REE Partition Coefficients Research Articles

REE, Y, Sc, and Li Partition between Aluminosilicate and Aluminofluoride Melts, Depending on Pressure and Water Content in the Model Granite System

Experiments on REE, Y, Sc, and Li partition between aluminosilicate (L) and aluminofluoride (LF) melts in the granite system at 800°C and 1, 2 kbar, containing up to 18 wt % F and 2 to 13 wt % H2O, show that all REE, Y, Sc, and Li are preferably distributed into the aluminofluoride melt, regardless of the experimental conditions. The partition coefficients of the elements Kd REE = $$C_{{{\text{REE}}}}^{{LF}}$$/$$C_{{{\text{REE}}}}^{L}$$ between these phases depend on pressure. The first data are obtained indicating that a pressure increase from 1 to 2 kbar at a temperature of 800°C leads to a significant decrease in Kd REE. The partition coefficients between the melts monotonously decrease from LREE to HREE at both 1 and 2 kbar. No clear relationships were found between Kd REE and the water concentration in the system. It is shown that Li strongly impacts the distribution of REE, Y and Sc, because Li, similar to F, causes the onset of liquid immiscibility in the system and facilitates REE, Y, and Sc enrichment in the salt melts. All of the experiments show a positive correlation between the partition coefficients Kd Li and Kd REE, Y, Sc between the salt and silicate melts. The dependence of this REE behavior on pressure in the system may be explained by a change in the structure of silicate and salt melts when H2O and F are dissolved in them and by complexation under various experimental conditions.

Incorporation of Rare Earths and Yttrium in Calcite: A Critical Re-evaluation

The reported partition coefficients of REE with calcite are reviewed and critically discussed. In some of the reported experimental sets, REE concentrations are found to be supersaturated with respect to individual REE2(CO3)3 but never to REE(OH)3. Although the solutions are unsaturated with respect to individual REY carbonates, REY including Y are incorporated in calcite surfaces, where they are overgrown by calcite. Charge balances may be obtained by building {REY–Na-(CO3)2}n or by exchange of 2Ca2+ against REY3+ + blank space calcite lattice. These surface compounds may either be homogeneously distributed or clustered. Both the size and frequency of clusters increase with [REY]/[Ca] or [ΣREY3+]/[Ca2+] in solution. If these surface precipitates are removed into solutions saturated with respect to ΣREE2(CO3)3, they start growing in the aqueous phase. In this case, the apparent DREY and kREY values decrease with increasing REY concentrations in solution. In previous studies, only the individual distribution coefficients are reported not considering that the entirety of REY determines their behavior in partitioning. Given enough time, these surface clusters equilibrate with the aqueous phase before being overgrown by calcite. In the double logarithmic plots of {REY}/{Ca} versus [REY]/[Ca] or [REY3+]/[Ca2+], two relationships evolve characterizing the REY distribution in marine calcite and experimental calcites grown in Mg2+-free solutions. The double logarithmic plots of partition coefficients of REYi3+ in calcite grown from seawater show a slope exceeding unity, whereas those from fluids without Mg2+ depict slopes less than unity being both in contrast to the Henderson–Kracek rule.

Clinopyroxene/Melt Trace Element Partitioning in Sodic Alkaline Magmas

Abstract Clinopyroxene is a key fractionating phase in alkaline magmatic systems, but its impact on metal enrichment processes, and the formation of REE + HFSE mineralisation in particular, is not well understood. To constrain the control of clinopyroxene on REE + HFSE behaviour in sodic (per)alkaline magmas, a series of internally heated pressure vessel experiments was performed to determine clinopyroxene–melt element partitioning systematics. Synthetic tephriphonolite to phonolite compositions were run H2O-saturated at 200 MPa, 650–825°C with oxygen fugacity buffered to log f O2 ≈ ΔFMQ + 1 or log f O2 ≈ ΔFMQ +5. Clinopyroxene–glass pairs from basanitic to phonolitic fall deposits from Tenerife, Canary Islands, were also measured to complement our experimentally-derived data set. The REE partition coefficients are 0·3–53, typically 2–6, with minima for high-aegirine clinopyroxene. Diopside-rich clinopyroxene (Aeg5–25) prefer the MREE and have high REE partition coefficients (DEu up to 53, DSm up to 47). As clinopyroxene becomes more Na- and less Ca-rich (Aeg25–50), REE incorporation becomes less favourable, and both the VIM1 and VIIIM2 sites expand (to 0·79 Å and 1·12 Å), increasing DLREE/DMREE. Above Aeg50 both M sites shrink slightly and HREE (VIri ≤ 0·9 Å ≈ Y) partition strongly onto the VIM1 site, consistent with a reduced charge penalty for REE3+ ↔ Fe3+ substitution. Our data, complemented with an extensive literature database, constrain an empirical model that predicts trace element partition coefficients between clinopyroxene and silicate melt using only mineral major element compositions, temperature and pressure as input. The model is calibrated for use over a wide compositional range and can be used to interrogate clinopyroxene from a variety of natural systems to determine the trace element concentrations in their source melts, or to forward model the trace element evolution of tholeiitic mafic to evolved peralkaline magmatic systems.

Experimental study of trace element distribution between calcite, fluorite and carbonatitic melt in the system CaCO3 + CaF2 + Na2CO3 ± Ca3(PO4)2 at 100 MPa

Here we present an experimental study of the distribution of a broad range of trace elements between carbonatite melt, calcite and fluorite. The experiments were performed in the CaCO3 + CaF2 + Na2CO3 ± Ca3(PO4)2 synthetic system at 650–900 °C and 100 MPa using rapid-quench cold-seal pressure vessels. Starting mixtures were composed of reagent-grade oxides, carbonates, Ca3(PO4)2 and CaF2 doped with 1 wt% REE–HFSE mixture. The results show that the distribution coefficients of all the analyzed trace elements for calcite and fluorite are below 1, with the highest values observed for Sr (0.48–0.8 for calcite and 0.14–0.3 for fluorite) and Y (0.18–0.3). The partition coefficients of REE gradually increase with increasing atomic number from La to Lu. The solubility of Zr, Hf, Nb and Ta in the synthetic F-rich carbonatitic melts, which were used in our experiments, is low and limited by crystallization of baddeleyite and Nb-bearing perovskite.

The effect of fluorine and chlorine on trace element partitioning between apatite and sediment melt at subduction zone conditions

The effect of F and Cl on trace element recycling during subduction-related sediment melting has been investigated by performing piston-cylinder experiments with a hydrous experimental pelite starting material (EPSM) with variable Cl (~0, 500, 1000, 2000, or 3000ppm) and F (~0, 700, or 1500ppm) concentrations, at 2.5GPa, 800°C. The variations of trace element concentrations in melt are systematically correlated with the variation of F (0.07–0.39wt%) and Cl (0.07–0.39wt%) contents. Trace elements Zn, V and Pb, and major elements Fe, Mg and Ca, show positive correlations with each other, and also with the Cl content in melt. The concentrations of light and medium rare earth elements (LMREE) increase with the Cl content in melt, whereas both F and Cl cause a decrease in the concentrations of high field strength elements (HFSE, such as Nb, Ta, Zr and Hf). Trace element (REE, Y, Sr, Th, U) concentrations in apatite are found to increase with the mole fraction of chlorapatite (ClAp). The preference for ClAp is stronger for cations with higher charge (e.g., Th4+, U4+>REE3+) and larger ionic radii (e.g., LREE>HREE).Trace element partition coefficients between apatite and melt show up to 4 times variation between experiments, e.g., DLaAp-melt=77–281; DSmAp-melt=176–519; DSrAp-melt=4–12 and DTh,UAp-melt=4–19. The REE partition coefficients between apatite and melt (DREEAp-melt) display a concave pattern with the peak at Sm/Nd and a negative Eu anomaly, and are significantly higher than previously reported values for partitioning experiments conducted at lower pressures and higher temperatures. The high values of DLREEAp-melt demonstrate the importance of apatite in terms of LREE partitioning during sediment melting, while allanite/monazite still dominates the partitioning of Th. In the absence of allanite/monazite, apatite-buffered melt is characterized by a significant enrichment of Th relative to La. Because of the contrasting behavior of LREE and HFSE in melt with the addition of Cl and F, the fractionation of these elements in slab-derived sediment melts will be enhanced by the presence of halogens.

A new method for estimating parent rock trace element concentrations from zircon

Zircon/bulk rock REE partition coefficients from natural samples correlate with REE concentration in zircon. The correlation is the strongest for the LREE and diminishes with decreasing ionic radius. The relationship between partition coefficient and REE concentration in zircon can be modeled as a power law and the coefficient (α) and exponent (β) terms for each of the REE are empirically determined using new and previously published data. A series of independent tests show that using variable partition coefficients based on the reported α and β terms commonly results in more accurate estimates of bulk rock REE concentrations than average partition coefficients, particularly for the LREE that have previously been difficult to constrain. These results provide a way to account for highly variable REE concentrations in zircon, which may be controlled by numerous processes such as surface enrichment, complex substitution mechanisms, or accidental sampling of sub-microscopic inclusions. The proposed method for estimating bulk rock REE concentrations is especially well-suited to detrital zircon investigations where there is no information available on the parent rock composition.

Reduced sediment melting at 7.5–12 GPa: phase relations, geochemical signals and diamond nucleation

Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5–12 GPa and 800–1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325–394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite–siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at 10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000–1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich ( 1). Aragonite and Fe–Mg carbonate have very different REE partition coefficients (DMst-Sd/L ~ 0.01 and DArg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in incompatible elements and displays a pronounced negative Ta–Nb anomaly but no Zr–Hf anomaly. Although all experiments were conducted in the diamond stability field, only graphite was observed in low-temperature experiments. Spontaneous diamond nucleation and the complete transformation of graphite to diamond were observed at temperatures above 1200–1300 °C. We speculate that the observed character of graphite–diamond transformation is controlled by relationships between the kinetics of metastable graphite dissolution and diamond nucleation in a hydrous silicocarbonate melt that is oversaturated in C.

LILE, REE, and HFSE partition coefficients between crystal and melt in migmatites of granulite facies of the Nimnyr block, Aldan shield

The behavior of Rb, Sr, Ba, Cr, V, Nb, Zr, REEs, and Y is studied in migmatites of granulite facies and the transitional zone to amphibolite facies in the western part of the Aldan granulite area. Our data allowed estimation of the partition coefficients of these elements in the crystal-melt system (Di) for orthopyroxene, garnet, clinopyroxene, and hornblende. The leucosomes of anatectic migmatites and diatectites (high-K charnockites and granites) were accepted as a melt, and the metapelites or previously granitized rocks (nebulites) and early leucosomes relative to late leucosome were the primary rocks and restite. The dependence of Di on the REE ionic radius is close to parabolic [7]. Our data allow identification of a qualitative link between the DiGrt/melt and the thermodynamic conditions of high-grade metamorphism and the accompanying partial melting, which leads to formation of a series of ultrametamorphic granitic rocks: lower temperature rocks (conditions of amphibolite facies) are characterized by higher DREE values relative to the zone of granulite facies. The late granitic rocks formed after diatectic charnockites are also characterized by higher DREE values relative to the preceding charnockites. For the conditions of granulite facies, the material belongs to rocks similar in the formation conditions; however, the series are strongly distinct in K content. The influence of the composition of the anatectic melt and acidity-alkalinity conditions on the partition coefficients of the studied elements is so strong that it eliminates the effect of temperature and pressure. The LREEs, Rb, Sr, and Ba will mostly accumulate in the garnet-orthopyroxene assemblage in the zone of melt origination, whereas HREEs will remain in restite along with Cr and V. Niobium and Zr may enrich the granitic melts. In contrast, the stability of amphibole in restite causes the depletion of melts in all REEs, Y, and Nb and enrichment in Rb, Sr, Ba, and, to a lesser extent, Zr.

A parameterized model for REE distribution between low-Ca pyroxene and basaltic melts with applications to REE partitioning in low-Ca pyroxene along a mantle adiabat and during pyroxenite-derived melt and peridotite interaction

Low-Ca pyroxenes play an important role in mantle melting, melt-rock reaction, and magma differentiation processes. In order to better understand REE fractionation during adiabatic mantle melting and pyroxenite-derived melt and peridotite interaction, we developed a parameterized model for REE partitioning between low-Ca pyroxene and basaltic melts. Our parameterization is based on the lattice strain model and a compilation of published experimental data, supplemented by a new set of trace element partitioning experiments for low-Ca pyroxenes produced by pyroxenite-derived melt and peridotite interaction. To test the validity of the assumptions and simplifications used in the model development, we compared model-derived partition coefficients with measured partition coefficients for REE between orthopyroxene and clinopyroxene in well-equilibrated peridotite xenoliths. REE partition coefficients in low-Ca pyroxene correlate negatively with temperature and positively with both calcium content on the M2 site and aluminum content on the tetrahedral site of pyroxene. The strong competing effect between temperature and major element compositions of low-Ca pyroxene results in very small variations in REE partition coefficients in orthopyroxene during adiabatic mantle melting when diopside is in the residue. REE partition coefficients in orthopyroxene can be treated as constants at a given mantle potential temperature during decompression melting of lherzolite and diopside-bearing harzburgite. In the absence of diopside, partition coefficients of light REE in orthopyroxene vary significantly, and such variations should be taken into consideration in geochemical modeling of REE fractionation in clinopyroxene-free harzburgite. Application of the parameterized model to low-Ca pyroxenes produced by reaction between pyroxenite-derived melt and peridotite revealed large variations in the calculated REE partition coefficients in the low-Ca pyroxenes. Temperature and composition of starting pyroxenite must be considered when selecting REE partition coefficients for pyroxenite-derived melt and peridotite interaction.

Experimental study of trace element partitioning between lunar orthopyroxene and anhydrous silicate melt: Effects of lithium and iron

Orthopyroxene (Opx) was present during a significant portion of crystallisation of the lunar magma ocean, but its influence on co-existing melt trace element contents is not well quantified. We performed high-pressure ( P, 1.1 to 3.2 GPa), high-temperature ( T, 1400 to 1600 °C) experiments on synthetic Fe-rich compositions at reducing conditions relevant to the lunar mantle to constrain trace element partitioning between Opx and anhydrous silicate melts. Opx–melt partition coefficients ( D Opx-melt) for a wide range of trace elements (LILE: Li, Ba; REE: La, Ce, Nd, Sm, Dy, Eu, Er, Tm Y, Yb, Lu; HFSE: Zr, Nb, Hf, Ta, Th, U); and transition metals (Sc, V, Mn, Co, Mo) show only very minor variations across the considered P– T range. REE partition coefficients increase from D La opx-melt = 0.0014 ± 0.0008 to D Lu opx-melt = 0.051 ± 0.007. D values for highly charged elements vary from D Th opx-melt = 0.0013 ± 0.0008 through D Nb opx-melt = 0.0018 ± 0.0006 and D U opx-melt = 0.0015 ± 0.0006 to D Ti opx-melt = 0.068 ± 0.0010. D Lu opx-melt/ D Hf opx-melt values of 6.3 ± 2.4 are at the high end of reported values for minerals that played a role during crystallisation of the lunar magma ocean, and higher than previously reported for Opx under identical oxygen fugacity conditions, implying Opx-rich cumulates in the lunar mantle have highly superchondritic Lu–Hf ratios. Lattice strain modelling of our REE partitioning data suggests that varying the concentration of divalent Fe in Opx very slightly decreases the ideal cation radius for M 3+ elements entering the M2 site, r 0 M2 , whereas the partitioning of M 3+ elements entering the M1 site is unaffected. A subtle increase in the maximum partition coefficient for M 3+ elements entering both the M1 and M2 sites with decreasing T is identified, when experiments carried out at similar reducing oxygen fugacities are considered. The presence of Li at concentrations of up to ~ 350 ppm does not have a measureable effect on the Opx–melt partitioning behaviour of REE or any other element, showing that charge-balancing of M 3+, M 4+ and M 5+ elements in Opx is likely dominated by a vacancy mechanism.

BaSO4／水溶液系におけるREE分配係数の温度変化（10～200℃）：固相REE3+の結合状態変化と分配反応のΔHrとΔSrの四組効果

BaSO4／水溶液系におけるREE分配係数の温度変化（10～200℃）：固相REE3+の結合状態変化と分配反応のΔHrとΔSrの四組効果

Carbonatites in China: A review for genesis and mineralization

Carbonatites are commonly related to the accumulation of economically valuable substances such as REE, Cu, and P. The debate over the origin of carbonatites and their relationship to associated silicate rocks has been ongoing for about 45 years. Worldwide, the rocks characteristically display more geochemical enrichments in Ba, Sr and REE than sedimentary carbonate rocks. However, carbonatite’s geochemical features are disputed because of secondary mineral effects. Rock-forming carbonates from carbonatites at Qinling, Panxi region, and Bayan Obo in China show REE distribution patterns ranging from LREE enrichment to flat patterns. They are characterized by a Sr content more than 10 times higher than that of secondary carbonates. The coarse- and fine-grained dolomites from Bayan Obo H8 dolomite marbles also show similar high Sr abundance, indicating that they are of igneous origin. Some carbonates in Chinese carbonatites show REE (especially HREE) contents and distribution patterns similar to those of the whole rocks. These intrusive carbonatites display lower platinum group elements and stronger fractionation between Pt and Ir relative to high-Si extrusive carbonatite. This indicates that most intrusive carbonatites may be carbonate cumulates. Maoniuping and Daluxiang in Panxi region are large REE deposits. Hydrothermal fluorite ore veins occur outside of the carbonatite bodies and are emplaced in wallrock syenite. The fluorite in Maoniuping has Sr and Nd isotopes similar to carbonatite. The Daluxiang fluorite shows Sr and REE compositions different from those in Maoniuping. The difference is reflected by both the carbonatites and rock-forming carbonates, indicating that REE mineralization is related to carbonatites. The cumulate processes of carbonate minerals make fractionated fluids rich in volatiles and LREE as a result of low partition coefficients for REE between carbonate and carbonatite melt and an increase from LREE to HREE. The carbonatite-derived fluid has interacted with wallrock to form REE ore veins. The amount of carbonatite dykes occurring near the Bayan Obo orebodies may support the same mineralization model, i.e. that fluids evolved from the carbonatite dykes reacted with H8 dolomite marble, and thus the different REE and isotope compositions of coarse- and fine-grained dolomite may be related to reaction processes.

Origin and tectonic implication of an UHP metamorphic mafic–ultramafic complex from the Sulu UHP terrane, eastern China: Evidence from petrological and geochemical studies of CCSD-Main Hole core samples

Study of the Maobei garnet peridotite and pyroxenite are significant, because these rocks were subjected to subduction-zone UHP metamorphism that is indicative of deep continental subduction. In order to better understand the origin of the Maobei peridotite and pyroxenite and the processes of continental subduction, we performed geochemical analyses on whole-rock and mineral samples. The studied samples were recovered in the main-hole of the Chinese Continental Scientific Drilling in the Sulu UHP terrane, east-central China. The garnet peridotites occur as lenses or layers in pyroxenite; they comprise garnet wehrlite and garnet dunite with minor interlayers of garnet websterite and garnet. Mini-bands, nodules or veins of eclogite and garnet clinopyroxenite (“internal”) also irregularly occur in garnet wehrlite. The peridotites are composed of olivine (Fo 83–84), garnet (Prp 51–56), ± diopside ± enstatite (En 86–87) ± titanoclinochumite, and have lower Mg/(Mg + Fe total) values of 0.79–0.83 and higher Al 2O 3 and CaO contents in comparison with the gneiss-hosted Sulu mantle peridotites. Garnet wehrlite displays variable REE patterns, from LREE-enriched to slightly LREE depleted relative to MREE and HREE; whereas, other ultramafic rocks show roughly flat REE patterns. In general, Rb, Ba and LREE increase, and compatible element (e.g. Cr, Co and Ni) abundances decrease from peridotite, pyroxenite to “internal eclogite” and “internal Grt-clinopyroxenite”. The calculated REE partition coefficients (D REE) between Cpx and Grt of the Maobei peridotite and pyroxenite decrease regularly from LREE (D Ce = 32–708) to HREE (D Yb = 0.01–0.10), which is comparable with natural mantle peridotite and eclogite crystallized at 800–1100 °C. The geochemical data and occurrence of these rocks suggest that the protoliths of the Maobei peridotites are cumulates derived by differentiation of basaltic magma at the lower continental crust. Thus, the “Internal eclogite and Grt-clinopyroxenite” result from post-cumulus crystallization of the trapped melt. Ti-clinohumite orthopyroxenite may have formed by reaction between peridotitic olivine and indigenous melt or country rock-derived (“exotic”) TiO 2-bearing fluids at high-P condition during continental subduction to mantle depths. The peak P−T estimates of 795–840 °C and 5.3–6.8 GPa of the Maobei peridotites and the available petrological data of country rocks indicate that the continental crust was subducted to a depth of ∼ 200 km.

Trace element partitioning between garnet lherzolite and carbonatite at 6.6 and 8.6 GPa with applications to the geochemistry of the mantle and of mantle-derived melts

We present experimental determinations of trace element partitioning between natural fertile lherzolite and near-solidus carbonatitic liquid (cbL) at pressures of 6.6 and 8.6 GPa and temperatures between 1265 and 1470 °C, conditions relevant for initial generation of CO 2-rich melt beneath oceanic ridges and for carbonate melt percolation in the deep source regions of ocean island basalts. Compared to previous experiments at lower pressures, which produced more aluminous cpx, our experimental cpx–melt pairs show lower partition coefficients for trivalent cations entering the M2 site ( D cpx/cbL Lu = 0.17, D cpx/cbL La = 0.006). D cpx/cbL U (0.002) and D cpx/cbL Th (0.001) also are distinctly lower than previous estimates. The garnet–carbonate melt partition coefficients for REE vary from highly incompatible La to moderately compatible Lu and are slightly lower than those from lower pressure experiments. From 6.6 to 8.6 GPa, HFSEs including Zr, Hf, and Ti range from moderately incompatible to slightly compatible, with D gamet/cbL Hf > D gamet/cbL Ti > D gamet/cbL Zr. U and Th remain highly incompatible in garnet at both pressures with D gamet/cbL U/ D gamet/cbL Th of 1.2–1.25 at 6.6 GPa and 1.35 at 8.6 GPa. Estimates of D gt.lherzolite/cbL, based on our newly measured partition coefficients, suggest that 30–60% of some of the highly incompatible elements can be removed by efficient extraction of 0.1% carbonatitic melt from the Earth's deep upper mantle, and that 0.1% C-rich melt extraction can create a residue that has Rb/Sr, U/Pb and Th/U ratios, respectively, 29, 12, and 6% lower and Sm/Nd ratio ~ 11% higher than the unmelted source. Our data also suggest that ancient carbonate melt extraction and metasomatism can decouple the Hf and Nd isotope systems. Garnet lherzolite derived carbonatitic melt has lower normalized HREEs and smaller Nb/Ta ratios than erupted natural carbonatites. Therefore, the trace element abundances of erupted carbonatites require either reaction with a shallower mantle peridotite with low modal garnet or derivation from an enriched source. The trace element abundances of deep carbonate-rich melts must become diluted by greater volumes of silicate melt produced in the shallower portions of sub-ridge basalt source regions. But, the observed 230Th and 231Pa excesses and variations of CO 2/Nb in erupted MORBs are a likely consequence of variable contributions of carbonate-rich melt.

Rare earth elements in tourmaline and chlorite from tin-bearing assemblages: Factors controlling fractionation of REE in hydrothermal systems

The REE distribution in minerals from tin-bearing ore-magmatic systems of the Russian Far East, including the Komsomolsk, Khingan, and Badzhal districts in the Amur region and the Kavalerovo, Lesozavodsk, Voznesenka, Furmanovo, and other districts in Primorsky krai, has been studied. The main attention was focused on tourmaline and chlorite; in addition, associated biotite, feldspar, apatite, fluorite, and carbonates were examined. The major factors affecting the REE distribution in the studied minerals are the temperature, Eh, and pH of the mineral-forming medium; crystal chemistry; partition coefficients of REE between fluid and minerals; and complexation that disturbs the coherent behavior of REE. Fluid evolution at different stages is characterized.

The effect of titanite and other HFSE-rich mineral (Ti-bearing andradite, zircon, eudialyte) fractionation on the geochemical evolution of silicate melts

We present trace element data for HFSE-rich minerals (titanite, eudialyte, Ti-bearing andradite, zircon) from plutonic rocks of the Eocene Tamazeght complex, High Atlas Mountains, Morocco. In most lithologies significant amounts of titanite are present and as such, titanite fractionation played a major role in the evolution of the HFSE budget of the whole complex. By combining our data with published titanite–melt partition coefficients we explore the effects of titanite fractionation on the evolution of geochemical parameters (Zr/Hf, Nb/Ta, La/Lu and Th/U ratios) during differentiation of silicate melts in detail. Based upon this, we further discuss the genetic relationships between the various rock types present in the Tamazeght complex and show that the above-mentioned element ratios can potentially be useful for distinguishing geochemically distinct melt reservoirs within a given plutonic rock suite. Zircon, eudialyte and Ti-bearing andradite are generally rare or are restricted to localized rock units. Despite their scarcity, each of them can have a significant effect upon the HFSE budget in their evolving magmas. Here, we derive first estimations of eudialyte–melt partition coefficients for REE. Application of these data to eudialyte-bearing rocks of the Ilímaussaq complex (South Greenland), and comparing the results to published estimations for the parental melts of these rocks yields consistent results and demonstrates the reliability of our estimations.

Petrogenesis of eclogites enclosed in mantle-derived peridotites from the Sulu UHP terrane: constraints from trace elements in minerals and Hf isotopes in zircon

Garnet clinopyroxenite and eclogite lenses are widespread in mantle-derived garnet peridotites from the Sulu UHP terrane, eastern China. In order to constrain their origin, major and trace element compositions of minerals from 6 eclogites and one garnet clinopyroxenite, and Hf isotopes of zircons from one eclogite, were analyzed by electron probe, LA-ICP-MS and LA- (MC) ICP-MS, respectively. Eclogitic garnets show a large variation in composition (Alm 20–48Prp 24–50Grs 15–38Sps 1), weakly correlated with garnets in their host peridotites. Garnets show LREE depletion and flat HREE patterns, with La n of 0.02–0.52 and Lu n of 5–75. Some garnets show zoning in HREE and Y with a U-shaped, concave-downward profile, but locally exhibit positive sharp variations in HREE and Y contents; such feature reflects disturbance in chemical–physical conditions during garnet growth. Clinopyroxene exhibits humped (mostly) or sinusoidal REE patterns, with La n of 0.3–6.0, Nd n of 2–14 and (La/Lu) n of 1.8–113 with a few exceptions. Partition coefficients of REE ( D) between coexisting clinopyroxene and garnet in eclogite show a large variation: D LREE and D HREE ranging from 10 to100 and from 0.1 to 0.01, respectively, similar to D REE values of the natural systems at 800–1100 °C. The D values (0.1–1) of HREE between Cpx and Grt from Grt clinopyroxenite and one eclogite differ distinctly from the other eclogites, which are consistent with high- T experimental data on garnet lherzolites. Zircons from the Xugou eclogite have no inherent core, which have low U/Th (most < 0.20) and 176Lu/ 177Hf (0.000008–0.0000637), and relative high 176Hf/ 177Hf (0.28241–0.28262) ratios. These features indicate a metamorphic signature, and document that metasomatism affected the eclogite protolith. The model ages ( T DM1) of zircons mostly cluster around 1.0–1.1 Ga, which probably reflects the metasomatic source. Bulk compositions of eclogite and Grt clinopyroxenite differ from those of Sulu eclogites in gneiss and MORB. The protoliths of these rocks may reflect the intrusion of asthenosphere-derived melts in Proterozoic. Eclogites with convex REE pattern and garnet clinopyroxenite were formed by high-pressure crystal accumulation whereas the LREE-enriched eclogites may represent crystallized melt; both eclogite and clinopyroxenite together with their host peridotite were metamorphosed at 700–965 °C and ≥ 4 GPa during the Triassic northward subduction of the Yangtze craton.

Chemical composition and ultrahigh-P metamorphism of garnet peridotites from the Sulu UHP terrane, China: Investigation of major, trace elements and Hf isotopes of minerals

The Zhimafang peridotite body recovered by a pre-pilot borehole (PP1) of the Chinese Continental Scientific Drilling Project occurs in gneiss from the southern Sulu ultrahigh-P (UHP) terrane, east-central China. Detailed petrographic observation of the freshest lherzolites reveals the existence of pre-peak mantle relics, rare enstatite inclusions (Opx1) in garnet, and coarse-grained diopside (Cpx1) in the peridotites. Matrix phases Ol + Grt + Opx + Cpx ± Phl represent the assemblage of the peak-stage. At least > 1.5 GPa pressure increase is recognized from the mantle setting to the peak-stage of subduction-zone UHP metamorphism at ~ 800 °C and 6.8 GPa for the peridotites. All peridotitic minerals have high Mg# (Ol, 91–93, Cpx, 93–94 and Opx, 92–94). Garnets are depleted in LREE, and have increased abundances from Pr through the MREE to a plateau of heavy REE (HREE) at about 10 times chondrite. In contrast, clinopyroxenes display humped REE patterns with high (La/Yb) N values of 27–68. Phlogopite is a major carrier of Ba (5205 ppm) and Th (5.5 ppm). Partition coefficients ( D Cpx/Grt) for REE between clinopyroxene and garnet decrease from LREE (~ 100) to HREE (< 1 but > 0.1), suggesting that clinopyroxene and garnet equilibrated at low- T (< 1100 °C). Zircons from three phlogopite and/or magnesite-bearing peridotites show very low 176Lu/ 177Hf values (between 10 − 3 and 10 − 6 ), and a wide range in 176Hf/ 177Hf ratios (0.28221–0.28250). The zircons with low 176Hf/ 177Hf and relatively high 176Lu/ 177Hf document that metasomatism affected the peridotite protolith. The model ages ( T DM) of zircons mostly cluster around 1.3–1.4 Ga, which probably reflects the metasomatic source. These chemical data combined with previous published bulk-rock major and trace element data indicate that the Zhimafang peridotites probably represent depleted and metasomatized subcontinental lithospheric mantle (SCLM) beneath the Sino-Korean craton. Investigation of the Sulu UHP metamorphic garnet peridotites provides additional insights into the Earth's geochemical and tectonic evolution, and enlarges our understanding of the exhumation of orogenic peridotites.

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt.

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 H 2O 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.