Experimental determination of REE partition coefficients between amphibole and basaltic to andesitic liquids at high pressure

Amphibole/liquid partition coefficients for the REE(D^amph/liq_REE) obtained from natural rocks increase systematically with bulk rock compositional change from basalt to rhyolite and are higher for the middle to heavy REE. Five new experimentally determined sets of D_REE (La, Sm, “Eu²⁺”, Ho, Lu)and 4 published sets are similar to these data and provide values for use in geochemical modelling of magmatic processes involving amphibole, over a range of temperature, pressure and oxygen fugacity. The partition coefficients increase significantly with decreasing temperature, and increase slightly with increasing oxygen fugacity. Pressure does not appear to have a major effect, although one data set suggests increased pressure lowers D^amph/liq_REE in a basaltic composition.     

Partition of Sr,Ba, Ca,Y, Eu2+, Eu3+, and other REE between plagioclase feldspar and magmatic liquid: an experimental study

Plagioclase feldspar/magmatic liquid partition coefficients for Sr, Ba, Ca, Y, Eu²⁺, Eu³⁺ and other REE have been determined experimentally at 1 atm total pressure in the temperature range 1150–1400°C. Natural and synthetic melts representative of basaltic and andesitic bulk compositions were used, crystallizing plagioclase feldspar in the composition range An₃₅–An₈₅. Partition coefficients for Sr are greater than unity at all geologically reasonable temperatures, and for Ba are less than unity above approximately 1060°C. Both are strongly dependent upon temperature. Partition coefficients for the trivalent REE are relatively insensitive to temperature. At fixed temperature they decrease monotonically from La to Lu. The partition of Eu is a strong function of oxygen fugacity. Under extreme reducing conditions D_Eu approaches the value of D_Sr.     

Partition coefficients for REE between garnets and liquids: implications of non-Henry's Law behaviour for models of basalt origin and evolution

Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg₃Al₂Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), D^{garnet liquid}_REE increases as the REE concentration in the garnet decreases. At higher concentrations, D_REE is constant. D^{grossular liquid}_REE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which D_REE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of D_REE^{garnet/liquid} for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (D^{pyrope/liquid} = 0.067(Ce), 0.108(Sm), 0.155(Tm) and D^{grossular/Liquid} = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined.     

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.     

Interpreting granulite facies events through rare earth element partitioning arrays

The use of rare earth element (REE) partition coefficients is an increasingly common tool in metamorphic studies, linking the growth or modification of accessory mineral geochronometers to the bulk silicate mineral assemblage. The most commonly used mineral pair for the study of high‐grade metamorphic rocks is zircon and garnet. The link from U–Pb ages provided by zircon to the P–T information recorded by garnet can be interpreted in relation to experimental data. The simplistic approach of taking the average REE abundances for zircon and garnet and comparing them directly to experimentally derived partition coefficients is imperfect, in that it cannot represent the complexity of a natural rock system. This study describes a method that uses all the zircon analyses from a sample, and compares them to different garnet compositions in the same rock. Using the most important REE values, it is possible to define zircon–garnet equilibrium using an array rather than an average. The array plot describes partitioning between zircon and garnet using D_Yb and D_Yb/D_Gd as the defining features of the relationship. This approach provides far more sensitivity to mineral reactions and diffusional processes, enabling a more detailed interpretation of metamorphic history of the sample.     

Amphibole megacrysts as a probe into the deep plumbing system of Merapi volcano,Central Java,Indonesia

Amphibole has been discussed to potentially represent an important phase during early chemical evolution of arc magmas, but is not commonly observed in eruptive arc rocks. Here, we present an in-depth study of metastable calcic amphibole megacrysts in basaltic andesites of Merapi volcano, Indonesia. Radiogenic Sr and Nd isotope compositions of the amphibole megacrysts overlap with the host rock range, indicating that they represent antecrysts to the host magmas rather than xenocrysts. Amphibole-based barometry suggests that the megacrysts crystallised at pressures of >500 MPa, i.e., in the mid- to lower crust beneath Merapi. Rare-earth element concentrations, in turn, require the absence of magmatic garnet in the Merapi feeding system and, therefore, place an uppermost limit for the pressure of amphibole crystallisation at ca. 800 MPa. The host magmas of the megacrysts seem to have fractionated significant amounts of amphibole and/or clinopyroxene, because of their low Dy/Yb ratios relative to the estimated compositions of the parent magmas to the megacrysts. The megacrysts’ parent magmas at depth may thus have evolved by amphibole fractionation, in line with apparently coupled variations of trace element ratios in the megacrysts, such as e.g., decreasing Zr/Hf with Dy/Yb. Moreover, the Th/U ratios of the amphibole megacrysts decrease with increasing Dy/Yb and are lower than Th/U ratios in the basaltic andesite host rocks. Uranium in the megacrysts’ parent magmas, therefore, may have occurred predominantly in the tetravalent state, suggesting that magmatic fO₂ in the Merapi plumbing system increased from below the FMQ buffer in the mid-to-lower crust to 0.6–2.2 log units above it in the near surface environment. In addition, some of the amphibole megacrysts experienced dehydrogenation (H₂ loss) and/or dehydration (H₂O loss), as recorded by their variable H₂O contents and D/H and Fe³⁺/Fe²⁺ ratios, and the release of these volatile species into the shallow plumbing system may facilitate Merapi’s often erratic eruptive behaviour.     

Distribution of REE between clinopyroxene and basaltic melt along a mantle adiabat: effects of major element composition, water, and temperature

The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D ₀, r ₀ and E) as functions of pressure, temperature, and compositions of cpx and melt. D ₀ is found to positively correlate with Al in tetrahedral site (Al ^T ) and Mg in the M2 site (Mg^M2) of cpx and negatively correlate with temperature and water content in the melt. r ₀ is negatively correlated with Al in M1 site (Al^M1) and Mg^M2 in cpx. And E is positively correlated with r ₀. During adiabatic melting of spinel lherzolite, temperature, Al ^T , and Mg^M2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.     

Distinct site preferences for heavy and light REE in amphibole and the prediction of Amph/LDREE

New experimental amphibole/melt partition coefficients from a variety of geologically relevant amphibole (pargasite, kaersutite, and K-richterite) and melt compositions obtained under conditions of interest to upper-mantle studies are combined with the results of X-ray single-crystal structure refinement. The ideal cation radii (r₀), calculated using the lattice-site elastic-strain model of Blundy and Wood (1994) under the hypothesis of complete REE (rare earth elements) ordering at ^[8]M4, mostly differ significantly from those obtained from both the structure refinement and the ionic radius of ^[8]Ca²⁺. Heavier REE may also strongly deviate from the parabolic trends defined by the other REE. On the basis of the crystal-chemical knowledge of major-element site-preference in amphibole and the occurrence of two sites with different co-ordination within the M4 cavity (M4 for Ca and Na, M4′ for Fe²⁺ and Mg), we propose a new model for REE incorporation. LREE order at the ^[8]M4 site, whereas HREE prefer the M4′ site with lower co-ordination in amphiboles with a significant cummingtonite component, and may also enter the M2 octahedron, at least in richterite. This more complex model is consistent with the observed ^Amph/LD, and drops the usual assumption that REE behave as a homogeneous group and order at the M4 site. The availability of multiple crystal-chemical mechanisms for REE³⁺ incorporation explains why measured and estimated ^Amph/LD_HREE may differ by up to one order of magnitude. When REE enter two different sites within the same cavity, a fit performed on the basis of a single curve may appear correct, but the values obtained for r₀ are biased towards those of the dominant site, and the Young's modulus is underestimated. When REE are incorporated in multiple sites in different cavities, the observed pattern cannot be reduced to a single curve, and the partition coefficients of heavy REE would be strongly underestimated by a single-site fit. The simplistic assumption that REE occupy a single site within the amphibole structure can thus substantially bias predictive models based on the elastic-strain theory. Our combined approach allows linkage between fine-scale site preference and the macroscopic properties of minerals and provides more reliable predictive models for mineral/melt partitioning. After the possible site-assignments have been identified, the shape of the Onuma curves constructed from accurately determined ^Amph/LD_REE now allows the active mechanisms for REE incorporation in amphiboles to be recognised even where site populations are not available. The REE preference for polyhedra with smaller size and lower co-ordination than those occupied by Ca invalidates the general idea that Ca acts as a “carrier” for REE. Received: 17 March 1999 / Accepted: 11 June 1999     

Sugarloaf Mountain,central Arizona,USA: A small-scale example of Miocene basalt-rhyolite magma mixing to yield andesitic magmas

Sugarloaf Mountain is a 200-m high volcanic landform in central Arizona, USA, within the transition from the southern Basin and Range to the Colorado Plateau. It is composed of Miocene alkalic basalt (47.2–49.1?wt.% SiO₂; 6.7–7.7?wt.% MgO) and overlying andesite and dacite lavas (61.4–63.9?wt.% SiO₂; 3.5–4.7?wt.% MgO). Sugarloaf Mountain therefore offers an opportunity to evaluate the origin of andesite magmas with respect to coexisting basalt. Important for evaluating Sugarloaf basalt and andesite (plus dacite) is that the andesites contain basaltic minerals olivine (cores Fo_76-86) and clinopyroxene (～Fs_9-18Wo_35-44) coexisting with Na-plagioclase (An_48-28Or_1.4–7), quartz, amphibole, and minor orthopyroxene, biotite, and sanidine. Noteworthy is that andesite mineral textures include reaction and spongy zones and embayments in and on Na-plagioclase and quartz phenocrysts, where some reacted Na-plagioclases have higher-An mantles, plus some similarly reacted and embayed olivine, clinopyroxene, and amphibole phenocrysts.Fractional crystallization of Sugarloaf basaltic magmas cannot alone yield the andesites because their ～61 to 64?wt.% SiO₂ is attended by incompatible REE and HFSE abundances lower than in the basalts (e.g., Ce 77–105 in andesites vs 114–166?ppm in basalts; Zr 149–173 vs 183–237; Nb 21–25 vs 34–42). On the other hand, andesite mineral assemblages, textures, and compositions are consistent with basaltic magmas having mixed with rhyolitic magmas, provided the rhyolite(s) had relatively low REE and HFSE abundances. Linear binary mixing calculations yield good first approximation results for producing andesitic compositions from Sugarloaf basalt compositions and a central Arizona low-REE, low-HFSE rhyolite. For example, mixing proportions 52:48 of Sugarloaf basalt and low incompatible-element rhyolite yields a hybrid composition that matches Sugarloaf andesite well ? although we do not claim to have exact endmembers, but rather, viable proxies. Additionally, the observed mineral textures are all consistent with hot basalt magma mixing into rhyolite magma. Compositional differences among the phenocrysts of Na-plagioclase, clinopyroxene, and amphibole in the andesites suggest several mixing events, and amphibole thermobarometry calculates depths corresponding to 8–16?km and 850° to 980?°C. The amphibole P-T observed for a rather tight compositional range of andesite compositions is consistent with the gathering of several different basalt-rhyolite hybrids into a homogenizing ‘collection' zone prior to eruptions. We interpret Sugarloaf Mountain to represent basalt-rhyolite mixings on a relatively small scale as part of the large scale Miocene (～20 to 15 Ma) magmatism of central Arizona. A particular qualification for this example of hybridization, however, is that the rhyolite endmember have relatively low REE and HFSE abundances.     

Inter-mineral Fe isotope variations in mantle-derived rocks and implications for the Fe geochemical cycle

Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in ⁵⁶Fe/⁵⁴Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ⁵⁶Fe_{clinopyroxene-olivine} fractionation and the δ⁵⁶Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ⁵⁶Fe_{clinopyroxene-garnet} fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.     

Experimental determination of REE partition coefficients between zircon,garnet and melt: a key to understanding high‐T crustal processes

The partitioning of rare earth elements (REE) between zircon, garnet and silicate melt was determined using synthetic compositions designed to represent partial melts formed in the lower crust during anatexis. The experiments, performed using internally heated gas pressure vessels at 7 kbar and 900–1000 °C, represent equilibrium partitioning of the middle to heavy REE between zircon and garnet during high‐grade metamorphism in the mid to lower crust. The D_REE (zircon/garnet) values show a clear partitioning signature close to unity from Gd to Lu. Because the light REE have low concentrations in both minerals, values are calculated from strain modelling of the middle to heavy REE experimental data; these results show that zircon is favoured over garnet by up to two orders of magnitude. The resulting general concave‐up shape to the partitioning pattern across the REE reflects the preferential incorporation of middle REE into garnet, with D_Gd (zircon/garnet) ranging from 0.7 to 1.1, D_Ho (zircon/garnet) from 0.4 to 0.7 and D_Lu (zircon/garnet) from 0.6 to 1.3. There is no significant temperature dependence in the zircon–garnet REE partitioning at 7 kbar and 900–1000 °C, suggesting that these values can be applied to the interpretation of zircon–garnet equilibrium and timing relationships in the ultrahigh‐T metamorphism of low‐Ca pelitic and aluminous granulites.     

An experimental investigation of the partitioning of REE between garnet and liquid with reference to the role of defect equilibria

The partitioning of samarium and thulium between garnets and melts in the systems Mg₃Al₂-Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D _Sm (D _Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D _Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10^–13 cm² s^–1 at 1,300 ° C and 2 × 10^–12 cm² s^–1 at 1,500 ° C, and for grossular, 8.3 × 10^–12 cm² s^–1 at 1,200 ° C and 4.6 × 10^–11 cm² s^–1 at 1,300 ° C. The equilibrium values of D _Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D _Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm₃Al₅O₁₂ in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) D_REE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg₃Al₂Si₃O₁₂-H₂O at low Sm concentrations. These change D _Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature.     

Compositional dependence of REE partitioning between diopside and melt at 1 atmosphere

The effects of composition on pyroxene-melt partitioning of several REE (rare earth elements), Y, and Sr were experimentally evaluated. Using the synthetic model systems anorthite–diopside, diopside–titanite and anorthite–diopside–titanite different diopsides were grown at atmospheric conditions in a double-ellipsoid mirror furnace. The single samples were melted and crystallised in a Pt/Au crucible with compositions corresponding to the invariant points of these systems. Rotational motion with approximately 25 rpm around the longitudinal axis of the crucible increases the prevailing convection flows. By this means, the exclusively diffusional transport of assembly groups onto the growing crystals is avoided. Quenching is achieved by dropping the crucible into water. Crystals up to 2 mm were obtained and analysed by electron microprobe. No inhomogeneities or compositional zonation, either in the diopsides or in the coexisting melts, were observed within the analytical uncertainty of the electron microprobe. The crystallised diopsides occur as both euhedral single crystals and large symplectitic lamellar intergrowths with anorthite or titanite. The chemical homogeneity and the texture indicate near-equilibrium conditions. The analyses show strong positive correlations between D_REE and tetrahedrally coordinated Al in diopside but are not affected by octahedral Al or Ti-concentration. By means of correlations and mass balances the incorporation of REE can be described by 2 different coupled substitutions:

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.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

High-precision high field strength element partitioning between garnet, amphibole and alkaline melt from Kakanui, New Zealand

The high field strength elements (HFSE: Zr, Hf, Nb, Ta, and W) are an important group of chemical tracers that are increasingly used to investigate magmatic differentiation processes. Successful modeling of these processes requires the availability of accurate mineral-melt partition coefficients (D). To date, these have largely been determined by ion microprobe or laser ablation-ICP-MS analyses of the run products of high-pressure, high-temperature experiments. Since HFSE are (highly) incompatible, relatively immobile, high-charge, and difficult to ionize, these experiments and their analysis are challenging. Here we explore whether high-precision analyses of natural mineral-melt systems can provide additional constraints on HFSE partitioning.The HFSE concentrations in natural garnet and amphibole and their alkaline host melt from Kakanui, New Zealand are determined with high precision isotope dilution on a multi-collector-ICP-MS. Major and trace element compositions combined with Lu-Hf isotopic systematics and detailed petrographic sample analysis are used to assess mineral-melt equilibrium and to provide context for the HFSE D measurements. The whole-rock nephelinite, ∼1 mm sized amphiboles in the nephelinite, and garnet megacrysts have similar initial Hf isotope ratios with a mean initial ¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282900 ± 0.000026 (2σ). In contrast, the amphibole megacrysts are isotopically distinct (¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282830 ± 0.000011). Rare earth element D values for garnet megacryst-nephelinite melt and ∼1 mm amphibole-nephelinite melt plotted as a function of ionic radii show classic near-parabolic trends that are in excellent agreement with crystal lattice-strain models. These observations are consistent with equilibrium between the whole-rock nephelinite, the ∼1 mm amphibole grains within the nephelinite and the garnet megacrysts.High-precision isotope dilution results for Zr and Hf in garnet (D_Zr = 0.220 ± 0.007 and D_Hf = 0.216 ± 0.005 [2σ]), and for all HFSE in amphibole are consistent with previous experimental findings. However, our measurements for Nb and Ta in garnet (D_Nb = 0.0007 ± 0.0001 and D_Ta = 0.0011 ± 0.0006 [2σ]) show that conventional methods may overestimate Nb and Ta concentrations, thereby overestimating both Nb and Ta absolute D values for garnet by up to 3 orders of magnitude and underestimating D_Nb/D_Ta by greater than a factor of 100. As a consequence, the role of residual garnet in imposing Nb/Ta fractionation may be less important than previously thought. Moreover, garnet D_Hf/D_W = 17 and D_Nb/D_Zr = 0.003 imply fractionation of Hf from W and Nb from Zr upon garnet crystallization, which may have influenced short-lived ¹⁸²Hf-¹⁸²W and ⁹²Nb-⁹²Zr isotopic systems in Hadean time.     

Experimental study of polybaric REE partitioning between olivine, pyroxene and melt of the Yamato 980459 composition: Insights into the petrogenesis of depleted shergottites

A synthetic composition representing the Yamato 980459 martian basalt (shergottite) has been used to carry out phase relation, and rare earth element (REE) olivine and pyroxene partitioning experiments. Yamato 980459 is a sample of primitive basalt derived from a reduced end-member among martian mantle sources. Experiments carried out between 1-2 GPa and 1350-1650 °C simulate the estimated pressure-temperature conditions of basaltic melt generation in the martian mantle. Olivine-melt and orthopyroxene-melt partition coefficients for La, Nd, Sm, Eu, Gd and Yb (D_REE values) were determined by LA-ICPMS, and are similar to the published values for terrestrial basaltic systems. We have not detected significant variation in D-values with pressure over the range investigated, and by comparison with previous studies carried out at lower pressure.We apply the experimentally obtained olivine-melt and orthopyroxene-melt D_REE values to fractional crystallization and partial melting models to develop a three-stage geochemical model for the evolution of martian meteorites. In our model we propose two ancient (∼4.535 Ga) sources: the Nakhlite Source, located in the shallow mantle, and the Deep Mantle Source, located close to the martian core-mantle boundary. These two sources evolved distinctly on the ε¹⁴³Nd evolution curve due to their different Sm/Nd ratios. By partially melting the Nakhlite Source at ∼1.3 Ga, we are able to produce a slightly depleted residue (Nakhlite Residue). The Nakhlite Residue is left undisturbed until ∼500 Ma, at which point the depleted Deep Mantle Source is brought up by a plume mechanism carrying with it high heat flow, melts and isotopic signatures of the deep mantle (e.g., ε¹⁸²W, ε¹⁴²Nd, etc.). The plume-derived Deep Mantle Source combines with the Nakhlite Residue producing a mixture that becomes a mantle source (herein referred to as “the Y98 source”) for Yamato 980459 and the other depleted shergottites with the characteristic range of Sm/Nd ratios of these meteorites. The same hot plume provides a heat source for the formation of enriched and intermediate shergottites. Our model reproduces the REE patterns of nakhlites and depleted shergottites and can explain high ε¹⁴³Nd in depleted shergottites. Furthermore, the model results can be used to interpret whole rock Rb-Sr and Sm-Nd ages of shergottites.     

Magmatic evolution of the differentiated ultramafic, alkaline and carbonatite intrusion of Vuoriyarvi (Kola Peninsula, Russia). A LA-ICP-MS study of apatite

The nature of the petrogenetic links between carbonatites and associated silicate rocks is still under discussion (i.e., [Gittins J., Harmer R.E., 2003. Myth and reality of the carbonatite–silicate rock “association”. Period di Mineral. 72, 19–26.]). In the Paleozoic Kola alkaline province (NW Russia), the carbonatites are spatially and temporally associated to ultramafic cumulates (clinopyroxenite, wehrlite and dunite) and alkaline silicate rocks of the ijolite–melteigite series [(Kogarko, 1987), (Kogarko et al., 1995), (Verhulst et al., 2000), (Dunworth and Bell, 2001) and (Woolley, 2003)]. In the small (≈ 20 km²) Vuoriyarvi massif, apatite is typically a liquidus phase during the magmatic evolution and so it can be used to test genetic relationships. Trace elements contents have been obtained for both whole rocks and apatite (by LA-ICP-MS). The apatites define a single continuous chemical evolution marked by an increase in REE and Na (belovite-type of substitution, i.e., 2Ca²⁺ = Na⁺ + REE³⁺). This evolution possibly reflects a fractional crystallisation process of a single batch of isotopically homogeneous, mantle-derived magma.The distribution of REE between apatite and their host carbonatite have been estimated from the apatite composition of a carbonatite vein, belonging to the Neskevara conical-ring-like vein system. This carbonatite vein is tentatively interpreted as a melt. So, the calculated distribution coefficients are close to partition coefficients. Rare earth elements are compatible in apatite (D > 1) with a higher compatibility for the middle REE (D_Sm : 6.1) than for the light (D_La : 4.1) and the heavy (D_Yb : 1) REE.     

Partitioning of trace elements between carbonate-silicate melts and mantle minerals: Experiment and petrological consequences

The partitioning of a number of trace elements (Ba, Nb, Zr, Y, REE, etc.) between orthopyroxene, garnet, and carbonate-silicate melt was experimentally studied using a belt apparatus at pressures of 3.5–4.2 GPa and temperatures of 1300–1500°C. The experimental products were investigated by electron microprobe analysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The experimental melts varied from carbonatitic (～5 wt % SiO₂) at low temperatures (1300–1350°C) to kimberlitic compositions (30 wt % SiO₂) at high temperatures (1500°C). The partition coefficients of most elements between orthopyroxene and melt (D _i ^Opx/L ) and garnet and melt (D _i ^Grt/L ) were almost independent of melt composition (temperature). The D _i ^Opx/L values ranged from <0.01 for the most incompatible Ba and light REE to 0.02–0.08 for moderately incompatible Zr, Y, and heavy REE. The D _i ^Grt/L values were approximately an order of magnitude higher, ～0.07 for light REE, 0.7 for Y, and 1.5 for Yb. The character of D _i ^Grt/L variations in the systems studied is in general similar to that established for silicate melts without volatile components. However, the differences in the behavior of moderately incompatible and compatible elements (e.g., light and heavy REE) in the experimental systems are less pronounced compared with CO₂-free systems. Considering carbonate-silicate and silicate melts as possible agents of mantle metasomatism, it can be concluded that the former can efficiently transport heavy REE, and the latter have a greater affinity for Nb, Ba, and light REE. A characteristic feature of mantle rocks enriched by carbonate-silicate melts is high Ba/La ratio coupled with relatively weakly fractionated REE distribution patterns. It was shown that the high degrees of enrichment observed in natural kimberlites can be explained by a two-stage scenario, including a preliminary invasion of carbonate-silicate melt into depleted harzburgites in the lower parts of the lithosphere and subsequent very low degree melting.     

Trace element distribution in Central Dabie eclogites

Coesite-bearing eclogites from Dabieshan (central China) have been studied by ion microprobe to provide information on trace element distributions in meta-basaltic mineral assemblages during high-pressure metamorphism. The primary mineralogy (eclogite facies) appears to have been garnet and omphacite, usually with coesite, phengite and dolomite, together with high-alumina titanite or rutile, or both titanite and rutile; kyanite also occurs occasionally as an apparently primary phase. It is probable that there was some development of quartz, epidote and apatite whilst the rock remained in the eclogite facies. A later amphibolite facies overprint led to partial replacement of some minerals and particularly symplectitic development after omphacite. They vary from very fine-grained dusty-looking to coarser grained Am + Di + Pl symplectites. The eclogite facies minerals show consistent trace element compositions and partition coefficients indicative of mutual equilibrium. Titanite, epidote and apatite all show high concentrations of REE relative to clinopyroxene. The compositions of secondary (amphibolite facies) minerals are clearly controlled by local rather than whole-rock equilibrium, with the composition of amphibole in particular depending on whether it is replacing clinopyroxene or garnet. REE partition coefficients for Cpx/Grt show a dependence on the Ca content of the host phases, with D _REE ^Cpx/Grt decreasing with decreasing D _Ca . This behaviour is very similar to that seen in mantle eclogites, despite differences in estimated temperatures of formation of 650–850 °C (Dabieshan) and 1000–1200 °C (mantle eclogites). With the exception of HREE in garnet, trace elements in the eclogites are strongly distributed in favour of minor or accessory phases. In particular, titanite and rutile strongly concentrate Nb and Zr, whilst LREE–MREE go largely into epidote, titanite and apatite. If these minor/accessory minerals behave in a refractory manner during melting or fluid mobilisation events and do not contribute to the melt/fluid, then the resultant melts and fluids will be strongly depleted in LREE–MREE. Received: 11 February 1999 / Accepted: 31 January 2000