Evidence for high-pressure core-mantle differentiation from the metal-silicate partitioning of lithophile and weakly-siderophile elements

Liquid Fe metal-liquid silicate partition coefficients for the lithophile and weakly-siderophile elements Ta, Nb, V, Cr, Si, Mn, Ga, In and Zn have been measured in multianvil experiments performed from 2 to 24 GPa, 2023-2873 K and at oxygen fugacities of −1.3 to −4.2 log units relative to the iron-wüstite buffer. Compositional effects of light elements dissolved in the metal liquid (S, C) have been examined and experiments were performed in both graphite and MgO capsules, specifically to address the effect of C solubility in Fe-metal on siderophile element partitioning. The results were used to examine whether there is categorical evidence that a significant portion of metal-silicate equilibration occurred under very high pressures during core-mantle fractionation on Earth. Although the depletion of V from the mantle due to core formation is significantly greater than that of Nb, our results indicate that both elements have similar siderophile tendencies under reducing conditions at low pressures. With increasing pressure, however, Nb becomes less siderophile than V, implying that average metal-silicate equilibration pressures of at least 10-40 GPa are required to explain the Nb/V ratio of the mantle. Similarly the moderately-siderophile, volatile element ratios Ga/Mn and In/Zn are chondritic in the mantle but both volatility and core-mantle equilibration at low pressure would render these ratios strongly sub-chondritic. Our results indicate that pressures of metal-silicate partitioning exceeding 30-60 GPa would be required to render these element ratios chondritic in the mantle. These observations strongly indicate that metal-silicate equilibration must have occurred at high pressures, and therefore support core-formation models that involve deep magma oceans. Moreover, our results allow us to exclude models that envisage primarily low-pressure (<1 GPa) equilibration in relatively small planetary bodies. We also argue that the core cannot contain significant U as this would require metal-silicate equilibration at oxygen fugacities low enough for significant amounts of Ta to have also been extracted from the mantle. Likewise, as In is more siderophile than Pb but similarly volatile and also quite chalcophile it would have been difficult for Pb to enter the core without reversing the relative depletions of these elements in the mantle unless metal-silicate equilibration occurred at high pressures >20 GPa.     

Effect of pressure, temperature, and oxygen fugacity on the metal-silicate partitioning of Te, Se, and S: Implications for earth differentiation

We have measured liquid Fe metal-liquid silicate partitioning (D_i) of tellurium, selenium, and sulfur over a range of pressure, temperature, and oxygen fugacity (1-19 GPa, 2023-2693 K, fO₂ −0.4 to −5.5 log units relative to the iron-wüstite buffer) to better assess the role of metallic melts in fractionating these elements during mantle melting and early Earth evolution. We find that metal-silicate partitioning of all three elements decreases with falling FeO activity in the silicate melt, and that the addition of 5-10 wt% S in the metal phase results in a 3-fold enhancement of both D_Te and D_Se. In general, Te, Se, and S all become more siderophile with increasing pressure, and less siderophile with increasing temperature, in agreement with previous work. In all sulfur-bearing experiments, D_Te is greater than D_Se or D_S, with the latter two being similar over a range of P and T. Parameterized results are used to estimate metal-silicate partitioning at the base of a magma ocean which deepens as accretion progresses, with the equilibration temperature fixed at the peridotite liquidus. We show that during accretion, Te behaves like a highly siderophile element, with expected core/mantle partitioning of >10⁵, in contrast to the observed core/mantle ratio of ∼100. Less extreme differences are observed for Se and S, which yielded core/mantle partitioning 100- to 10 times higher, respectively, than the observed value. Addition of ∼0.5 wt% of a meteorite component (H, EH or EL ordinary chondrite) is sufficient to raise mantle abundances to their current level and erase the original interelement fractionation of metal-silicate equilibrium.     

Trace element partitioning between ilmenite, armalcolite and anhydrous silicate melt: Implications for the formation of lunar high-Ti mare basalts

We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300-1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO-FeO-MgO-Al₂O₃-TiO₂-SiO₂ system. Ilmenite-melt and armalcolite-melt partition coefficients (D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( 0.0020 ± 0.0010 to 0.069 ± 0.010 for ilmenite; 0.0048 ± 0.0023 to 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: 0.0013 ± 0.0008, 0.0035 ± 0.0015 and 0.039 ± 0.005, and for armalcolite 0.008 ± 0.003, 0.0048 ± 0.0022 and 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. 0.28 ± 0.05 and : 0.76 ± 0.07). Both minerals fractionate the high field strength elements with D_Ta/D_Nb and D_Hf/D_Zr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with D_Hf/D_W = 12-13 compared to 6.7-7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite (D ∼ 7.5) and V in armalcolite (D ∼ 8.1). D values show no clear variation with pressure in the small range covered.Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals.Our results are used to model the Lu-Hf-Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO₂ contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.     

The effect of Si on metal-silicate partitioning of siderophile elements and implications for the conditions of core formation

We have determined the liquid metal-liquid silicate partitioning of Ni, Co, Mo, W, V, Cr and Nb at 1.5 GPa/1923 K and 6 GPa/2123 K under conditions of constant silicate melt composition with variable amounts of Si in the Fe-rich metallic liquid. Partitioning of Ni, Co, Mo, W and V is sensitive to the Si content of the metal with, in all five cases, increasing Si tending to make the element more lithophile than for conditions where the metal is Si-free. In contrast, metal-silicate partitioning of Cr and Nb is, at constant silicate melt composition, insensitive to the Si content of the metal.The implications of our data are that if, as indicated by the Si isotopic composition of the silicate Earth ( [Georg et al., 2007] and [Fitoussi et al., 2009]), the core contains significant amounts of Si, the important siderophile elements Ni, Co, W and Mo were more lithophile during accretion and core formation than previously believed.We use our new data in conjunction with published metal-silicate partitioning results to develop a model of continuous accretion and core segregation taking explicit account of the partitioning of Si (this study) and O (from Ozawa et al., 2008) between metal and silicate and their effects on metal-silicate partitioning of siderophile elements. We find that the effect of Si on the siderophile characteristics of Ni, Co and W means that the pressures of core segregation estimated from these elements are ∼5 GPa lower than those derived from experiments in which the metal contained negligible Si (e.g., Wade and Wood, 2005). The core-mantle partitioning of Cr and Nb requires that most of Earth accretion took place under conditions which were much more reducing than those implied by the current FeO content of the mantle and that the oxidation took place late in the accretionary process. Paths of terrestrial accretion, oxidation state and partitioning which are consistent with the current mantle contents of Ni, Co, W, V, Cr and Nb lead to Si and O contents of the core of ∼4.3 wt.% and 0.15%, respectively.     

Systematics of metal-silicate partitioning for many siderophile elements applied to Earth’s core formation

Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO₂ conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO₂ yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO₂ conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.     

Metal-silicate partitioning of cesium: Implications for core formation

Here we present the first set of metal-silicate partitioning data for Cs, which we use to examine whether the primitive mantle depletion of Cs can be attributed to core segregation. Our experiments independently varied pressure from 5 to 15 GPa, temperature from 1900 to 2400 °C, metallic sulfur content from pure Fe to pure FeS, silicate melt polymerization, expressed as a ratio of non-bridging oxygens to tetrahedrally coordinated cations (nbo/t) from 1.26 to 3.1, and fO₂ from two to four log units below the iron-wüstite buffer. The most important controls on the partitioning behavior of alkalis were the metallic sulfur content, expressed as X_S, and the nbo/t of the silicate liquid. Normalization of X_S to 0.5 yielded the following expressions for D-values as a function of nbo/t: log D_Na = −2.0 + 0.44 × (nbo/t), log D_K = −2.4 + 0.67 × ( nbo/t), and log D_Cs = −3.2 + 1.17 × (nbo/t). Normalization of nbo/t to 2.7 resulted in the following equations for D-values as a function of S content: log D_Na = −4.1 + 6.4 × X_S, log D_K = −7.7 + 13.9 × X_S, and log D_Cs = −12.1 + 23.3 × X_S.There appears to be a negative pressure effect up to 15 GPa, but it should be noted that this trend was not present before normalization, and is based on only two measurements. There is a positive trend in cesium’s metal-silicate partition coefficient with increasing temperature. D_Cs exhibits the largest change and increased by a factor of three over 500 °C. The effect of oxygen fugacity has not been precisely determined but in general, lowering fO₂ by two log units resulted in a rise in all D-values of approximately an order of magnitude. In general, the sensitivity of partition coefficients to changing parameters increased with atomic number.The highest D-value for Cs observed in this study is 0.345, which was obtained at nbo/t of 2.7 and a metal phase of pure FeS. This metallic composition has far more S than has been suggested for any credible core-forming metal. We therefore conclude that the depletion of Cs in Earth’s mantle is either caused by radically different behavior of Cs at pressures higher than 15 GPa or is not related to core formation. Even so, we have shown that a planet with a sufficient S inventory may incorporate significant amounts of alkali elements into its core.     

Fluorine and chlorine abundances in lunar apatite: Implications for heterogeneous distributions of magmatic volatiles in the lunar interior

Apatite has been analyzed from mare basalts, the magnesian-suite, the alkali-suite, and KREEP-rich impact-melt rocks using an electron probe microanalysis routine developed specifically for apatite. We determined that all the lunar apatite grains analyzed are predominantly fluorine rich; however, they also contain varying concentrations of chlorine and a missing structural component that, after ruling out other possibilities, we attribute to OH. Apatite grains from mare basalts are compositionally distinct from the apatite grains in the magnesian-suite, the alkali-suite, and KREEP-rich impact-melt rocks, which all had similar apatite compositions. Apatite grains in mare basalts are depleted in chlorine, and many of the analyzed grains have stoichiometry that suggests a significant OH component (i.e., >0.08 structural formula units), whereas apatite grains in the magnesian suite, alkali suite, and KREEP-rich impact melts are enriched in chlorine and do not typically have a missing structural component that could be attributed to OH⁻ (within the detection limit of 0.08 sfu). From these data, we infer that residual liquids in the mare basalts were enriched in H₂O and fluorine relative to chlorine at the time of apatite crystallization, whereas residual liquids in magnesian-suite, alkali-suite, and KREEP-rich impact melts were enriched in chlorine relative to H₂O and fluorine at the time of apatite crystallization. The relative volatile abundance that we determined for the mare basalts is identical to the previously determined relative volatile abundance for the lunar picritic glasses. This result indicates that the observed relative volatile abundance signature of the picritic glass source is the same as that in the mare basalt source regions. The magnesian-suite, alkali-suite, and KREEP-rich impact-melt rocks likely reflect a volatile source with different volatile abundances than the sources of mare volcanics. Moreover, the magnesian-suite, alkali-suite, and KREEP-rich impact-melt rocks may reveal the relative volatile abundance of urKREEP, the residual melt of the magma ocean. This difference in relative magmatic volatile abundance among the lithologic groups investigated cannot be explained by degassing of a single source composition (relative to magmatic volatiles). The most reasonable explanation for the compositional disparity is a difference in the relative volatile abundances in the magmatic source regions of the Moon. Therefore, we conclude that the Moon has a heterogeneous distribution of magmatic volatiles within its interior, with a chemical divide (with respect to magmatic volatiles) existing between magmas that arise by partial melting of the lunar mantle and magmas that have seen significant contamination by a KREEP component.     

REE partitioning between monazite and garnet: Implications for petrochronology

Rare‐earth element and Y partitioning between garnet and monazite was measured in metamorphic rocks from western Norway to provide more confidence in tying monazite U/Th–Pb dates to P–T conditions recorded in garnet. A subset of samples has low‐Y garnet mantles and low‐Y monazite cores that gave Y‐partitioning temperatures similar to independently determined metamorphic temperatures. In combination with previously published data, these monazite–garnet pairs have temperature‐dependent partitioning of the HREE from Dy to Lu, and nonsystematic partitioning of the LREE from La–Gd. The temperature‐dependent partitioning must be considered when using HREE to assess which portions of garnet and monazite might have coexisted, but experiments are needed to place the dependence on a firm footing.     

High-pressure phase equilibria and element partitioning experiments on Apollo 15 green C picritic glass: Implications for the role of garnet in the deep lunar interior

We report results of nominally anhydrous near-liquidus experiments on a synthetic analog to very low-titanium Apollo 15 green C lunar picritic glass from ∼2 to 5 GPa. Apollo 15 green C glass (A15C) is saturated with garnet and pyroxene on the liquidus at ∼3 GPa. However, such an assemblage is unlikely to represent the lunar-mantle source region for this glass, and instead an olivine + orthopyroxene-dominated source is favored, in accord with earlier lower-pressure experiments on A15C. Near-liquidus garnet has a slight but significant majorite component at ∼5 GPa in this iron-rich bulk composition, as expected from our previous work in ordinary-chondritic bulk compositions. Ion microprobe measurements of partitioning of Sr, Ba, Sc, Nd, Sm, Dy, Yb, Y, Zr, Hf, and Th between garnet and coexisting melt in these experiments are the first garnet partition coefficients (D values) available that are directly relevant to lunar compositions. D values for these garnets differ significantly compared to D values for garnets grown in more magnesian, terrestrial bulk compositions, which until now are all that have been available in modeling the possible role of garnet in the lunar interior. For example, D values for heavy rare earth elements are lower than are those from terrestrial basaltic systems. These partitioning values are well-described by the lattice-strain partitioning model, but predictive relationships for garnet partitioning using that model fail to match the measured values, as was the case in our earlier work on chondritic compositions. Using our new D values in place of the “terrestrial” values in a variety of models of lunar petrogenesis, we suggest that garnet is unlikely to be present in the source regions for very titanium-poor lunar liquids despite its appearance on the liquidus of A15C.     

The variety of lithologies in the Yamato-86032 lunar meteorite: Implications for formation processes of the lunar crust

We performed a petrologic, mineralogical, geochemical, and isotopic study of several lithologies in the Y-86032 feldspathic breccia. This study leads us to conclude that Y-86032 likely originated on the lunar farside. Y-86032 is composed of several types of feldspathic clasts, granulitic breccias, and minor basaltic clasts set in a clastic matrix. We identify an “An97 anorthosite” that has An contents similar to those of nearside FANs. Mg′ (= molar Mg/(Mg + Fe) × 100) values vary significantly from ∼45 to ∼80 covering the ranges of both nearside FANs and the Mg′ gap between FANs and the Mg-suite. A light-gray feldspathic (LG) breccia making up ∼20% of the investigated slab (5.2 × 3.6 cm²) mainly consists of fragments of anorthosites (“An93 anorthosite”) more sodic than nearside FANs. LG also contains an augite-plagioclase clast which either could be genetically related to the An93 anorthosite or to slowly-cooled basaltic magma intruded into the precursor rock. The Na-rich nature of both An93 anorthosite and this clast indicates that the LG breccia was derived from a relatively Na-rich but incompatible-element-poor source. The Mg′ variation indicates that the “An97 anorthosite” is a genomict breccia of several types of primary anorthosites. Granulitic breccias in Y-86032 have relatively high Mg′ in mafic minerals. The highest Mg′ values in mafic minerals for the “An97 anorthosite” and granulitic breccias are similar to those of Mg-rich lithologies recently described in Dhofar 489. Basaltic clasts in the dark-gray matrix are aluminous, and the zoning trends of pyroxene are similar to those of VLT or LT basalts. The crystallization of these basaltic clasts pre-date the lithification age of the clastic matrix at ∼3.8 Ga. The low K contents of plagioclase in both the anorthositic and basaltic clasts and generally low incompatible element abundances in all the lithologies in Y-86032 indicate that KREEP was not involved during the formation of the precursor lithologies. This observation further suggests that urKREEP did not exist in the source regions of these igneous lithologies. All these facts support the idea that Y-86032 was derived from a region far distant from the PKT and that the lithic clasts and fragments are indigenous to that region. An An97 anorthositic clast studied here has distinct Sm-Nd isotopic systematics from those previously found for another An97 anorthositic clast and “An93 anorthosite”, and suggests either that An97 anorthosites come from isotopically diverse sources, or that the Sm-Nd isotopic systematics of this clast were reset ∼4.3 Ga ago. These lines of geochemical, isotopic, and petrologic evidence suggest that the lunar crust is geochemically more heterogeneous than previously thought.     

试论月球科学与类地行星研究的学科属性

我国月球探测一期工程获国家批准立项和“嫦娥一号”卫星成功发射及运行这一历史性事件标志着我国已继人造地球卫星、载人航天阶段之后,开始进入人类航天活动的第三领域——深空探测。无疑此时探讨人类这一伟大社会实践活动的自然科学意义,特别是深空探测对象的科学内涵具有重要的现实意义。随着相关技术的开发、创新和成熟,工作重点将逐渐转移到深空探测对象本身的科学研究上来,即认识地球之外的行星体以及更深刻地重新审视地球。本文讨论了现阶段深空探测对象——月球及类地行星的基本物质属性,回顾美国和前苏联两国探月计划实施历史的启示,Apollo计划的演变．科学内容的纳入及宇航员地学素养的要求,Apollo登月计划的实施对月球科学本身的促进,以及对20世纪地球科学发展、人才队伍建设和分析技术进步等的重大影响,总结了前苏联探月计划的成败及其教训,并对我国月球探测工程立项历史等方面进行了分析。在此基础上,论述了月球科学及类地行星研究的地球科学属性,并强调指出地球科学家应将月球及整个类地行星研究纳入到地球系统科学的框架之中。     

Experimental partitioning of uranium between liquid iron sulfide and liquid silicate: Implications for radioactivity in the Earth’s core

Measurable uranium (U) is found in metal sulfide liquids in equilibrium with molten silicate at conditions appropriate for a planetary magma ocean: 1-10 GPa, 1750-2100 °C, 0-28 wt% S, and fO₂ 2 log units below IW. However, the transfer of U from metal sulfide to silicate under our experimental conditions is so complete that insufficient U would remain so as to be of any importance to the core’s heat budget. U content in the sulfide phase increases strongly with S content but shows no significant variability with either pressure or temperature. Maximum is 0.001 while most values are considerably lower.     

High precision iron isotope measurements of terrestrial and lunar materials

We present the analytical methods that have been developed for the first high-precision Fe isotope analyses that clearly identify naturally-occurring, mass-dependent isotope fractionation. A double-spike approach is used, which allows rigorous correction of instrumental mass fractionation. Based on 21 analyses of an ultra pure Fe standard, the external precision (1-SD) for measuring the isotopic composition of Fe is ±0.14 ‰/mass; for demonstrated reproducibility on samples, this precision exceeds by at least an order of magnitude that of previous attempts to empirically control instrumentally-produced mass fractionation (Dixon et al., 1993). Using the double-spike method, 15 terrestrial igneous rocks that range in composition from peridotite to rhyolite, 5 high-Ti lunar basalts, 5 Fe-Mn nodules, and a banded iron formation have been analyzed for their iron isotopic composition. The terrestrial and lunar igneous rocks have the same isotopic compositions as the ultra pure Fe standard, providing a reference Fe isotope composition for the Earth and Moon. In contrast, Fe-Mn nodules and a sample of a banded iron formation have iron isotope compositions that vary over a relatively wide range, from δ⁵⁶Fe = +0.9 to −1.2 ‰; this range is 15 times the analytical errors of our technique. These natural isotopic fractionations are interpreted to reflect biological (“vital”) effects, and illustrate the great potential Fe isotope studies have for studying modern and ancient biological processes.     

Mobility of iridium in terrestrial environments: Implications for the interpretation of impact-related mass-extinctions

Traditionally, iridium has been considered an element of low mobility, but its behavior is still debated. Ir concentration in a soil affected by a catastrophic mining spill in 1998 that covered the soil with a layer of tailings offers the opportunity to analyse an exceptional Ir-bearing horizon 10 years after deposition. This has enabled comparisons with the values of past Ir-bearing horizons associated to impact-related mass-extinction events. Iridium concentration in the tailings (0.349 ppm) was 5-fold higher than the anomaly in the K-Pg at The Moody Creek Mine section (the highest values obtained from terrestrial sections). The oxidative weathering of the tailings caused the release of Ir and infiltration into the soil. Iridium distribution in depth indicates redistribution throughout the profile in relation to the change in the physico-chemical properties of the soil. With regard to the background concentration in the soil (0.056 ppm), anomalous values of Ir (0.129 ppm) can be detected to 11 cm below the layer of tailings. The correlation analysis between the Ir concentration and the main properties and constituents of the soils indicated a significant correlation with sulfur, iron, clay content, and pH. Selective extractions were made to study the forms in which Ir can be mobilized in the soil. The residual/insoluble fraction was >90% of the total Ir concentration in soil. Soluble-in-water concentration of Ir (1.5% of total) was detected in the uppermost 2-3 cm of the soil, which were directly affected by the leaching of acidic waters coming from the oxidation of the pyrite tailings. Iridium retention in the affected part of the soil reached 9% of the total Ir concentration; this retention could be related to the amorphous iron forms dissolved by the oxalic-oxalate extraction. However, according to our research, original Ir abundance could be secondarily modified, and then a direct analysis of the iridium values recorded in sediments could induce misinterpretations. The comparison between the actual example and the fossil record belonging to terrestrial settings, can be considered as a valuable approach, especially when Iridium data were used by researchers to interpret the impact-related mass-extinction events in the past.     

Possible europium-normal rare-earth abundances estimated from the lunar samples,and the terrestrial analogue

From the mathematical analysis of the rare-earth data on some of the Apollo 12 samples studied by Hubbard et al. (1971), the possible europium-normal primitive rare-earth pattern, in which europium is normal with respect to the adjacent rare-earth elements, has been estimated. A fact that the igneous rocks (Japanese geosynclinal basalts) appearing to reflect the analogous effect occur locally on the earth enhances our interests in the pattern resulting from the above estimation.     

Reflectance spectrophotometry extended to u.v. for terrestrial,lunar and meteoritic samples

Extension of remote sensing of planetary bodies to the ultraviolet is now feasiable up to 2000 Å from earth-orbiting telescopes and spacecraft. The benefits of this extension is analysed on the basis of laboratory spectra taken on a large variety of terrestrial, lunar and meteoritic samples. Knowledge of the albedo for two wavelengths at 2300 and 6500 Å permits classification of a surface into one of the following types: lunar, carbonaceous chondrites, ordinary chondrites, achondrites or acidic rocks, basaltic rocks, irons. For lunar-type surfaces, a simple albedo measurement at 6500 Å can be converted into quantitative abundance determinations of silicate, aluminium oxide and iron; a large amount of telescopic lunar photometry data is available for mapping these abundances. Extension of the photometry to 2300 Å permits quantitative measurement of TiO₂ abundances. For asteroids and non-icy satellites, rock-type classification and constraints in chemical abundances of Si, Al, Fe and Ti can be derived from photometry at 2300 and 6500 Å. The IUE telescope already orbiting the earth, the Space Telescope to come, the lunar polar orbiter and other spacecraft under prospect are potentially available to provide the photometric observations at 6500 and 2300 Å required.     

SIMS U-Pb study of zircon from Apollo 14 and 17 breccias: Implications for the evolution of lunar KREEP

We report the results of a SIMS U-Pb study of 112 zircons from breccia samples from the Apollo 14 and 17 landing sites. Zircon occurs in the breccia matrices as rounded, irregular shaped, broken and rarely euhedral grains and as constituent minerals in a variety of lithic clasts ranging in composition from ultra-mafic and mafic rocks to highly evolved granophyres. Crystallisation of zircon in magmatic rocks is governed by the zirconium saturation in the melt. As a consequence, the presence of zircon in mafic rocks on the Moon implies enrichment of their parent melts in the KREEP component. Our SIMS results show that the ages of zircons from mafic to ultramafic clasts range from ca. 4.35 Ga to ca. 4.00 Ga demonstrating multiple generations of KREEPy mafic and ultramafic magmas over this time period. Individual zircon clasts in breccia matrices have a similar age range to zircons in igneous clasts and all represent zircons that have been incorporated into the breccia from older parents. The age distributions of zircons from breccias from both the Apollo 14 and Apollo 17 landing sites are essentially identical in the range 4.35-4.20 Ga. However, whereas Apollo 14 zircons additionally show ages from 4.20 to 3.90 Ga, no zircons from Apollo 17 samples have primary ages less than ca. 4.20 Ga. Also, in contrast to previous suggestions that the magmatism in the lunar crust is continuous our results show that the zircon age distribution is uneven, with distinct peaks of magmatic activity at ca. 4.35 Ga, ca. 4.20 Ga in Apollo 14 and 17 and a possible third peak in zircons from Apollo 14 at ca. 4.00 Ga. To explain the differences in the zircon age distributions between the Apollo 14 and 17 landing sites we propose that episodes of KREEP magmatism were generated from a primary reservoir, and that this reservoir contracted over time towards the centre of Procellarum KREEP terrane. We attribute the peaks in KREEP magmatism to impact induced emplacement of KREEP magma from a primary mantle source or to a progressive thermal build-up in the mantle source until the temperature exceeds the threshold for generation of KREEP magma, which is transported into the crust by an unspecified possibly plume-like process.     

Strain partitioning in banded and/or anisotropic rocks: Implications for inferring tectonic regimes

Among the many concepts that have contributed to the development of structural geology in the last half-century, two are particularly important. These are: (i) the link between the symmetry of the structure, the vorticity of the associated deformation process and the tectonic regime, and (ii) the widespread partitioning of strain. However, a clear understanding of these concepts and the links between them are not always apparent in structural analyses carried out to determine the prevailing tectonic regime of an area through the use of structural symmetries and kinematic indicators. This contribution, based on field studies from Cap de Creus, experimental data and theoretical concepts, highlights some of the problems encountered when attempting to deduce the type of strain and associated regional tectonic regime from field structures. The relation between the symmetry of a structure and its associated kinematics is not unique. For example, it is demonstrated that in mechanically anisotropic materials, symmetry variations do not necessarily reflect marked vorticity variations, but rather the angular variations between the kinematic framework and the anisotropy planes. Because of widespread strain partitioning, local and general kinematics do not generally match. This mismatch is especially accentuated in rheologically heterogeneous rocks. Nevertheless, correct interpretations are possible by performing continuous multi-scale structural analyses in which the impact of strain partitioning and of the presence of material anisotropies and heterogeneities are considered.     

Trace element partitioning between carbonatitic melts and mantle transition zone minerals: Implications for the source of carbonatites

The occurrence of CO₂-rich lavas (carbonatites, kimberlites) and carbonate-rich xenoliths provide evidence for the existence of carbonatitic melts in the mantle. To model the chemical composition of such melts in the deep mantle, we experimentally determined partition coefficients for 23 trace elements (including REE, U-Th, HFSE, LILE) between deep mantle minerals and carbonatite liquids at 20 and 25 GPa and 1600 °C. Under these conditions, majoritic garnet and CaSiO₃ perovskite are the main reservoirs for trace elements. This study used both femtosecond LA-ICP-MS and SIMS techniques to measure reliable trace element concentrations. Comparison of the two techniques shows a general agreement, except for Sc and Ba. Our experimentally determined partition coefficients are consistent with the lattice strain model. The data suggest an effect of melt structure on partition coefficients in this pressure range. For instance, strain-free partition coefficient (D₀) for majorite-carbonatite melts do not follow the order of cation valence, , observed for majorite-CO₂-free silicate melts. The newly determined partition coefficients were combined with trace element composition of majoritic garnets found as inclusions in diamond to model trace element patterns of deep-seated carbonatites. The result compares favorably with natural carbonatites. This suggests that carbonatites can originate from the mantle transition zone.