid residues contain pristine Pb from Tissint. The acid residue, which shows the most depleted REE signature, also has the least radiogenic Pb isotopic composition ( 206 Pb/ 204 Pb = 10.948, 207 Pb/ 204 Pb = 11.187, 208 Pb/ 204 Pb = 30.228). A two-stage mantle evolution model based on this composition indicates that the Tissint mantle has the lowest μ -value ( 238 U/ 204 Pb = 1.62 ± 0.09 ) among the shergottite sources.

Mars Science Laboratory's Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking mission's krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. However, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stable isotopes, unmeasured by Viking. The new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, however, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.

This perspective is a very personal account of the history and evolution of experimental trace element partitioning, although I cannot hope to exhaustively cover all aspects of this discipline. Therefore, I emphasise issues with which I am most familiar: (i) partitioning between mafic silicates and silicate melt; (ii) solid metal-liquid metal partitioning – especially the effects of non-metals; and (iii) metal-silicate liquid partitioning. I first entered the field of experimental partitioning as a grad-student in the mid-1970’s and so was able to see some of the growing pains of this discipline up close and personal. Also where appropriate, I will mention applications of experimental partitioning data to geologic and planetary problems.

[Figure][1] Spinel is a very important rock-forming mineral that is found in basalts from Earth, Mars, the Earth’s Moon, and basaltic meteorites. Spinel can be used as a sensitive indicator of petrologic and geochemical processes that occur in its host rock. This paper highlights the role of increasing f O2 (from IW-1 to FMQ+2) in converting a >90% normal spinel to an ~25% magnetite (inverse) spinel, the trajectory of D Vspinel/melt as it relates to the ratio of V3+/V4+ in the melt, and the crystal chemical attributes of the spinel that control the intrinsic compatibility of both V3+ and V4+. This work examines the nuances of the V partitioning and provides a crystal chemical basis for understanding Fe3+, Cr, and V substitution into the octahedral sites of spinel. Understanding this interplay is critical for using spinels as both indicators of planetary parentage and reconstructing the redox history of magmatic systems on the terrestrial planets. Three potential examples for this use are provided. In addition, this work helps explain the ubiquitous miscibility gap between spinels with changing ulvospinel contents. [1]: pending:yes

The apparent lack of plate tectonics on all terrestrial planets other than Earth has been used to support the notion that for most planets, once a primitive crust forms, the crust and mantle evolve geochemically-independent through time. This view has had a particularly large impact on models for the evolution of Mars and its silicate interior. Recent data indicating a greater potential that there may have been exchange between the martian crust and mantle has led to a search for additional geochemical evidence to support the alternative hypothesis, that some mechanism of crustal recycling may have operated early in the history of Mars. In order to study the most juvenile melts available to investigate martian mantle source(s) and melting processes, the trace element compositions of olivine-hosted melt inclusions for two incompatible-element-depleted olivine-phyric shergottites, Yamato 980459 (Y98) and Tissint, and the interstitial glass of Y98, have been measured by Secondary Ionization Mass Spectrometry (SIMS). Chondrite-normalized Rare Earth Element (REE) patterns for both Y98 and Tissint melt inclusions, and the Y98 interstitial glass, are characteristically light-REE depleted and parallel those of their host rock. For Y98, a clear flattening and upward inflection of La and Ce, relative to predictions based on middle and heavier REE, provides evidence for involvement of an enriched component early in their magmatic history; either inherited from a metasomatized mantle or crustal source, early on and prior to extensive host crystallization. Comparing these melt inclusion and interstitial glass analyses to existing melt inclusion and whole-rock data sets for the shergottite meteorite suite, defines mixing relationships between depleted and enriched end members, analogous to mixing relationships between whole rock Sr and Nd isotopic measurements. When considered in light of their petrologic context, the origin of these trace element enriched and isotopically evolved signatures represents either (1) crustal assimilation during the final few km of melt ascent towards the martian surface, or (2) assimilation soon after melt segregation, through melt–rock interaction with a portion of the martian crust recycled back into the mantle.

Melting experiments of a synthesized, alkali-bearing, H-chondrite composition were conducted at ambient pressure with three distinct oxygen fugacity conditions (IW-1, IW, and IW+2). Oxygen fugacity conditions significantly influence the compositions of partial melts. Partial melts at IW-1 are distinctly enriched in SiO2 relative to those of IW and IW+2 melts. The silica-enriched, reduced (IW-1) melts are characterized by high alkali contents and have silica-oversaturated compositions. In contrast, the silica-depleted, oxidized (≥IW) melts, which are also enriched in alkali contents, have distinctly silica-undersaturated compositions. These experimental results suggest that alkali-rich, felsic, asteroidal crusts as represented by paired achondrites Graves Nunataks 06128 and 06129 should originate from a low-degree, relatively reduced partial melt from a parent body having near-chondritic compositions. Based on recent chronological constraints and numerical considerations as well as our experimental results, we propose that such felsic magmatism should have occurred in a parent body that is smaller in size and commenced accreting later than those highly differentiated asteroids having basaltic crusts and metallic cores.

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. Based on in situ hydrogen isotope (D/H) analyses of quenched and impact glasses in Martian meteorites, we provide evidence for the existence of a distinct but ubiquitous water/ice reservoir ( D / H = ∼ 2 – 3 times Earth's ocean water) that lasted from at least the time when the meteorites crystallized (173–472 million years ago) to the time they were ejected by impacts (0.7–3.3 million years ago), but possibly much longer. The origin of this reservoir appears to predate the current Martian atmospheric water ( D / H = ∼ 5 – 6 times Earth's ocean water) and is unlikely to be a simple mixture of atmospheric and primordial water retained in the Martian mantle (D/H ≈ Earth's ocean water). This reservoir could represent hydrated crust and/or ground ice interbedded within sediments. Our results corroborate the hypothesis that a buried cryosphere accounts for a large part of the initial water budget of Mars.

In this work we present a series of experiments that examine the relationship between oxygen fugacity and Cr valence ratio in olivine grown from a basaltic liquid. These experiments are specifically targeted for an olivine-rich martian basalt composition that was modeled after the bulk chemistry of the meteorite Yamato 980459 (i.e., Y-98). The chromium valence ratio in the olivine crystals was measured with X-ray absorption near edge spectroscopy (XANES) at the Advanced Photon Source, Argonne National Laboratory. Results from the XANES measurements indicate that the ratio of divalent to trivalent Cr in the olivine is not only systematically correlated with f O 2 , but is also reflective of the molar Cr 3+ /Cr 2+ in the silicate liquid from which it grew. In this way, measurements of Cr valence in olivine phenocrysts can yield important information about the oxygen fugacity and molar Cr 3+ /Cr 2+ of its parental liquid in the absence of a quenched melt phase. Although the results from the experiments presented in this work specifically apply to the Y-98 parental melt, the concepts and XANES analytical techniques discussed within the text present a novel, generalized methodology that may be applicable to any olivine-bearing basalt. Furthermore, the XANES-based measurements are made on a micrometer-scale, thus potential changes of the Cr 3+ /Cr 2+ in the melt during crystallization could be examined with a great deal of spatial detail.

A spiked (with REE, V, Sc) martian basalt Y980459 composition was used to synthesize olivine, spinel, and pyroxene at 1200 C at 5 oxygen fugacities: IW-1, IW, IW+1, IW+2, and QFM. The high spike levels for REE were used for two specific reasons. First, we wanted to be able to analyze REE by both electron microprobe and ion probe. Second, we wanted the most important "Others" components, (i.e., those outside the pyroxene quadrilateral such as Al, Cr3+, Fe3+, REE3+, V3+, V4+, etc.) to be REE3+Mg (Si,Al)2O6. At the doped levels we used, the most important "Others" component is REE3+ in the M2 site coupled with Al in the tetrahedral site. The goal of this paper is to explain the significant increase in the value of D(sub V)(sup pyroxene/melt) with increased Wo content of the pyroxene. We compare augite (Wo approx. 33), pigeonite (Wo approx. 13) and orthopyroxene (Wo approx 3.8). We also show olivine for comparison. The crystal chemical factors which account for this remarkable increase of DV with Wo are twofold. First, with Ca in the M2 site (as in diopside, CaMgSi2O6) the site is large and 8-coordinated while Mg in the M2 site (as in enstatite, Mg2Si2O6) the site is smaller and 6- coordinated. Second, tetrahedral Al in the pyroxene chains provides charge balance and makes the M2 site larger and more compliant for the introduction of REE.

[1] The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) measured a Mars atmospheric14N/15N ratio of 173 ± 11 on sol 341 of the mission, agreeing with Viking's measurement of 168 ± 17. The MSL/SAM value was based on Quadrupole Mass Spectrometer measurements of an enriched atmospheric sample, with CO2 and H2O removed. Doubly ionized nitrogen data at m/z 14 and 14.5 had the highest signal/background ratio, with results confirmed by m/z 28 and 29 data. Gases in SNC meteorite glasses have been interpreted as mixtures containing a Martian atmospheric component, based partly on distinctive14N/15N and40Ar/14N ratios. Recent MSL/SAM measurements of the40Ar/14N ratio (0.51 ± 0.01) are incompatible with the Viking ratio (0.35 ± 0.08). The meteorite mixing line is more consistent with the atmospheric composition measured by Viking than by MSL.

A spiked (with REE, V, Sc) martian basalt Yamato 980459 (Y98) composition was used to synthesize olivine, spinel, and pyroxene at 1200 °C at five oxygen fugacities: IW−1, IW, IW+1, IW+2, and QFM. These run products were analyzed by electron microprobe, ion microprobe, and X-ray absorption near-edge spectroscopy to establish four oxybarometers based on vanadium partitioning behavior between the following pairs of phases: V spinel-melt, V/(Cr+Al) spinel-melt, olivine-melt, and spinel-olivine. The results for the spinel-melt, olivine-melt, and V/(Cr+Al) spinel-melt are applicable for the entire oxygen fugacity range while the spinel-olivine oxybarometer is only applicable between IW−1 and IW+1. The oxybarometer based on V partitioning between spinel-olivine is restricted to basalts that crystallized under low oxygen fugacities, some martian, all lunar, as well as samples from 4 Vesta. The true potential and power of the new spinel-olivine oxybarometer is that it does not require samples representative of a melt composition or samples with some remnant of quenched melt present. It just requires that the spinel-olivine pairs were in equilibrium when the partitioning of V occurred. We have applied the V spinel-olivine oxybarometer to the Y98 meteorite as a test of the method.

Volatile elements have influenced the differentiation and eruptive behavior of Martian magmas and played an important role in the evolution of Martian climate and near-surface environments. However, the abundances of volatiles, and in particular the amount of water in the Martian interior, are disputed. A record of volatile reservoirs is contained in primitive Martian basalts (shergottites). Olivine-hosted melt inclusions from a geochemically depleted shergottite (Yamato 980459, representing a very primitive Martian melt) possess undegassed water with a chondritic and Earth-like D/H ratio (δD≤275‰). Based on volatile measurements in these inclusions, the water content of the depleted shergottite mantle is calculated to be 15–47 ppm, which is consistent with the dry mantle hypothesis. In contrast to D/H in the depleted shergottite, melt from an enriched shergottite (Larkman Nunatak 06319), which either formed by melting of an enriched mantle or by assimilation of crust, exhibits an extreme δD of ∼5000‰, indicative of a surface reservoir (e.g., the Martian atmosphere or crustal hydrosphere). These data provide strong evidence that the Martian mantle had retained the primordial low-δD component until at least the time of shergottite formation, and that young Martian basalts assimilated old Martian crust.

The pKa value of protonated Jeffamine (bis(3-aminopropyl) terminated polyethylene glycol) in solution and attached as a monolayer to graphite surfaces has been determined using potentiometric titration. The protonated Jeffamine was found to have a pKa value of 9.7 in solution at 25 degrees C, whereas this value decreases to 7.1 when it is attached to a graphite surface. Potentiometric titrations from 25 to 40 degrees C allowed us to determine the surface pKa of the protonated Jeffamine at each temperature studied and hence to determine the enthalpy, entropy and Gibbs energy changes associated with the deprotonation of the amino-terminated surface bound Jeffamine groups. It was found that the enthalpic contribution is negligibly small and the evaluation of these thermodynamic parameters controlling the shift in surface pKa value indicates that this process is controlled by entropic contribution arising from the ordering/disordering of solvent molecules at the carbon-water interface. This suggests that the long chain Jeffamine molecules are oriented on the carbon surface rather than existing in the bulk solution.

A strategy has been established for the synthesis of peptidomimetics derived from unsaturated carbohydrates, and exemplified by the use of methyl 2,6-anhydro-7-azido-3,7-deoxy-4,5-O-isopropylidene-D-lyxo-hept-2-enonate 9 as a dipeptide ‘monomer’ which can be elaborated from either end. Selective reduction of 9 gives a protected pseudodipeptide ester suitable for use as an amino component, and saponification gives an azido acid suitable for use as a carboxyl component. The ‘dimer’ product of coupling these two components with TBTU can be similarly elaborated at either end to give a ‘trimer’, and a further cycle of selective reduction and coupling gave a ‘tetramer’, 17, a pseudo-octapeptide. Copyright © 2003 European Peptide Society and John Wiley & Sons, Ltd.

The thermodynamics of and the kinetic parameters controlling the sequestration of the toxic heavy-metal ion Cd(II) from aqueous media by using a novel material consisting of glassy carbon microspheres (10-20 microm in diameter) chemically modified with L-cysteine methyl ester are presented. In an effort to reduce the cost and increase the efficiency of toxic-metal-ion removal, this modification strategy was expanded to attach L-cysteine methyl chemically ester to less-expensive graphite powders (2-20 microm in diameter), and the thermodynamic and kinetic parameters of the sequestration of Cd(II), Cu(II), and As(III) toxic metal ions are presented. It was found that the use of chemically modified graphite powder greatly increased both the rate and the amount of metal ions removed from aqueous media. This work has important potential applications to filtration of drinking water and environmental remediation.

L-Cysteine methyl ester modified glassy carbon powder (CysOMe-GC) has been shown to have potential for the removal of toxic heavy metal ions, such as copper(II), cadmium(II) and arsenic(III), from “real” water samples. To develop this material for environmental applications we must develop an understanding of the thermodynamic parameters controlling the uptake of metal ions by the modified carbon powder. Here we characterise the material using X-ray photoelectron spectroscopy (XPS), before investigating the effect of varying the solution pH, the concentration of copper(II) ions and the mass of CysOMe-GC powder added to the solution using square wave voltammetry (SWV). This data allows us to understand the thermodynamics controlling the copper(II) ion uptake and elucidate that the adsorption of copper(II) onto the CysOMe modified surface is controlled by a Freundlich isotherm.

"Bamboo-like" multiwalled (b-MWCNT), "hollow-tube" multiwalled (h-MWCNT) and single-walled carbon nanotubes (SWCNT), chemically modified with 1-anthraquinonyl (AQ) or 4-nitrophenyl (NP) groups, are characterized using voltammetric, electron microscopic and Raman spectroscopic techniques. The pKa values of the AQ-modified CNTs are found to be shifted by greater than three units when compared to the pKa values of anthrahydroquinone (AHQ, the reduced form of AQ) in aqueous solution to beyond pH 14. These large changes in the surface pKa values of the modified CNTs are explored further by comparing the pKa values of CNTs modified with an anthraquinonyl-2-carboxylic acid group. These groups are attached to the CNT surface via the formation of an amide bond with an aminophenyl "spacer" unit derived from the chemical reduction of NP modified CNTs. The location of reactive sites on the CNT surface is investigated and their influence on the pKa of the modified materials is discussed. Comparison with modified pyrolytic graphite electrodes exposing pure edge-plane or pure basal-plane crystal faces indicates that the modifying aryl groups are predominantly located on edge-plane like defects at the tube ends of MWCNTs. The effect of polymer formation on electron transfer kinetics of b-MWCNTs and h-MWCNTs is also discussed. In contrast SWCNTs show both significant side-wall functionalisation and fast electron transfer kinetics which is attributed to their different electronic structure. This journal is © The Royal Society of Chemistry.

Quinone groups on the surface of edge-plane and basal-plane pyrolytic graphite electrodes, and, for the first time, "bamboo-like" multi-walled carbon nanotubes (b-MWCNTs), are labelled with a voltammetric "tag", namely 2,4-dinitrophenylhydrazine (2,4-DNPH). The voltammetric response of these materials is studied in both aqueous and non-aqueous electrolyte solutions, and mechanisms are proposed for each media involving the voltammetrically controlled cleavage of the 2,4-DNPH adduct. Thus, these materials can be used for potentiometrically controlled chemical release, and as such may find application in, for example, drug delivery systems. In aqueous media, this cleavage results in the conversion of the surface quinonyl groups into surface arylnitroso species. This conversion is confirmed by studying the voltammetric response of the arylnitroso/arylhydroxylamine redox couple, formed after cleavage of the 2,4-DNPH adduct in the presence of l-glutathione, which has been shown in our previous work to react with arylnitroso species on the surface of graphitic carbon materials. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

A method of constructing a "designer interface" consisting of either monolayers or multilayers of chemically modified microbeads is reported, whereby the shape of the interface as well as the interfacial chemistry imparts "diffusional protection" to the underlying surface material. © The Royal Society of Chemistry 2006.

Further studies on the use in peptide synthesis of N(π)-phenacyl protection for histidine side chains have shown that whilst this prevents the side chain-induced racemisation which can occur if there is a lone pair of electrons available at the π-nitrogen, there are concomitant drawbacks. As an alternative approach to the racemisation problem, the effect of halogenation of the heterocyclic ring carbons (to diminish the availability of the π-nitrogen lone pair) has been investigated. This gives derivatives which are convenient in both classical and solid-phase applications, the halogen modifying groups being removed at the last stage by catalytic hydrogenolysis over a rhodium catalyst. Racemisation is suppressed as expected, but it is not eliminated completely: direct blockade of the π-nitrogen appears to be indispensable for its complete prohibition. Protection of the π-nitrogen with a benzyloxymethyl group has now been found to be much more satisfactory than the use of the phenacyl group for this purpose. A π-benzyloxymethyl substituent not only prohibits side chain-induced racemisation but also gives derivatives with convenient physical properties which can be incorporated into well established classical and solid-phase strategies without the need for any novel or additional operations or changes in protocol. The protecting group is stable to basic conditions, to trifluoroacetic acid, and to aqueous solutions of carboxylic acids, but is cleaved cleanly and rapidly by hydrogen bromide in trifluoroacetic acid or by catalytic hydrogenolysis. N(α)-t-Butoxycarbonyl-N(π)-benzyloxymethyl-L-histidine has been prepared in good yield by a simple procedure from an easily accessible intermediate and isolated as a crystalline solid; its use has been demonstrated by a number of exercises including a solid-phase synthesis of 5-isoleucine-angiotensin II and a classical synthesis of trihistidine.

International audience; The Highly Siderophile Elements (HSE) are powerful tracers of planetary differentiation. Despite the importance of their partitioning between silicate and metal for the understanding of planetary core formation, especially for the Earth and Mars, there is still a huge discrepancy between conclusions based on different high temperature (HT) experimental studies. These disagreements may be due to the presence of HSE micro and nanonuggets in HT experiments. The formation of these nuggets is still interpreted in different ways. One hypothesis is that these HSE nuggets formed during the quench of the silicate melt, while another hypothesis supposes that these nuggets formed before the quench and represented artefacts of HT experiments. The goal of this work is to clarify whether the presence of HSE nuggets in silicate melts is linked to a quench effect or not. Understanding the formation of these HSE nuggets represents thus a necessary step towards the resolution of the Earth's core formation scenarios. We performed new HT experiments (1275–2000 • C) at different oxygen fugacities (fO 2), between ambient air up to ∼5 log units below the Iron-Wüstite buffer [IW-5], for two different silicate compositions (synthetic martian and terrestrial basalts) mixed with a metallic mixture of Pt–Au– Pd–Ru. Our 1275–1600 • C experiments were contained in either olivine, diopside or graphite crucible; experiments at 2000 • C were performed using a levitation method, so no capsule was necessary. Our samples contained quenched silicate melts, minerals (olivine, pyroxene, spinel depending on the run), a two-phase metallic bead and nano and micro-nuggets of HSE. Our samples underwent fine textural, structural and analytical characterizations. The distribution of the nuggets was not homogeneous throughout the quenched silicate melt. HSE nuggets were present within crystals. Dendritic textures from the quenched silicate melt formed around HSE nuggets, which could be crystallized, showing that the nuggets acted as nucleation sites during the quench. Thus they predated the quench. Finally, these nuggets also had strong heterogeneities suggesting at least a two-stage formation process under reducing conditions. Consequently, our observations clearly show that these HSE nuggets formed before the quench in the silicate melt. Our results agreed with previous studies, which concluded that HSE abundances in the Earth's mantle require the late accretion of chondritic material subsequent to core formation. However, the effects of metallic Si, O, H, or the effect of pressure on the HSE partitioning are still not fully understood. Further work to constrain these effects is to be encouraged to understand the Earth's core formation.

article i nfo Article history: Solid metal/liquid metal partitioning experiments were conducted at 9 GPa and 1323-1873 K in the Fe-S system. Analysis of the experimental charges by in situ laser ablation inductively coupled plasma mass spectrometry enabled partitioning results to be obtained for a total of 21 trace elements (Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Ag, Sn, Sb, W, Re, Os, Ir, Pt, Au, Pb, and Bi). This new, elevated pressure dataset for the Fe-S system allows a direct comparison to the extensive data available at 0.1 MPa and permits evaluation of the effect of pressure on partitioning in this system. The majority of the elements studied exhibit different solid metal/liquid metal partitioning behaviors at 9 GPa than at 0.1 MPa. Additionally, the nature of these differences varies significantly between the 21 trace elements studied, spanning the range of behaviors of partitioning from more strongly into solid metal, to less strongly into solid metal, and to becoming insensitive to the metallic liquid composition. We conclude that pressure affects solid metal/liquid metal partitioning behavior in the Fe-S system and discuss the implications for fractionations due to Earth's core solidification and for planetary differentiation models.

The high average density and low surface FeO content of the planet Mercury are shown to be consistent with very low oxygen fugacity during core segregation, in the range 3–6 log units below the iron–wustite buffer. These low oxygen fugacities, and associated high metal content, are characteristic of high-iron enstatite (EH) and Bencubbinite (CB) chondrites, raising the possibility that such materials may have been important building blocks for this planet. With this idea in mind we have explored the internal structure of a Mercury sized planet of EH or CB bulk composition. Phase equilibria in the silicate mantle have been modeled using the thermodynamic calculator p-MELTS, and these simulations suggest that orthopyroxene will be the dominant mantle phase for both EH and CB compositions, with crystalline SiO 2 being an important minor phase at all pressures. Simulations for both compositions predict a plagioclase-bearing “crust” at low pressure, significant clinopyroxene also being calculated for the CB bulk composition. Concerning the core, comparison with recent high pressure and high temperature experiments relevant to the formation of enstatite meteorites, suggest that the core of Mercury may contain several wt.% silicon, in addition to sulfur. In light of the pressure of the core–mantle boundary on Mercury (∼7 GPa) and the pressure at which the immiscibility gap in the system Fe–S–Si closes (∼15 GPa) we suggest that Mercury’s core may have a complex shell structure comprising: (i) an outer layer of Fe–S liquid, poor in Si; (ii) a middle layer of Fe–Si liquid, poor in S; and (iii) an inner core of solid metal. The distribution of heat-producing elements between mantle and core, and within a layered core have been quantified. Available data for Th and K suggest that these elements will not enter the core in significant amounts. On the other hand, for the case of U both recently published metal/silicate partitioning data, as well as observations of U distribution in enstatite chondrites, suggest that this element behaves as a chalcophile element at low oxygen fugacity. Using these new data we predict that U will be concentrated in the outer layer of the mercurian core. Heat from the decay of U could thus act to maintain this part of Mercury’s core molten, potentially contributing to the origin of Mercury’s magnetic field. This result contrasts with the Earth where the radioactive decay of U represents a negligible contribution to core heating.

Brownleeite, ideally stoichiometric MnSi, is a manganese silicide not previously observed in nature that was discovered within an interplanetary dust particle that likely originated from a comet. Three submicrometer brownleeite grains were found, with one of them poikilitically enclosed by Mn-bearing forsterite. Owing to the small size of the brownleeite grains, it was not possible to determine conventional macroscopic properties of this mineral; however, the chemical composition and crystal structure were well constrained by extensive quantitative energy dispersive X-ray analysis and electron diffraction using transmission electron microscopy (TEM). The crystal system for brownleeite is cubic ( a = 4.557 A) with space group P 2 1 3, cell volume = 94.63 A 3 , Z = 4, density (calculated) = 2.913 g/cm 3 , and empirical formula: (Mn 0.77 Fe 0.18 Cr 0.05 )Si. These brownleeite grains likely formed as high-temperature condensates either in the early Solar System or in the outflow of an evolved star or supernova explosion.

Syntheses of the sequential polypeptide elastin models poly-(Gly-Val-Gly-Val-Pro) and poly-(Gly-Val-Pro-Gly) are described.

ortho-Quinones can be differentiated from other oxygen-containing surface functional groups on the surfaces of graphite, glassy carbon, "bamboo-like", and "hollow-tube" multiwalled carbon nanotubes and single-walled carbon nanotubes by chemically labeling them with either an inorganic hexamminechromium(III) complex or organic 1,2-phenylenediamine derivatives. Both types of labels can be observed using cyclic voltammetry or by X-ray photoelectron spectroscopy and used to quantify the numbers and relative distribution of orifto-quinones from other oxygen-containing species on the surface including electroactive para-quinones which are not labeled. Labeling of ortho-quinones with 1,2-phenylenediamine derivatives results in the formation of phenazine-like adducts on the graphitic surface which have a distinct voltammetry particularly from that of the underivatized para-quinones. © 2007 American Chemical Society.

In order to quantify possible fractionation of U and Pb into a metallic core, we have performed piston cylinder and multi-anvil press experiments at high pressure (up to 20 GPa) and high temperature (up to 2400 °C) and obtained the distribution coefficient Dmetal–silicate and the exchange partition coefficient Kmetal–silicate for these elements between metal and silicates (mineral or liquid). D Pb metal–silicate and D U metal–silicate depend strongly on the S content of the metallic phase, and also on the oxygen fugacity, in agreement with an effective valence state of 4 for U in silicates and 2 for Pb in silicates. K Pb d metal–silicate and K U d metal–silicate show no discernable pressure and temperature trend. U remains lithophile even at high pressure and high temperature but its lithophile nature decreases at very low oxygen fugacity. From our experimental data, it was possible to calculate the U and Pb contents of the cores of Mars and Earth under core-mantle equilibrium conditions at high pressure and high temperature. From the Dmetal–silicate of the present study, we obtained that: 0.008 ppm Our results suggest that the low concentration of Pb in the terrestrial mantle could not be explained by an early Pb sequestration in the Earth’s core even if S is the dominant light element of the core. If we assume a magma ocean scenario, U might produced a maximum value of 1.5% of the total heat budget of the core with a segregation occurring below ΔIW-3. The values found in the present study for U in the Martian core suggest that the magnetic field activity of Mars before ∼0.5 b.y. after its formation would be difficult to ascribe to the decay of U alone.

Of water and methane on Mars The Curiosity rover has been collecting data for the past 2 years, since its delivery to Mars (see the Perspective by Zahnle). Many studies now suggest that many millions of years ago, Mars was warmer and wetter than it is today. But those conditions required an atmosphere that seems to have vanished. Using the Curiosity rover, Mahaffy et al. measured the ratio of deuterium to hydrogen in clays that were formed 3.0 to 3.7 billion years ago. Hydrogen escapes more readily than deuterium, so this ratio offers a snapshot measure of the ancient atmosphere that can help constrain when and how it disappeared. Most methane on Earth has a biological origin, so planetary scientists have keenly pursued its detection in the martian atmosphere as well. Now, Webster et al. have precisely confirmed the presence of methane in the martian atmosphere with the instruments aboard the Curiosity rover at Gale crater. Science , this issue p. 412 , p. 415 ; see also p. 370

Carbon has been proposed as a potential light element in planetary cores, included in models of planetary core formation, and found in meteoritic samples and minerals. To better understand the effect of C on the partitioning behavior of elements, solid/liquid partition coefficients ( D = (solid metal)/(liquid metal)) were determined for 17 elements (As, Au, Co, Cr, Cu, Ga, Ge, Ir, Ni, Os, Pd, Pt, Re, Ru, Sb, Sn, and W) over a range of C contents in the Fe–Ni–C system at 1 atm. The partition coefficients for the majority of the elements increased as the C content of the liquid increased, an effect analogous to that of S for many of the elements. In contrast, three of the elements, Cr, Re, and W, were found to have anthracophile (C-loving) preferences, partitioning more strongly into the metallic liquid as the C content increased, resulting in decreases to their partition coefficients. For half of the elements examined, the prediction that partitioning in the Fe–Ni–S and Fe–Ni–C systems could be parameterized using a single set of variables was not supported. The effects of S and C on elemental partitioning behavior can be quite different; consequently, the presence of different non-metals can result in different fractionation patterns, and that uniqueness offers the opportunity to gain insight into the evolution of planetary bodies.

The redox states of volcanic and impact melts from the Earth, Moon, and Mars have been estimated from the valence state of V in basaltic glasses (Sutton et al. 2005). The V valence has been determined using synchrotron micro X-ray absorption near-edge structure spectroscopy (XANES) (Sutton et al. 2005), which allows for in situ measurements on samples with a micrometer spatial resolution and ~100 ppm elemental sensitivity. Here, we interpret those results for the natural samples and compare them to the literature. The results show that terrestrial melts are dominated by V 4+ , lunar samples by V 3+ , with Martian melts a mixture of both V 3+ and V 4+ . The f O 2 estimates derived from the V valence are consistent with those determined by other proven methods, whereby terrestrial basalts experience f O 2 conditions within 1 or 2 log units of the QFM buffer, lunar basalts equilibrate at 1 to 2 log units below the IW buffer, and Martian basalts fall somewhere between the QFM and IW buffer. The results illustrate the usefulness of this technique; i.e., a robust oxybarometer covering over six orders of magnitude, applicable to samples that record f O 2 conditions from reduced extraterrestrial bodies to the oxidized Earth.

A series of oxetane δ-amino acid scaffolds derived from L-rhamnose and D-xylose provide a new class of templated sugar amino acids (SAA), which can be considered as D/L-alanine-D-serine and glycine-L-serine dipeptide isosteres. © 2004 Elsevier Ltd. All rights reserved.

An efficient multigram ring contraction of a 1,4-lactone 2-O-triflate derived from l-rhamnose - with retention of configuration in the ring closure - is the key step in the preparation of a series of oxetanes, which are pseudoenantiomeric analogues of the naturally occurring antibiotic oxetin, an oxetane cis-β-amino acid. Subsequent nucleophilic displacements of the corresponding triflates by azide proceed in consistently excellent yields, without any elimination, to provide syntheses of scaffolds for analogues of the antibiotic. © 2004 Elsevier Ltd. All rights reserved.

A series of experiments on a synthetic, pigeonite-saturated, basaltic shergottite were carried out to constrain the variation of D (Eu/Gd) pigeonite/melt and D (Eu/Sm) pigeonite/melt with oxygen fugacity ( f O2 ). The experiments have been run under both dry and hydrous conditions. The shergottite was doped with 0.1, 0.5, and 1.0 wt.% Eu, Gd, and Sm oxides in different experiments and was equilibrated at liquidus conditions for 24 hours. D (Eu/Gd) pigeonite/melt in dry melts ranges from 0.156 ± 0.014 ( f O2 = IW − 1) to 0.630 ± 0.102 (IW + 3.5). D (Eu/Sm) pigeonite/melt in dry melts ranges from 0.279 ± 0.021 (IW − 1) to 1.114 ± 0.072 (IW + 3.5). Due to difficulties with low- f O2 experiments, hydrous distribution coefficients were measured, but were not used in the calibration of the Eu-oxybarometers. These two Eu-oxybarometers provide an accurate way to measure f O2 recorded during pigeonite crystallization, thereby yielding a record of f O2 during the earliest period of Martian meteorite parent magma crystallization history. Using this new calibration, Martian meteorite pigeonite cores record f O2 values of IW − 0.6 (±0.3) (QUE94201) to IW + 1.9 (±0.6) (Shergotty). These new values differ in magnitude, but not trend, from previously published data. The pigeonite Eu-oxybarometer yields an f O2 range in the basaltic shergottites of 2 to 3 orders of magnitude. Several processes have been proposed to explain the origin of this f O2 range, the majority of which rely on assimilation of an oxidized source. A potential correlation between this new pigeonite data and recent Fe-Ti oxide data, however, is consistent with intrinsic f O2 differences in the magma source region being responsible for the measured f O2 variations. This implies that the Martian meteorite source region, the mantle or lithosphere, may be heterogeneous in nature. However, the process of assimilation cannot be completely ruled out in that an assimilation event that took place before crystallization commenced would result in the overprinting of the source region f O2 signature.

Many solar system processes involve a metallic liquid, and the composition of the metallic liquid, such as the liquid's concentrations of S, P, and C, will influence the partitioning of elements during such processes. We present a method for parameterizing solid metal-liquid metal partition coefficients for siderophile (metal-loving) elements as a function of the metallic liquid composition. Our parameterization method is based on an older theory of Jones and Malvin (1990), which stated that the metallic liquid is composed of metal and non-metal-bearing domains, and the domains are the dominant influence on the partitioning behavior. By revising the means by which the metal domains are calculated, our revised parameterization method is able to match experimental partitioning data from the Fe-Ni-S, Fe-Ni-P, Fe-Ni-S-P, and Fe-Ni-C systems. Mathematical expressions were derived for the solid metal-liquid metal partitioning of 13 siderophile elements. Elements that are chalcophile (S-loving), P-loving, or C-loving prefer the non-metal-bearing domains in the metallic liquid and, consequently, aren't fit by the parameterization method presented here. Possible applications for our parameterization method include modeling the crystallization of iron meteorites, planetary differentiation, and the solidification of Earth's inner core.

We have evaluated the highly siderophile element (HSE) signatures of the martian (SNC) meteorites using new and literature data. These Ir and Os concentrations correlate with the Mg# [molar Mg/(Mg+Fe)], Cr and Ni, suggesting that olivine or chromite acts as a host for compatible siderophiles. Our analysis agrees with others who have suggested that the martian mantle has chondritic relative abundances of siderophiles. We also agree that, unlike the Sr and Nd isotopic systems, there is no evidence from Os isotopes for crustal assimilation. Comparisons of the siderophile element ratios of ALH 84001 to younger SNCs give no indication of a change in the martian siderophile element pattern over time. D 2002 Published by Elsevier Science B.V.

A composition approximating the lithology A groundmass ofthe Elephant Moraine (EET) 79001 martian basalt (Eg; McSween and Jarosewich, 1983) has been used to investigate the petrogenesis ofthe meteorite and the behavior ofCr and V at different oxygen fugacities. Crystallization experiments were carried out over a range of temperatures, and oxygen fugacities of either iron-wustite (IW) or IW + 2 (i.e., 1.5 log units below the quartz-fayalite-magnetite (QFM) buffer). Comparison oftrace element concentrations (obtained by secondary ion mass spectrometry (SIMS) analysis) in experimental silicates with those of natural silicates supports the Fe-Ti oxide-derived oxygen fugacity of QFM -1.8 ± 0.3 for this basalt (Herd et al., 2001). Experimental distribution coefficients, in conjunction with SIMS analyses of rims from the olivine and pyroxene xenocrysts in lithology A, as well as analyses of lithology A groundmass pigeonite cores, are used to calculate coexisting liquid concentrations of V and Cr. Liquid compositions derived from pigeonite xenocryst rims and groundmass pigeonite cores are similar, suggesting that the rims of orthopyroxene xenocrysts are overgrowths, which have not previously been accounted for when reconstructing the groundmass composition. This implies that the Eg composition requires modification. A similar exercise for the ferroan rims on olivine xenocrysts yields very different liquid compositions, indicating that these rims are not overgrowths but are part of the xenocryst assemblage. These results are shown to be consistent with the petrography of lithology A xenocrysts.

The oxygen fugacity of the Dar al Gani 476 martian basalt is determined to be quartz-fayalite-magnetite (QFM) −2.3 ± 0.4 through analysis of olivine, low-Ca pyroxene, and Cr-spinel and is in good agreement with revised results from Fe-Ti oxides that yield QFM −2.5 ± 0.7. This estimate falls within the range of oxygen fugacity for the other martian basalts, QFM −3 to QFM −1. Oxygen fugacity in martian basalts correlates with 87Sr/86Sr, 143Nd/144Nd, and La/Yb ratios, indicating that the mantle source of the basalts is reduced and that assimilation of crust-like material controls the oxygen fugacity. This allows constraints to be placed on the oxidation state of the martian mantle and on the nature of assimilated crustal material. The assimilated material may be the product of early and extensive hydrothermal alteration of the martian crust, or it may be amphibole- or phlogopite-bearing basaltic rock within the crust. In either case, water may play a significant role in the oxidation of basaltic magmas on Mars, although it may be secondary to assimilation of ferric iron-rich material.

International audience; The Curiosity rover discovered fine-grained sedimentary rocks, which are inferred to represent an ancient lake and preserve evidence of an environment that would have been suited to support a martian biosphere founded on chemolithoautotrophy. This aqueous environment was characterized by neutral pH, low salinity, and variable redox states of both iron and sulfur species. Carbon, hydrogen, oxygen, sulfur, nitrogen, and phosphorus were measured directly as key biogenic elements; by inference, phosphorus is assumed to have been available. The environment probably had a minimum duration of hundreds to tens of thousands of years. These results highlight the biological viability of fluvial-lacustrine environments in the post-Noachian history of Mars.