Trace element partitioning between apatite and silicate melts

We present new experimental apatite/melt trace element partition coefficients for a large number of trace elements (Cs, Rb, Ba, La, Ce, Pr, Sm, Gd, Lu, Y, Sr, Zr, Hf, Nb, Ta, U, Pb, and Th). The experiments were conducted at pressures of 1.0 GPa and temperatures of 1250 °C. The rare earth elements (La, Ce, Pr, Sm, Gd, and Lu), Y, and Sr are compatible in apatite, whereas the larger lithophile elements (Cs, Rb, and Ba) are strongly incompatible. Other trace elements such as U, Th, and Pb have partition coefficients close to unity. In all experiments we found D_Hf > D_Zr, D_Ta ≈ D_Nb, and D_Ba > D_Rb > D_Cs. The experiments reveal a strong influence of melt composition on REE partition coefficients. With increasing polymerisation of the melt, apatite/melt partition coefficients for the rare earth elements increase for about an order of magnitude. We also present some results in fluorine-rich and water-rich systems, respectively, but no significant influence of either H₂O or F on the partitioning was found. Furthermore, we also present experimentally determined partition coefficients in close-to natural compositions which should be directly applicable to magmatic processes.     

Distribution of groups I and II elements between liquidus phases of fluorine-saturated Si-Al-Na-K-Li-H-O system

Experimental data allow modeling the behavior of the named elements during formation of fluorine- saturated leucocratic rocks of silicic and alkaline compositions. The distribution of alkaline and alkaliearth elements is discussed at equilibrium between the silica-alumina melt with fluoride phases (crystalline and liquid) and with feldspar. Cryolite crystals form during saturation of silica-alumina melt of normal alkalinity with fluorine. Continuous solid solution of sodium-potassium cryolite is stable at 800°C. The equilibrium between melt and crystals continues up to the maximum molar fraction of 0.1 lithium end member in cryolite, at which two fluoride phases (crystalline and liquid) coexist with the silica-alumina melt of fixed composition. Separation of salt melts during late differentiation stages of granite and alkaline rocks is a regular process continuing the natural evolution of ore-magmatic systems. At equilibrium of two liquid phases, the silica phase is relatively enriched in potassium, and the fluoride phase is substantially enriched in sodium. This detected effect is the only currently possible mechanism for the occurrence of the potassium differentiation trends of granite melts. All effects related to crystallization cause enrichment in sodium. In other cases (with Ca, Sr, Mg, Rb, and Cs), separation of the second liquid phase acts in the same direction and enhances the action of crystallization. Comparison between partition coefficients allows derivation of the following affinity rows of alkaline elements for fluoride melt: Li > Na > K > Rb≈Cs and Mg > Ca > Sr > Ba. Hence, the known rule for joining strong bases with strong acids and weak bases with weak acids is fulfilled.     

Composition of Li-F granite melt and its evolution during the formation of the ore-bearing Orlovka massif in Eastern Transbaikalia

By the example of the Orlovka massif of Li-F granites in Eastern Transbaikalia, the major- and trace-element (Li, Be, B, Ta, Nb, W, REE, Y, Zr, and Hf) compositions of the parental melt and the character of its variations during the formation of the differentiated rock series were quantitatively estimated for the first time on the basis of electron and ion microprobe analysis and Raman spectroscopy of rehomogenized glasses of melt inclusions in quartz. It was shown that the composition of the Orlovka melt corresponded to a strongly evolved alumina-saturated granitoid magma (A/CNK = 1.12–1.55) rich in normative albite, poor in normative quartz, and similar to ongonite melts. This magma was strongly enriched in water (up to 9.9 ± 1.1 wt %) and fluorine (up to 2.8 wt %). Most importantly, this massif provided the first evidence for high B₂O₃ contents in melts (up to 2.09 wt %). The highest contents of trace elements were observed in the melt from pegmatoid bodies in the amazonite granites of the border zone: up to 5077 ppm Li, 6397 ppm Rb, 313 ppm Cs, 62 ppm Ta, 116 ppm Nb, and 62 ppm W. Compared with the daughter rock, the Orlovka melt was depleted at all stages of formation in SiO₂ (by up to 6 wt %), Na₂O (by up to 2.5 wt %), and, to a smaller extent, in Ti, Fe, Mg, Sr, and Ba, but was enriched in Mn, Rb, F, B, and H₂O.     

Magmatic Evolution of Changbaishan Tianchi Volcano,China–North Korea: Evidence from Mineral-Hosted Melt and Fluid Inclusions

Data on mineral-hosted melt, fluid, and crystalline inclusions were used to study the composition and evolution of melts that produced rocks of Changbaishan Tianchi volcano, China–North Korea, and estimate their crystallization parameters. The melts crystallized within broad ranges of temperature (1220–700°C) and pressure (3100–1000 bar), at a drastic change in the redox potential: Δ log \(f_{O_2}\) from NNO + 0.92 to +1.42 for the basalt melts, NNO –1.61 to –2.09 for the trachybasaltic andesite melts, NNO –2.63 to –1.89 for the comendite melts, and NNO –1.55 to –3.15 for the pantellerite melts. The paper reports estimates of the compositions of melts that produced the continuous rock series from trachybasalt to comendite and pantellerite. In terms of trace-element concentrations, all of the mafic melts are comparable with OIB magmas. The silicic melts are strongly enriched in trace elements and REE. The most strongly enriched melts contain concentrations of certain elements almost as high as in ores of these elements. The paper reports data on H2O concentrations in melts of different composition. It is demonstrated that the variations in the H₂O concentrations were controlled by magma degassing. Data are reported on the Sr and Nd composition of the rocks. The deviations in the Sr isotopic composition are proportional to the ⁸⁷Sr/⁸⁶Sr ratio and could be produced in a melt with a high enough ⁸⁷Sr/⁸⁶Sr ratio during a geologically fairly brief time period. The evolution of melts that produced rocks of the volcano was controlled by crystallization differentiation of the parental basalt magmas at insignificant involvement of melt mixing and liquid immiscibility of silicate and sulfide melts. The alkaline salic rocks were generated in shallow-sitting (13–3.5 km) magmatic chambers in which the melts underwent profound differentiation that gave rise to pantellerites and comendites strongly enriched in trace elements (Th, Nb, Ta, Zr, and REE). Data on the composition of the magmas and parameters of their derivation are used to develop a generalized petrologic–geodynamic model for the origin of Changbaishan Tianchi volcano.     

矿物—熔体间元素分配系数资料及主要变化规律

本文提供了不同成分的8大类主岩(偏铝质(超)基性岩、过碱性(超)基性岩、偏铝质中性岩、过碱性中性岩、偏铝质酸性岩、过碱性酸性岩、过铝质酸性岩、超酸性岩)中28个矿物(橄榄石、单斜辉石、斜方辉石、角闪石、黑云母、金云母、斜长石、钾长石、石英、磁铁矿、钛铁矿、石榴石、锆石、磷灰石、绿帘石、黄玉、榍石、堇青石、蓝方石、石榴石、霞石、白磷钙矿、镁铁钛矿、板钛矿、黄长石、钙钛矿、尖晶石、金红石)的69个化学元素(Li、Rb、Cs、K、Na、Ca、Sr、Ba、Mn、Fe、Mg、Cu、Pb、Zn、Co、Ni、Be、La、Ce、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y、Sc、Cr、In、Ga、Al、B、Cd、Sb、Bi、U、Th、Zr、Hf、Si、Ti、Ge、Sn、Mo、Nb、Ta、W、V、P、F、Cl、S、N、O、C、As、Pu、Re、Os、He、Ne、Ar、Xe、Kr)和1个化学一价原子团OH的分配系数。综合分析对比表明,矿物、熔体的成分和结构是分配系数的最重要的控制因素。对前人未讨论过的矿物结构和熔体铝过饱和度这两个因素应引起重视。最后,本文分析了矿物-熔体间元素分配系数的研究现状、存在问题,指出了这一领域今后的研究方向。     

Zonation des éléments en traces au cours de la croissance des cristaux dans les bains silicatés: l'exemple de Rb,Cs, Sr et Ba dans le système Qz-Ab-Or-H2O

An indirect method was used to study Na, K, Rb, Cs, Sr and Ba partition coefficients between crystals and silicate melt. Equilibria between a hydrothermal solution and the melt at 800°C and 2 kb and between a hydrothermal solution and crystals at 750°C and 2 kb were separately achieved.For major element partitioning (Na and K), the results obtained here are in good agreement with those of Tuttle and Bowen (1958) which allow us to follow crystal evolution during a fractional crystallization process where the growth of zoned crystals takes place.For minor elements Rb, Cs, Sr, Ba, melt/aqueous solution partition coefficients depend on Na/K as well as the silica content of the melt. These effects are rather small for Rb and Cs, but are much more important for the alkaline earths. The feldspar/aqueous solution partition coefficients also depend on Na/K.The variations of the partition coefficients feldspar/melt are complex in the part of the Qz-Ab-Or diagram located below the cotectic line.During fractional crystallization following the Rayleigh law (assuming that there are no kinetic phenomena) Sr (D > 10) is almost totally removed from the melt in the early stages whereas Cs (D < 0.1) remains in the melt during the whole process. Rb and Ba have partition coefficients closer to unity. The variation of these coefficients, due to changes in bulk composition of liquid and crystals during fractional crystallization, can lead to complex zoning with possible concentration maxima at some stages. Similar phenomena can be expected in non-ideal natural solid solutions, even if no discontinuities can be detected in the physicochemical evolution of the parent magma.     

Silicate perovskite-melt partitioning of trace elements and geochemical signature of a deep perovskitic reservoir

We have determined the partitioning of a wide range of trace elements between silicate melts and CaSiO₃ and MgSiO₃ perovskites using both laser ablation-ICPMS and ion microprobe techniques. Our results show that, with the exception of Sc, Zr, and Hf, all trace elements we considered are incompatible in MgSiO₃ perovskite, from highly incompatible for U, Th, Ba, La, Sr and monovalent elements to slightly incompatible for heavy rare earth elements. MgSiO₃ perovskite-melt partition coefficients increase slightly with Al content in the perovskite. These observations contrast strongly with partitioning between CaSiO₃ perovskite and silicate melts. In the latter case, all rare earth elements are clearly compatible as are U and Th. Our data also suggest that, contrary to pressure and temperature, melt composition can significantly affect CaSiO₃ perovskite-melt partitioning; partition coefficients for rare earth elements and U and Th increase with decreasing CaO melt content. The presence of ∼0.4 wt% water in melt makes little difference, however. Partitioning of trace elements into the large site of both MgSiO₃ and CaSiO₃ perovskites follows the near-parabolic dependence on ionic radius predicted from the lattice strain model. The peaks of the parabolae are much higher for the CaSiO₃ phase, perhaps suggesting that the mechanisms of charge compensation for heterovalent substitution are different in the two cases. Our partitioning data have been used to assess the potential effect of perovskite fractionation into the lower mantle during early Earth history. Crystallisation of less than 8% of a mixture of CaSiO₃ and MgSiO₃ perovskites could have led to a ‘layer’ enriched in U and Th without disturbing the chondritic pattern of refractory lithophile elements in the primitive upper mantle. The resultant reservoir could have high Sm/Nd, U/Pb, Sr/Rb, Lu/Hf ratios similar to the HIMU component of ocean island basalts, but would not balance the observed depletion of the primitive upper mantle in Si and Nb.     

Effects of alteration on element distributions in archean tholeiites from the Barberton greenstone belt,South Africa

Major and trace element and modal analyses are presented for unaltered, epidotized, and carbonated tholeiite flows from the Barberton greenstone belt. Au, As, Sb, Sr, Fe⁺³, Ca, Br, Ga, and U are enriched and H₂O, Na, Mg, Fe⁺², K, Rb, Ba, Si, Ti, P, Ni, Cs, Zn, Nb, Cu, Zr, and Co are depleted during epidotization. CO₂, H₂O, Fe⁺², Ti, Zn, Y, Nb, Ga, Ta, and light REE are enriched and Na, Sr, Cr, Ba, Fe⁺³, Ca, Cs, Sb, Au, Mn, and U are depleted during carbonization-chloritization. The elements least affected by epidotization are Hf, Ta, Sc, Cr, Th, and REE; those least affected by carbonization-chloritization are Hf, Ni, Co, Zr, Th, and heavy REE. Both alteration processes can significantly change major element concentrations (and ratios) and hence caution should be used in distinguishing tholeiites from komatiites based on major elements alone. The amount of variation of many of the least mobile trace elements in the altered flows is approximately the same as allowed by magma model calculations. Hence, up to about 10% carbonization and 60% epidotization of tholeiite do not appreciably affect the interpretation of trace-element models for magma generation.     

Melting of hydrous pyroxenites with alkali amphiboles in the continental mantle: 2. Trace element compositions of melts and minerals

The trace element compositions of melts and minerals from high-pressure experiments on hydrous pyroxenites containing K-richterite are presented. The experiments used mixtures of a third each of the natural minerals clinopyroxene, phlogopite and K-richterite, some with the addition of 5% of an accessory phase ilmenite, rutile or apatite. Although the major element compositions of melts resemble natural lamproites, the trace element contents of most trace elements from the three-mineral mixture are much lower than in lamproites. Apatite is required in the source to provide high abundances of the rare earth elements, and either rutile and/or ilmenite is required to provide the high field strength elements Ti, Nb, Ta, Zr and Hf. Phlogopite controls the high levels of Rb, Cs and Ba.Since abundances of trace elements in the various starting mixtures vary strongly because of the use of natural minerals, we calculated mineral/melt partition coefficients (D_Min/melt) using mineral modes and melting reactions and present trace element patterns for different degrees of partial melting of hydrous pyroxenites. Rb, Cs and Ba are compatible in phlogopite and the partition coefficient ratio phlogopite/K-richterite is high for Ba (1 3 6) and Rb (12). All melts have low contents of most of the first row transition elements, particularly Ni and Cu ((0.1–0.01) × primitive mantle). Nickel has high D_Min/melt for all the major minerals (12 for K-richterite, 9.2 for phlogopite and 5.6 for Cpx) and so behaves at least as compatibly as in melting of peridotites. Fluorine/chlorine ratios in melts are high and D_Min/melt for fluorine decreases in the order apatite (2.2) > phlogopite (1.5) > K-richterite (0.87). The requirement for apatite and at least one Ti-oxide in the source of natural lamproites holds for mica pyroxenites that lack K-richterite. The results are used to model isotopic ageing in hydrous pyroxenite source rocks: phlogopite controls Sr isotopes, so that lamproites with relatively low ⁸⁷Sr/⁸⁶Sr must come from phlogopite-poor source rocks, probably dominated by Cpx and K-richterite. At high pressures (>4 GPa), peritectic Cpx holds back Na, explaining the high K₂O/Na₂O of lamproites.     

Rare earth partitioning between immiscible carbonate and silicate liquids and CO2 vapor: Results and implications for the formation of light rare earth-enriched rocks

Melting relations at 5 and 20 kbar on the composition join sanidine-potassium carbonate are dominated by a two-liquid region that covers over 60% of the join at 1,300 ° C. At this temperature, the silicate melt contains approximately 19 wt% carbonate component at 5 kbar and 32 wt% carbonate component at 20 kbar. The conjugate carbonate melt contains less than 5 wt% silicate component, and it varies less as a function of temperature than does the silicate melt.Partition coefficients for Ce, Sm, and Tm between the immiscible carbonate and silicate melts at 1,200 ° and 1,300 ° C at 5 and 20 kbar are in favor of the carbonate melt by a factor of 2–3 for light REE and 5–8 for heavy REE. The effect of pressure on partitioning cannot be evaluated independently because of complementary changes in melt compositions.Minimum REE partition coefficients for CO₂ vapor/carbonate melt and CO₂ vapor/silicate melt can be calculated from the carbonate melt/silicate melt partition coefficients, the known proportions of melt, and maximum estimates of the proportion of CO₂ vapor. The vapor phase is enriched in light REE relative to both melts at 20 kbar and enriched in all REE, especially the light elements, at 5 kbar. The enrichment of REE in CO₂ vapor relative to both melts is 3–4 orders of magnitude in excess of that in water vapor (Mysen, 1979) at 5 kbar and is approximately the same as that in water vapor at 20 kbar.Mantle metasomatism by a CO₂-rich vapor enriched in light REE, occurring as a precursor to magma genesis, may explain the enhanced REE contents and light REE enrichment of carbonatites, alkali-rich silicate melts, and kimberlites. Light REE enrichment in fenites and the granular suite of nodules from kimberlites attests to the mobility of REE in CO₂-rich fluids under both mantle and crustal conditions.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Effect of melt composition on the partitioning of trace elements between titanite and silicate melt

Isobaric and isothermal experiments were performed to investigate the effect of melt composition on the partitioning of trace elements between titanite (CaTiSiO₅) and a range of different silicate melts. Titanite-melt partition coefficients for 18 trace elements were determined by secondary ion mass spectrometry (SIMS) analyses of experimental run products. The partition coefficients for the rare earth elements and for Th, Nb, and Ta reveal a strong influence of melt composition on partition coefficients, whereas partition coefficients for other studied monovalent, divalent and most quadrivalent (i.e., Zr, Hf) cations are not significantly affected by melt composition. The present data show that the influence of melt composition may not be neglected when modelling trace element partitioning.It is argued that it is mainly the change of coordination number and the regularity of the coordination space of trace elements in the melt structure that controls partition coefficients in our experiments. Furthermore, our data also show that the substitution mechanism by which trace elements are incorporated into titanite crystals may be of additional importance in this context.     

Element partitioning between immiscible borosilicate liquids: A high-temperature centrifuge study

The main objectives of this study were to investigate conditions for stable and metastable liquid immiscibility in dry borosilicate synthetic systems and to evaluate effects of temperature and bulk melt composition on two-liquid element partitioning and boron speciation. To distinguish between the stable immiscibility and quench heterogeneity, we used high-temperature centrifuge phase separation. For the case of stable liquid immiscibility, silica-rich (LS) and borate-rich (LB) conjugate liquids formed two distinct layers separated by a sharp meniscus. The liquids were quenched into glasses, which were analysed by electron microprobe. Some of the glasses were also studied by Raman spectroscopy. We used several synthetic mixtures along the danburite-anorthite (CaB₂Si₂O₈-CaAl₂Si₂O₈) and danburite-reedmergnerite (CaB₂Si₂O₈-NaBSi₃O₈) joins. In addition, we studied four complex, six-component, Mg-bearing compositions with variable Na₂O and Al₂O₃ contents. The experiments show that the width of the LS-LB miscibility gap decreases more rapidly with the B-Al substitution (in the danburite-anorthite join) than with the Ca-Na substitution, implying that interactions between network-forming elements have a greater effect on borate-silicate unmixing than the nature of network-modifying cations. Ca and Mg partition strongly to the depolymerised borate-rich liquid with LB-LS partition coefficients of ∼40 and higher. On the other hand, two-liquid partition coefficients of Na and Al in most cases are close to 1 and show complex variations with temperature and bulk melt composition. Raman spectra of LB glasses quenched at different temperatures suggest that the proportion of trigonal boron in bulk boron content decreases with decreasing temperature. The change in boron speciation appears to affect Al and Na two-liquid partitioning in such a way that at low temperatures, the latter element becomes more compatible with LS.     

In Situ Multi-Element Analysis of the Mount Pinatubo Quartz-Hosted Melt Inclusions by NIR Femtosecond Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

Microscopic melt inclusions found in magmatic minerals are undoubtedly one of the most important sources of information on the chemical composition of melts. This paper reports on the successful application of near-infrared (NIR) femtosecond laser ablation (LA) - inductively coupled plasma-mass spectrometry to in situ determination of incompatible trace elements (Li, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Ta, Th, U) and ore metals (As, Mo, Pb) in individual melt inclusions hosted in quartz from the Mount Pinatubo dacites, Philippines. The determined elements cover a concentration range of five orders of magnitude. Femtosecond LA-ICP-MS analyses of twenty-eight individual melt inclusions demonstrate the efficiency of the microanalytical technique and suggests a spectacular homogeneity of the entrapped melt, at least with respect to the following incompatible trace elements: Rb, Sr, Nb, Cs, Ba, La, Ce, Pr, Nd, Pb, Th. The analytical precision (1s) for Na, Ca, Rb, Sr, Y, Nb, Ba and LREE ranged from 3 to 20%. Comparison of trace element concentrations in Mt. Pinatubo melt inclusions determined by femtosecond LA-ICP-MS with those of melt inclusions previously analysed by secondary ion mass spectrometry analysis (SIMS) and those of matrix glasses previously determined by nanosecond LA-ICP-MS showed an agreement typically within 30–40%. The homogeneity of trace element concentrations of the Mt. Pinatubo melt inclusions and the matrix glasses is consistent with the melt inclusion origin as homogeneous rhyolitic melt that was trapped in quartz phenocrysts at the final crystallisation stages of the host adakite (dacite) magma.     

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon

Partition coefficients (^zircon/meltD_M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D_REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D_REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D_REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques.D_REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce⁴⁺ in the melt results in elevated D_Ce compared to neighboring REE due to the similar valence and size of Ce⁴⁺ and Zr⁴⁺. Predicted ^zircon/meltD values for Ce⁴⁺ and Ce³⁺ indicate that the Ce⁴⁺/Ce³⁺ ratios of the melt ranged from about 10⁻³ to 10⁻². Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D_M < 1.0), and Ti, Y and Nb showing compatible behavior (D_M > 1.0).The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D_REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D_Yb from this study. Using D_Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.     

Trace element geochemistry of Amba Dongar carbonatite complex,India: Evidence for fractional crystallization and silicate-carbonate melt immiscibility

Carbonatites are believed to have crystallized either from mantle-derived primary carbonate magmas or from secondary melts derived from carbonated silicate magmas through liquid immiscibility or from residual melts of fractional crystallization of silicate magmas. Although the observed coexistence of carbonatites and alkaline silicate rocks in most complexes, their coeval emplacement in many, and overlapping initial⁸⁷Sr/⁸⁶Sr and¹⁴³Nd/¹⁴⁴Nd ratios are supportive of their cogenesis; there have been few efforts to devise a quantitative method to identify the magmatic processes. In the present study we have made an attempt to accomplish this by modeling the trace element contents of carbonatites and coeval alkaline silicate rocks of Amba Dongar complex, India. Trace element data suggest that the carbonatites and alkaline silicate rocks of this complex are products of fractional crystallization of two separate parental melts. Using the available silicate melt-carbonate melt partition coefficients for various trace elements, and the observed data from carbonatites, we have tried to simulate trace element distribution pattern for the parental silicate melt. The results of the modeling not only support the hypothesis of silicate-carbonate melt immiscibility for the evolution of Amba Dongar but also establish a procedure to test the above hypothesis in such complexes.     

Genesis of kalsilite melilitite at Cupaello,Central Italy: Evidence from melt inclusions

The paper presents data on primary carbonate–silicate melt inclusions hosted in diopside phenocrysts from kalsilite melilitite of Cupaello volcano in Central Italy. The melt inclusions are partly crystalline and contain kalsilite, phlogopite, pectolite, combeite, calcite, Ba–Sr carbonate, baryte, halite, apatite, residual glass, and a gas phase. Daughter pectolite and combeite identified in the inclusions are the first finds of these minerals in kamafugite rocks from central Italy. Our detailed data on the melt inclusions in minerals indicate that the diopside phenocrysts crystallized at 1170–1190°C from a homogeneous melilitite magma enriched in volatile components (CO₂, 0.5–0.6 wt % H₂O, and 0.1–0.2 wt % F). In the process of crystallization at the small variation in P-T parameters two-phase silicate-carbonate liquid immiscibility occurred at lower temperatures (below 1080–1150°C), when spatially separated melilitite silicate and Sr-Ba-rich alkalicarbonate melts already existed. The silicate–carbonate immiscibility was definitely responsible for the formation of the carbonatite tuff at the volcano. The melilitite melt was rich in incompatible elements, first of all, LILE and LREE. This specific enrichment of the melt in these elements and the previously established high isotopic ratios are common to all Italian kamafugites and seem to be related to the specific ITEM mantle source, which underwent metasomatism and enrichment in incompatible elements.     

The effect of sodium and titanium on crystal-melt partitioning of trace elements

Eclogite of recycled slab origin has often been invoked in the source region of mid-ocean ridge and ocean-island basalts. Melts of this eclogitic material are expected to be enriched in incompatible elements including major elements such as Na and Ti. In order to investigate the controls on trace element chemistry of a melt from such a recycled component we have performed trace element partitioning experiments in the simple systems CMAS (CaO-MgO-Al₂O₃-SiO₂), NCMAS (Na₂O-CMAS) and Ti-CMAS (TiO₂-CMAS) at 3 GPa and 1298-1500°C using analogue eclogitic compositions.We show that sodium has a profound effect on clinopyroxene-melt partition coefficients. NCMAS is characterized by elevated partition coefficients, relative to CMAS for all elements except Li. The increase is more pronounced for more highly charged cations, resulting in negative partitioning anomalies for Li, Sr, Ba and Pb. In contrast to sodium, titanium has very little effect on trace element partitioning for all elements except Nb and Ta, which are retained by the rutile that is saturated in this run.     

Major and trace element variation in ilmenite in the Skaergaard Intrusion: petrologic implications

Ilmenite separates from the floor (LS), roof (UBS), and wall (MBS) sequences of the Skaergaard Intrusion were analyzed for major and trace elements using DCP-AES and ICP-MS techniques. In all three sequences, FeO progressively increases, and MgO and Al₂O₃ progressively decrease with differentiation. Although trace element abundances are, in general, higher in UBS ilmenite than in MBS and LS ilmenite, all three sequences have similar trends for trace element abundance vs. crystallization. Ba, Cs, Rb, Sr, Th, U, Y, and the REEs are excluded elements in ilmenite, and remained at low abundances during differentiation. Cr, Ni, Sc, and V are included elements in ilmenite and other mafic phases, and decreased during differentiation. V contents in ilmenite, however, do not decrease significantly until the upper part of the middle zone, suggesting that magnetite did not begin to affect the magma differentiation trend until much later than when it first appears in the intrusion. Hf, Nb, Ta, and Zr, which are strongly excluded elements in silicates, are included elements in ilmenite. The element ratios Zr/Hf, Y/Ho, Nb/Ta, and U/Th are relatively constant in Skaergaard ilmenite from different parts of the intrusion, suggesting that fluid transport did not significantly effect these elements during differentiation or post-solidification cooling. Calculated partition coefficients for ilmenite in the Skaergaard Intrusion are similar to those reported from previous studies of lunar and terrestrial basalts and kimberlites, and for most elements are significantly lower than those reported for ilmenite in rhyolitic magma. Similar D_i's for Zr, Hf, Nb, and Ta suggest that ilmenite crystallization did not significantly affect Zr/Nb or Hf/Ta in the Skaergaard magma, but the ratios of Zr, Hf, Nb, or Ta to other high field strength elements, such as Th, U, Y, or the REEs, may have been altered by ilmenite fractionation.     

Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.