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.     

大圆筒结构倾覆稳定分析的有限元法

大直径圆筒结构的倾覆稳定性是设计中考虑的一个重要问题。采用弹塑性有限元法,求解大圆筒结构在指定波浪条件下的荷载-位移关系曲线;通过荷载-位移关系的上限,确定结构的极限承载力;定义极限承载力与设计荷载的比值为结构的倾覆稳定安全系数,从而判断结构的倾覆稳定安全裕度。该方法避免了现行极限平衡分析方法确定土压力和转动中心的困难,可以考虑土与结构的相互作用和复杂的边界条件。通过对某工程实例的分析,初步验证了该方法的可行性。     

Experimental constraints on major and trace element partitioning during partial melting of eclogite

Isobaric partial melting experiments were performed on an Fe-free synthetic composition to simulate partial melting of subducted oceanic crust. Nominally anhydrous experiments at 3.0 GPa yielded melts in equilibrium with garnet (13 to 16 mol.% grossular) and aluminous clinopyroxene (14 to 16 wt.% Al₂O₃). Melt compositions show decreasing Si and alkalis and increasing Ca, Mg, and Ti contents with increasing temperatures. Experiments at 1200 and 1300°C were rutile saturated, whereas experiments at 1400°C contained no residual rutile. We argue that during the initial stages of subduction, accessory rutile is likely to be stable in subsolidus eclogites of average midocean ridge basalt composition and that only large degrees of partial melting will eradicate rutile from an eclogitic source. At 3 GPa, any eclogites with a bulk TiO₂ content of ≥1.5 wt.% rutile will produce rutile-saturated partial melts, except at very high degrees of melting. At higher pressures, all bulk Ti may dissolve in clinopyroxene and garnet, leaving no accessory rutile.Trace element partition coefficients for 24 trace elements between clinopyroxene, garnet, and melt were determined by secondary-ion mass spectrometry analysis of experimental run products at 1400°C and 3 GPa. Partition coefficients for the rare earth elements agree well with previous studies and have been evaluated using the lattice strain model. Partitioning data for high-field strength elements indicate complementary D_Zr/D_Hf for clinopyroxene and garnet. Partial melting of an eclogitic component of different modal compositions may therefore explain both subchondritic and superchondritic Zr/Hf ratios. Superchondritic Zr/Hf has recently been observed in some ocean island basalts (OIB), and this may be taken as further evidence for components of recycled oceanic crust in OIB. The data also indicate slight Nb/Ta fractionation during partial melting of bimineralic eclogite, which is not, however, sufficient to explain some recently observed Nb/Ta fractionation in island arc rocks. Accessory rutile, however, can explain such fractionation.     

Evolution of major mineral compositions and trace element abundances during fractional crystallization of a model lunar composition

The evolution of major mineral compositions and trace element abundances during fractional crystallization of a model lunar magma ocean have been calculated. A lunar bulk composition consistent with petrological constraints has been selected. Major mineral compositions have been calculated using published studies of olivine-melt, plagioclase-melt, and pyroxene-olivine equilibria. Trace element abundances have been calculated using experimentally-determined partition coefficients where possible. In the absence of experimental determinations, published partition coefficients obtained by analyzing phase separates from porphyritic volcanic rocks have been used. Trace elements studied are La, Sm, Eu, Lu, Rb, Sr( Eu²⁺), Ni, Co, and Cr.The first mineral to crystallize is olivine, which varies in composition from Fo₉₈ at the liquidus to Fo₉₅ at 50% solidification. Orthopyroxene crystallizes from 50 to 60% solidification with a restricted composition range of En₉₅-En₉₃. Plagioclase and Ca-rich clinopyroxene (X_Wo arbitrarily set equal to 0.5) co-crystallize during the final 40% solidification. Plagioclase changes in composition from An₉₇ to approximately An₉₃, while clinopyroxene evolves from En₄₆ to approximately En₄₀. The concomitant evolution of major element abundances in the melt is also discussed.The concentration of Ni in the melt decreases rapidly because solid-melt partition coefficients are significantly greater than unity at all stages of crystallization. The concentration of Cr in the melt increases slowly during olivine crystallization, then drops precipitously during the crystallization of orthopyroxene and clinopyroxene. The concentration of Co in the melt decreases slowly during olivine and orthopyroxene crystallization, after which it returns slowly to its initial concentration. Rubidium and Sr are not fractionated relative to one another until the onset of plagioclase crystallization. Ratios of Rb/Sr, normalized to their initial concentrations in the magma, do not rise above 10 until 95% of the magma has solidified. The ratios of Eu/Sm and La/Lu, normalized to their initial concentrations in the magma, remain essentially unfractionated until the onset of crystallization of clinopyroxene plus plagioclase, at which point the normalized La/Lu ratio increases to approximately 1.3 at 100% solidification and the normalized Eu/Sm ratio decreases to approximately 0.2 at 100% solidification.The model calculations are used to place approximate constraints on the bulk composition of the primitive Moon. Consideration of the effect on plagioclase composition of the activities of NaO_0.5 and SiO₂ in the melt suggests that the primitive Moon contained less than 0.4 wt % NaO_0.5 and approximately 42–43 wt % SiO₂. Concentrations of the REE in model lunar anorthosites are consistent with the returned samples. Concentrations of the REE in several model ‘highland basalts’ (considered to be representative of the average lunar terrae) are too low when compared with returned samples. Several possible explanations of this discrepancy are considered. The possible role of spinel in a twostage geochemical evolution of mare basalt liquids is discussed.     

Crystallization of titaniferous chromite,magnesian ilmenite and armalcolite in tholeiitic suites in the Karoo Igneous Province

Titaniferous chromite (up to 8 wt% TiO₂) and magnesian ilmenite (up to 10 wt% MgO) coexist at the base of the differentiated tholeiitic Mount Ayliff Intrusion in the Karoo Province of southern Africa, suggesting that the original magma was TiO₂-rich. Picritic lavas with 3% TiO₂ from the Lebombo monocline of the Karoo Province also contain microphenocrysts of magnesian ilmenite (up to 6 wt% mgO) and armalcolite (up to 7 wt% MgO). These oxide mineral associations and compositions are atypical of tholeiitic magmas, in which chromite usually has less than 1 wt% TiO₂, ilmenite less than 3 wt% MgO and armalcolite is rarely a primary mineral. Experiments have been conducted at one atmosphere pressure on a range of compositions to determine the effect of TiO₂ on the crystallization and composition of chromite, ilmenite and armalcolite. The results indicate that increasing the TiO₂ content of picritic magmas increases the TiO₂ content of the spinel, mainly at the expense of Al₂O₃, whereas Cr₂O₃ is not affected. Spinel compositions in the Mount Ayliff Intrusion (with over 45 wt% Cr₂O₃, less than 10 wt% Al₂O₃ and 8 wt% TiO₂) were duplicated in experiments on a picrite at temperatures of about 1,200°C at the Ni/NiO buffer. Increasing fO₂ from fayalite-magnetite-quartz to Ni/NiO buffer is shown to increase the crystallization temperature of armalcolite and to decrease that of ilmenite. The total FeO content of the liquid has little influence on the crystallization temperature of these phases. The TiO₂ content of the liquid, when either ilmenite or armalcolite crystallizes, varies inversely with SiO₂ content. The MgO content of the liquid at which ilmenite or armalcolite crystallizes depends upon the TiO₂ content of the starting composition, with naturally occurring and experimetally determined saturation being demonstrated for liquids with 5 wt% MgO and 5.5 wt% TiO₂. The partition coefficent for MgO between armalcolite or ilmenite and liquid is about 1.5. Observed magnesian armalcolite and ilmenite compositions in picrite lavas (both minerals) and in the Mount Ayliff Intrusion (ilmenite only) are consistent with crystallization from a TiO₂-rich magma with approximately 5 wt% MgO. The Fe ₂ ³⁺ TiO₅ component of armalcolite in the picrite lavas matches those formed experimentally at temperatures of 1,150–1,110°C and fO₂ of the Ni/NiO to Ni/NiO+1 log unit. Similarities also exist between the compositions of chromite, ilmenite and armalcolite and liquid fraction-ation trends of some Hawaiian high-TiO₂ lavas and the experimental studies presented here.     

The partitioning of Fe and Mg between olivine and carbonate and the stability of carbonate under mantle conditions

We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K _d (X _Fe ^carb X _Mg ^ol /X _Fe ^ol X _Mg ^carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W _FeMg ^ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO₃ a W _FeMg ^carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K _d substantially enabling us to calculate W _CaMg ^carb -W _CaFe ^carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO₂(CMS)–CO₂ system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO₂. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.     

The major element composition of the upper mantle estimated from the composition of lherzolites

The compilation of analyses of continental and oceanic spinel Iherzolites show that these two types of Iherzolites have very similar compositions. Their composition range differ from that of African garnet Iherzolites, and the data suggest that the mantle beneath Africa has an anomalous composition. If the composition of the upper mantle may be estimated from that of Iherzolites, the compositions of spinel Iherzolite should form the basis for this estimate. It is suggested that the compositions of spinel Iherzolite represent both undepleted and depleted compositions, and a representative composition for the primitive mantle is proposed on this basis.     

Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ−2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750–1500 for Cu; 600–1200 for Ni; 35–42 for Co; 35–53 for Pb; and 1–2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380–500 for Cu; 520–750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3–6 for Pb; 0.1–2 for As; 1–2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu–Au deposits and magmatic sulfide deposits.I show that the metasomatized arc mantle may no longer contain sulfide after >10–14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions.Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO₂ > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10–14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and/or Au-rich magmas, but they do have equivalent potential as normal arc magmas in forming magmatic-hydrothermal Cu–Au deposits in terms of their Cu–Au contents. (3) It is not clear whether partial melting of subducting metabasalts generates Cu-rich adakitic magmas, however adakitic magmas may extract Cu and Au via interaction with mantle peridotite. Furthermore, partial melting of sulfide-bearing cumulates in the deep oceanic crust may be able to generate Cu- and Au-rich magmas. (4) The stabilization of MSS during partial melting may explain the genetic link between Au-Cu mineralization and the metasomatized lithospheric mantle.The chalcophile element tonnage, ratio, and distribution in magmatic sulfide deposits depend on a series of factors. This study reveals that oxygen fugacity also plays an important role in controlling Cu and Ni tonnage and Cu/Ni ratio in magmatic sulfide deposits. Cobalt, Zn, As, Sn, Sb, Mo, Ag, Pb, and Bi concentrations and their ratios in sulfide, due to their different partitioning behavior between sulfide liquid and MSS, can be useful indices for the distribution of platinum-group elements and Au in magmatic sulfide deposits.     

热力学计算模拟对初始月幔结构的约束SCIEI北大核心CSCD

月球岩浆洋结晶形成的初始月球内部结构是其后续演化过程的开端,其结晶过程受月球岩浆洋的初始深度和物质组成这两个参数的制约。由于缺少直接来自月球深部的岩石样品,目前关于月球岩浆洋演化过程的探讨主要依赖实验和计算模拟手段。岩浆洋模型中形成的月壳厚度是否与探测结果一致是月球岩浆洋演化模型合理性的重要约束。最新的GRAIL(Gravity Recovery and Interior Laboratory)探测数据推算月壳厚度为34~43km,低于阿波罗时期认为的约70km,这对已有的月球岩浆洋演化模型提出了挑战。本文采用并修正FXMOTR程序包,针对月球岩浆洋在不同的初始深度和物质组成情况下的结晶过程,进行了一系列热力学计算模拟。通过量化月球岩浆洋的初始深度和物质组成对月壳厚度的影响,结合关于月球内部微量元素分配的研究结果,对比了月球岩浆洋结晶后期的残余熔体与原始克里普组分(urKREEP)的成分。本文的模拟结果显示,一个全月幔熔融且初始成分为月球初始上月幔组成(LPUM)的岩浆洋将在其深部结晶2.5%石榴子石,形成的月壳厚度符合GRAIL的约束,并且结晶出了合适的urKREEP成分。在此模型的基础上获取了月球初始的内部成分和密度结构,并对后期月幔翻转(Overturn)的程度进行了探讨。     

Trace element partitioning between silicate minerals and carbonatite at 25 kbar and application to mantle metasomatism

Summary Experiments at 25 kbar and 1000°C, on a model trace element-enriched carbonatite-eridotite mix, produced augite + pargasite ± garnet ± dolomite coexisting with a carbonatite melt. Proton microprobe analysis of the phases showed that key trace elements (Rb, Ba, Sr, Nb, Ta, Zr, Y and REE) all partitioned strongly into the melt (with the exception of Y, Ho and Lu in garnet), verifying that carbonatite is potentially a highly effective metasomatizing agent. The data also indicate that carbonatitic metasomatism will impart higher Ba/Rb, Ba/Nb, Nb/Ta, Sr/Ta, La/Ta, and lower Zr/Y, with little change to Sr/Nb, in affected mantle.

---

Spurenelementverteilung zwischen Silikatmineralen und Karbonatit bei 25 kbar: Anwendung für die Mantel-Metasomatose

Zusammenfassung Experimente mit einer Modell-mischung von Karbonatit-Peridotit, angereichert mit Spurenelementen, produzierten bei 25 kbar und 1000°C Augit + Pargasit ± Granat ±Dolomit coexistierend mit einer Karbonatitschmelze. Protonmikrosonden-Analyse der Phasen zeigte, dass alle Schlüsselspurenelemente (Rb, Ba, Sr, Nb, Ta, Zr, Y and REE) stark in der Schmelze angereichert werden (mit der Ausnahme von Y, Ho und Lu in Granat), was beweist, dass Karbonatit potentiell ein sehr effektives Agens für Metasomatose ist. Die Daten zeigen weiterhin, dass karbonatitische Metasomatose in betroffenen Mantel höhere Ba/Rb, Ba/Nb, Nb/Ta, Sr/Ta, La/Ta und niedrigere Zr/Y produziert, mit geringen Äderungen für Sr/Nb.

---

---

With 1 Figure     

The effect of oxygen fugacity on the partitioning of Re between crystals and silicate melt during mantle melting

Interpretation of Re-Os isotopic systematics applied to mantle and mantle-derived rocks is currently hindered by the poorly understood behaviour of Re and Os during partial melting. Of particular interest is the incompatibility of Re and how it partitions between melt and the different mantle phases. Here, we study the partitioning behaviour of Re between the common upper mantle minerals (garnet, spinel, clinopyroxene, orthopyroxene, and olivine) and silicate melt under temperature (1275-1450 °C) and pressure (1.5-3.2 GPa) conditions relevant for basaltic magma genesis, over a range of oxygen fugacity (?O₂) large enough (QFM+5.6 to QFM−2.9) to demonstrate the effects of changing the oxidation state of Re from 4+ to 6+. Rhenium crystal/silicate-melt partition coefficients vary by 4-5 orders of magnitude, from moderately compatible to highly incompatible, for pyroxenes, garnet, and spinel as the oxidation state of Re changes from 4+ to 6+, but Re in either oxidation state is incompatible in olivine. Because the changeover from the one Re oxidation state to the other occurs over the range of ?O₂s pertinent to partial melting in the Earth’s mantle, bulk Re crystal/silicate-melt partition coefficients during mantle melting are also expected to vary significantly according to the oxidation state of the system. For instance, assuming QFM−0.7 and QFM+1.6 as average ?O₂ for mid-ocean ridge (MORBs) and island arc (IABs) basalts, respectively, a difference of at least one order of magnitude for bulk Re partition coefficients is expected (excluding any influence from a sulphide phase). Hence, Re is probably much more incompatible during the genesis of IABs compared to MORBs. Our results also demonstrate that Re⁴⁺ has a partitioning behaviour similar to Ti⁴⁺ rather than Yb, and is accordingly not a sensitive indicator of garnet in the source. The lower concentrations of Re observed in ocean island basalts (OIBs) compared to MORBs are therefore not a result of being generated deeper in the mantle where garnet is stable, leaving the hypothesis of late-stage loss of Re from OIB lavas by degassing as the most plausible explanation.     

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.     

Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene,olivine, armalcolite,ilmenite, and silicate glass during mare basalt petrogenesis

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO₂) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (>?100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti³⁺ under fO₂ conditions relevant to lunar magmatism (IW ??1.5 to ??1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% ^[IV]Ti⁴⁺ in the pyroxene. In addition, our results can help to better constrain the Ti³⁺/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.     

The significance of groundmass ilmenite and megacryst ilmenite in kimberlites

Criteria are suggested for distinguishing xenocrystic ilmenites from those indigenous to the host kimberlite. For instance, in contrast to groundmass grains, ilmenite xenocrysts usually are larger, have reaction rims of leucoxene and perovskite, exhibit strong magnesium enrichment outward, and sometimes have exsolution lamellae and deformation features. Most of the abundant ilmenite macrocrysts found in kimberlite appear to have been phenocrysts in a crystal mush unrelated to kimberlite. On the other hand, kimberlitic groundmass ilmenite is rare, but consistently more magnesian than the cores of macrocrysts. Strong Mg-enrichment patterns evident in the ilmenite macrocrysts probably developed during their attempt to equilibrate with the more magnesian, fractionating kimberlitic liquid. The hypothesis of extensive reaction of ilmenite with kimberlite melt/ fluid has implications with regard to the following: (1) the degree of differentiation of kimberlite melts; (2) the genesis of mantle megacrysts; (3) the reactivity of kimberlite; and (4) the usefulness of groundmass ilmenite as a petrogenetic indicator.     

The influence of carbon on trace element partitioning behavior

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.     

Experimental comparison of trace element partitioning between clinopyroxene and melt in carbonate and silicate systems, and implications for mantle metasomatism

Experiments in the systems diopside-albite (Di-Ab) and diopside-albite-dolomite (Di-Ab-Dmt), doped with a wide range of trace elements, have been used to characterise the difference between clinopyroxene-silicate melt and clinopyroxene-carbonate melt partitioning. Experiments in Di-Ab-Dmt yielded clinopyroxene and olivine in equilibrium with CO₂-saturated dolomitic carbonate melt at 3 GPa, 1375 °C. The experiments in Di-Ab were designed to bracket those conditions (3 GPa, 1640 °C and 0.8 GPa, 1375 °C), and so minimise the contribution of differential temperature and pressure to partitioning. Partition coefficients, determined by SIMS analysis of run products, differ markedly for some elements between Di-Ab and Di-Ab-Dmt systems. Notably, in the carbonate system clinopyroxene-melt partition coefficients for Si, Al, Ga, heavy REE, Ti and Zr are higher by factors of 5 to 200 than in the silicate system. Conversely, partition coefficients for Nb, light REE, alkali metals and alkaline earths show much less fractionation (<3). The observed differences compare quantitatively with experimental data on partitioning between immiscible carbonate and silicate melts, indicating that changes in melt chemistry provide the dominant control on variation in partition coefficients in this case. The importance of melt chemistry in controlling several aspects of element partitioning is discussed in light of the energetics of the partitioning process. The compositions of clinopyroxene and carbonate melt in our experiments closely match those of near-solidus melts and crystals in CMAS-CO₂ at 3 GPa, suggesting that our partition coefficients have direct relevance to melting of carbonated mantle lherzolite. Melts so produced will be characterised by elevated incompatible trace element concentrations, due to the low degrees of melting involved, but marked depletions of Ti and Zr, and fractionated REE patterns. These are common features of natural carbonatites. The different behaviour of trace elements in carbonate and silicate systems will lead to contrasted styles of trace element metasomatism in the mantle. Received: 15 July 1999 / Accepted: 18 February 2000     

Heat-producing elements in the lunar mantle: Insights from ion microprobe analyses of lunar pyroclastic glasses

We provide new estimates for the abundance of heat-producing elements in the lunar mantle by using SIMS techniques to measure the concentrations of thorium and samarium in lunar pyroclastic glasses. Lunar pyroclastic glasses are utilized in this study because they represent quenched products of near-primary melts from the lunar mantle and as such, they provide compositional information about the mantle itself. Thorium and samarium were measured because: (1) Th is not significantly fractionated from Sm during partial melting of the pyroclastic glass source regions, which are dominated by olivine and pyroxene. Therefore, the Th/Sm ratios that we measure in the pyroclastic glasses reflect the Th/Sm ratio of the pyroclastic glass source regions. (2) Strong correlations between Th, U, and K on the Moon allow us to use measured Th concentrations to estimate the concentrations of U and K in the pyroclastic glasses. (3) Th, Sm, U, and K are radioactive elements and as such, their concentrations can be used to investigate heat production in the lunar mantle.The results from this study show that the lunar mantle is heterogeneous with respect to heat-producing elements and that there is evidence for mixing of a KREEP component into the source regions of some of the pyroclastic glasses. Because the source regions for many of the glasses are deep (?400 km), we propose that a KREEP component was transported to the deep lunar mantle. KREEP enriched sources produce 138% more heat than sources that do not contain KREEP and therefore, could have provided a source of heat for extended periods of nearside basaltic magmatism. Data from this study, in conjunction with models for the fractional crystallization of a lunar magma ocean, are used to show that the average lunar mantle contains 0.15 ppm Th, 0.54 ppm Sm, 0.039 ppm U, and 212 ppm K. This is a greater enrichment in radiogenic elements than some earlier estimates, suggesting a more prolonged impact of radiogenic heat on nearside basaltic volcanism.     

Experimental determination of rare earth element partitioning between hydrous silicate melt,amphibole and garnet peridotite minerals at upper mantle pressures and temperatures

Partition coefficients of Ce, Sm and Tm involving garnet peridotite minerals, amphibole and hydrous silicate melt have been determined experimentally in the temperature and pressure ranges 950–1075°C and 10–25 kbar.Only several parts per million to several tens of parts per million of rare earth element (REE) can dissolve in the minerals before the crystal-liquid partition coefficients begin to vary as a function of REE content. The concentration ranges of constant partition coefficient increase with increasing temperature and are also positively correlated with the magnitude of the crystal-liquid partition coefficients. The upper concentration limits of constant partition coefficient and the value of the crystal-liquid partition coefficient for REE decrease in the order garnet > clinopyroxene > amphibole > orthopyroxene > olivine.Partition coefficients may vary by at least an order of magnitude as a function of bulk composition of the liquid phase (e.g. changing from basaltic to andesitic). The approximate ranges of the values of the partition coefficients as a function of bulk liquid composition are as follows:

$\text{Ce}\text{Sm}\text{Tm}\text{K}{}^{\mathrm{<mtext>ga-liq</mtext>}}\text{0.01–0.1}\text{0.3–3.4}\text{1–10}\text{K}{}^{\mathrm{<mtext>cpx-liq</mtext>}}\text{0.05–0.4}\text{0.09–0.7}\text{0.04–0.4}\text{K}{}^{\mathrm{<mtext>amph-liq</mtext>}}\text{0.04–0.4}\text{0.08–0.8}\text{0.07–0.7}\text{K}{}^{\mathrm{<mtext>opx-liq</mtext>}}\text{0.04–0.1}\text{0.05–0.1}\text{0.08–0.1}\text{K}{}^{\mathrm{<mtext>ol-liq</mtext>}}\text{0.01–0.02}\text{0.01–0.02}\text{0.01–0.02}$

where the values increase with increasing acidity of the melt.     

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH.