Extension of lattice strain theory to mineral/mineral rare-earth element partitioning: An approach for assessing disequilibrium and developing internally consistent partition coefficients between olivine, orthopyroxene, clinopyroxene and basaltic melt

Olivine/melt and orthopyroxene/melt rare-earth element (REE) partition coefficients consistent with clinopyroxene/melt partition coefficients were determined indirectly from subsolidus partitioning between olivine, orthopyroxene, and clinopyroxene after suitable correction for temperature. Heavy- and middle-REE ratios for olivine/clinopyroxene and orthopyroxene/clinopyroxene pairs correlate negatively with effective cationic radius, whereas those for the light REEs correlate positively with cationic radius, generating a U-shaped pattern in apparent mineral/clinopyroxene partition coefficients versus cationic radius. Lattice strain models of partitioning modified for subsolidus conditions yield negative correlations of olivine/clinopyroxene and orthopyroxene/clinopyroxene with respect to cationic radii, predicting well the measured partitioning behaviors of the heavy and middle REEs but not that of the light REEs. The light-REE systematics cannot be explained with lattice strain theory and, instead, can be explained by disequilibrium enrichment of the light REEs in melt inclusions or on the rims of olivine and orthopyroxene. Realistic light-REE partition coefficients were thus extrapolated from the measured heavy- and middle-REE partition coefficients using the lattice strain model. Light REE olivine/melt and orthopyroxene/melt partition coefficients calculated in this manner are lower than most published values, but agree reasonably well with partitioning experiments using the most recent in situ analytical techniques (secondary-ionization mass spectrometry and laser ablation inductively coupled plasma mass spectrometry). These new olivine/melt and orthopyroxene/melt partition coefficients are useful for accurate modeling of the REE contents of clinopyroxene-poor to -free lithologies, such as harzburgitic residues of melting. Finally, the application of the lattice strain theory to subsolidus conditions represents a framework for assessing the degree of REE disequilibrium in a rock.     

LA-ICPMS analyses of silicate melt inclusions in co-precipitated minerals: Quantification, data analysis and mineral/melt partitioning

We present a new approach to determine the composition of silicate melt inclusions (SMI) using LA-ICPMS. In this study, we take advantage of the occurrence of SMI in co-precipitated mineral phases to quantify their composition without depending on additional sources of information. Quantitative SMI analyses are obtained by assuming that the ratio of selected elements in SMI trapped in different phases are identical. In addition Fe/Mg exchange equilibrium between olivine and melt was successfully used to quantify LA-ICPMS analyses of SMI in olivine. Results show that compositions of SMI from the different host minerals are identical within their uncertainty. Thus (1) the quantification approach is valid; (2) analyses are not affected by the composition of the host phase; (3) the derived melt compositions are representative of the original melt, excluding significant syn- or postentrapment modification such as boundary layer effects or diffusive reequilibration with the host mineral. With this data we established a large dataset of mineral/melt partition coefficients for the investigated mineral phases in hydrous calc-alkaline basaltic-andesitic melts. The clinopyroxene/melt and plagioclase/melt partition coefficients are consistent with the lattice strain model of Blundy and Wood [Blundy, J., Wood B., 1994. Prediction of crystal-melt partition-coefficients from elastic-moduli. Nature372, 452-454].     

Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

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

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

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.     

Constraints from melt inclusions and their host olivines on the petrogenesis of Oligocene-Early Miocene Xindian basalts, Chifeng area, North China Craton

The geochemical characteristics of melt inclusions and their host olivines provide important information on the processes that create magmas and the nature of their mantle and crustal source regions. We report chemical compositions of melt inclusions, their host olivines and bulk rocks of Xindian basalts in Chifeng area, North China Craton. Compositions of both bulk rocks and melt inclusions are tholeiitic. Based on petrographic observations and compositional variation of melt inclusions, the crystallizing sequence of Xindian basalts is as follows: olivine (at MgO > ~5.5 wt%), plagioclase (beginning at MgO = ~5.5 wt%), clinopyroxene and ilmenite (at MgO < 5.0 wt%). High Ni contents and Fe/Mn ratios, and low Ca and Mn contents in olivine phenocrysts, combining with low CaO contents of relatively high MgO melt inclusions (MgO > 6 wt%), indicate that Xindian basalts are possibly derived from a pyroxenite source rather than a peridotite source. In the CS-MS-A diagram, all the high MgO melt inclusions (MgO > 6.0 wt%) project in the field between garnet + clinopyroxene + liquid and garnet + clinopyroxene + orthopyroxene + liquid near 3.0 GPa, further suggesting that residual minerals are mainly garnet and clinopyroxene, with possible presence of orthopyroxene, but without olivine. Modeling calculations using MELTS show that the water content of Xindian basalts is 0.3–0.7 wt% at MgO = 8.13 wt%. Using 20–25 % of partial melting estimated by moderately incompatible element ratios, the water content in the source of Xindian basalts is inferred to be ≥450 ppm, much higher than 6–85 ppm in dry lithospheric mantle. The melting depth is inferred to be ~3.0 GPa, much deeper than that of tholeiitic lavas (<2.0 GPa), assuming a peridotite source with a normal mantle potential temperature. Such melting depth is virtually equal to the thickness of lithosphere beneath Chifeng area (~100 km), suggesting that Xindian basalts are derived from the asthenospheric mantle, if the lithospheric lid effect model is assumed.     

The influence of melt structure on trace element partitioning near the peridotite solidus

This experimental study examines the mineral/melt partitioning of Na, Ti, La, Sm, Ho, and Lu among high-Ca clinopyroxene, plagioclase, and silicate melts analogous to varying degrees of peridotite partial melting. Experiments performed at a pressure of 1.5 GPa and temperatures of 1,285 to 1,345 °C produced silicate melts saturated with high-Ca clinopyroxene, plagioclase and/or spinel, and, in one case, orthopyroxene and garnet. Partition coefficients measured in experiments in which clinopyroxene coexists with basaltic melt containing ~18 to 19 wt% Al₂O₃ and up to ~3 wt% Na₂O are consistent with those determined experimentally in a majority of the previous studies, with values of ~0.05 for the light rare earths and of ~0.70 for the heavy rare earths. The magnitudes of clinopyroxene/melt partition coefficients for the rare earth elements correlate with pyroxene composition in these experiments, and relative compatibilities are consistent with the effects of lattice strain energy. Clinopyroxene/melt partition coefficients measured in experiments in which the melt contains ~20 wt% Al₂O₃ and ~4 to 8 wt% Na₂O are unusually large (e.g., values for Lu of up to 1.33±0.05) and are not consistent with the dependence on pyroxene composition found in previous studies. The magnitudes of the partition coefficients measured in these experiments correlate with the degree of polymerization of the melt, rather than with crystal composition, indicating a significant melt structural influence on trace element partitioning. The ratio of non-bridging oxygens to tetrahedrally coordinated cations (NBO/T) in the melt provides a measure of this effect; melt structure has a significant influence on trace element compatibility only for values of NBO/T less than ~0.49. This result suggests that when ascending peridotite intersects the solidus at relatively low pressures (~1.5 GPa or less), the compatibility of trace elements in the residual solid varies significantly during the initial stages of partial melting in response to the changing liquid composition. It is unlikely that this effect is important at higher pressures due to the increased compatibility of SiO₂, Na₂O, and Al₂O₃ in the residual peridotite, and correspondingly larger values of NBO/T for small degree partial melts.Editorial responsibility: T.L. Grove     

Trace element abundances in megacrysts and their host basalts: Constraints on partition coefficients and megacryst genesis

In an effort to obtain information about mineral/melt trace element partitioning during the high pressure petrogenesis of basic rocks, we determined rare earth and other trace element abundances in megacrysts of clinopyroxene, orthopyroxene, amphibole, mica, anorthoclase, apatite and zircon, and in their host basalts. In general, the ranges of mineral/melt partition coefficients established from experimental partitioning studies and phenocryst/matrix measurements overlap with the ranges of megacryst/host abundance ratios. Our data for Hf, Sc, Ta and Th partitioning represent some of the only estimates available. Consideration of phase equilibria, major element partitioning and isotopic ratios indicate that most of the pyroxene and amphibole megacrysts may have been in equilibrium with their host magmas at high pressures (mostly 10–25 kb). In contrast, it is unlikely that mica, anorthoclase, apatite and zircon megacrysts formed in equilibrium with their host basalts; instead, we conclude that they were precipitated from more evolved magmas and have been mixed into their present host magmas. Consequently, the trace element abundance ratios for megacryst/host should not be interpreted as partition coefficients, but only as guides for understanding trace element partitioning during high pressure petrogenesis. With this caveat, we conclude that the megacryst/ host trace element abundance data indicate that mineral/melt partition coefficients in basaltic systems during high pressure fractionation are not drastically different from partition coefficients valid for low pressure fractionation.     

Experimentally determined mineral-melt partition coefficients for Sc,Y and REE for olivine,orthopyroxene, pigeonite,magnetite and ilmenite

Our current lack of understanding of the partitioning behavior of Sc, Y and the REE (rare-earth elements) can be attributed directly to the lack of a sufficiently large or chemically diverse experimental data set. To address this problem, we conducted a series of experiments using several different natural composition lavas, doped with the elements of interest, as starting compositions. Microprobe analyses of orthopyroxene, pigeonite, olivine, magnetite, ilmenite and co-existing glasses in the experimental charges were used to calculate expressions that describe REE partitioning as a function of a variety of system parameters. Using expressions that represent mineral-melt reactions (versus element ratio distribution coefficients) it is possible to calculate terms that express low-Ca pyroxene-melt partitioning behavior and are independent of both pyroxene and melt composition. Compositional variations suggest that Sc substitution in olivine involves either a paired substitution with Al or, more commonly, with vacancies. The partitioning of Sc is dependent both on melt composition and temperature. Our experimentally determined olivine-melt REE Ds (partition coefficients) are similar to, but slightly higher than those reported by McKay (1986) and support their conclusions that olivines are strongly LREE depleted. Y and REE mineral/melt partition coefficients for magnetite range from 0.003 for La to 0.02 for Lu. Ilmenite partition coefficients range from 0.007 for La to 0.029 for Lu. These experimental values are two orders of magnitude lower than many of the published values determined by phenocryst/matrix separation techniques.     

Metasomatism in mantle xenoliths from the Letlhakane kimberlites: estimation of element fluxes

A suite of metasomatised xenoliths from the Letlhakane kimberlite (Botswana) forms a metasomatic sequence from garnet peridotite to garnet phlogopite peridotite to phlogopite peridotite. Before the modal metasomatism, most of the Letlhakane xenoliths were depleted harzburgites that had been subjected to an earlier cryptic metasomatic event. Modal phlogopite and clinopyroxene - Cr-spinel increase at the expense of garnet and orthopyroxene with increasing degrees of metasomatism. The most metasomatised xenolith is a wehrlite. With progressive modal metasomatism, the clinopyroxene becomes enriched in Sr, Sc and the LREE, orthopyroxene becomes depleted in Ca and Ni, but enriched in Al and Mn, and olivine becomes depleted in Al and V. Garnet chemical composition largely remains unchanged. The garnet replacement reaction seen in most xenoliths allows the measurement of the flux of trace elements through detailed modal analysis of the pseudomorphs. Mass balance calculations show that the modally metasomatised rocks became enriched in incompatible elements such as Sr, Na, K, the LREE and the HFSE (Ti, Zr and Nb). Major elements (Al, Cr and Fe) and garnet-compatible trace elements (V, Y, Sc, and the HREE) were removed during this metasomatic process. The modal metasomatism caused a strong depletion in Al, and the results challenge previous suggestions that this metasomatic process merely occurred within an Al-poor environment. The data suggest that the xenoliths represent the mantle wallrock adjacent to a major conduit for an alkaline basic silicate melt (with high contents of volatile and incompatible elements). The volatile and incompatible element-enriched component of this melt percolated into the wallrock along a strong temperature gradient and caused the observed range of metasomatism.     

Rare earth element partitioning between minerals from anhydrous spinel peridotite xenoliths

REE abundances in minerals from spinel peridotite xenoliths from West Germany, the south-western U.S. and Mongolia decrease in the order clinopyroxene > orthopyroxene > olivine > spinel. While clinopyroxenes are similar in absolute chondrite-normalized concentrations to those known from other studies, orthopyroxenes and olivines are significantly lower in LREE although comparable in HREE. Spinels are much lower in all REE than any previously reported values and are completely negligible for the REE budget of peridotites.Partition coefficients for most orthopyroxene/clinopyroxene pairs increase systematically from La to Lu. Olivine/clinopyroxene and spinel/clinopyroxene partition coefficients increase from the intermediate rare earth elements to Lu and normally are higher for La compared to Sm.The application of Nagasawa's (1966) elastic lattice model suggests that all heavy but only minor amounts of the light REE substitute into structural positions of orthopyroxene and olivine.Significant differences between orthopyroxene/clinopyroxene partition coefficients for various xenoliths may be assigned to dependences upon equilibration temperature and bulk chemistry.Apart from grain surface contaminations, fluid inclusions which are practically always present in mantle minerals, can highly concentrate light rare earth elements and thus may be responsible for unexpectedly high concentrations of incompatible elements frequently reported for mantle olivines or orthopyroxenes.     

Fluid and melt inclusions in the Mesozoic Fangcheng basalt from North China Craton: implications for magma evolution and fluid/melt-peridotite reaction

Melt inclusions and fluid inclusions in the Fangcheng basalt were investigated to understand the magma evolution and fluid/melt-peridotite interaction. Primary silicate melt inclusions were trapped in clinopyroxene and orthopyroxene phenocrysts in the Fangcheng basalt. Three types of melt inclusions (silicate, carbonate, and sulfide) coexisting with fluid inclusions occur in clinopyroxene xenocrysts and clinopyroxene in clinopyroxenite xenoliths. In situ laser-ablation ICP-MS analyses of major and trace element compositions on individual melt inclusions suggest that the silicate melt inclusions in clinopyroxene and orthopyroxene phenocrysts were trapped from the same basaltic magma. The decoupling of major and trace elements in the melt inclusions indicates that the magma evolution was controlled by melt crystallization and contamination from entrapped ultramafic xenoliths. Trace element patterns of melt inclusions are similar to those of the average crust of North China Craton and Yangtze Craton, suggesting a considerable crustal contribution to the magma source. Calculated parental melt of the Fangcheng basalt has features of low MgO (5.96 wt%), high Al₂O₃ (16.81 wt%), Sr (1,670 ppm), Y (>35 ppm), and high Sr/Y (>40), implying that subducted crustal material was involved in the genesis of the Fangcheng basalt. The coexisting fluid and melt inclusions in clinopyroxene xenocrysts and in clinopyroxene of xenoliths record a rare melt-peridotite reaction, that is olivine + carbonatitic melt₁ (rich in Ca) = clinopyroxene + melt₂ ± CO₂. The produced melt₂ is enriched in LREE and CO₂ and may fertilize the mantle significantly, which we consider to be the cause for the rapid replacement of lithospheric mantle during the Mesozoic in the region.     

SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1080–1200°C

Trace element partition coefficients (D's) for up to 13 REE, Nb, Ta, Zr, Hf, Sr and Y have been determined by SIMS analysis of seven garnets, four clinopyroxenes, one orthopyroxene and one phlogopite crystallized from an undoped basanite and a lightly doped (200 ppm Nb, Ta and Hf) quartz tholeiite. Experiments were conducted at 2–7.5 GPa, achieving near-liquidus crystallization at relatively low temperatures of 1080–1200°C under strongly hydrous conditions (5–27 wt.% added water). Garnet and pyroxene D_REE show a parabolic pattern when plotted against ionic radius, and conform closely to the lattice strain model of Blundy and Wood (Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454). Comparison, at constant pressure, between hydrous and anhydrous values of the strain-free partition coefficient (D₀) for the large cation sites of garnet and clinopyroxene reveals the relative importance of temperature and melt water content on partitioning. In the case of garnet, the effect of lower temperature, which serves to increase D₀, and higher water content, which serves to decrease D₀, counteract each other to the extent that water has little effect on garnet–melt D₀ values. In contrast, the effect of water on clinopyroxene–melt D₀ overwhelms the effect of temperature, such that D₀ is significantly lower under hydrous conditions. For both minerals, however, the lower temperature of the hydrous experiments tends to tighten the partitioning parabolas, increasing fractionation of light from heavy REE compared to anhydrous experiments.

Three sets of near-liquidus clinopyroxene–garnet two-mineral D values increase the range of published experimental determinations, but show significant differences from natural two-mineral D's determined for subsolidus mineral pairs. Similar behaviour is observed for the first experimental data for orthopyroxene–clinopyroxene two-mineral D's when compared with natural data. These differences are in large part of a consequence of the subsolidus equilibration temperatures and compositions of natural mineral pairs. Great care should therefore be taken when using natural mineral–mineral partition coefficients to interpret magmatic processes.

The new data for strongly hydrous compositions suggest that fractionation of Zr–Hf–Sm by garnet decreases with increasing depth. Thus, melts leaving a garnet-dominated residuum at depths of about 200 km or greater may preserve source Zr/Hf and Hf/Sm. This contrasts with melting at shallower depths where both garnet and clinopyroxene will cause Zr–Hf–Sm fractionation. Also, at shallower depths, clinopyroxene-dominated fractionation may produce a positive Sr spike in melts from spinel lherzolite, but for garnet lherzolite melting, no Sr spike will result. Conversely, clinopyroxene megacrysts with negative Sr spikes may crystallize from magmas without anomalous Sr contents when plotted on mantle compatibility diagrams. Because the characteristics of strongly hydrous silicate melt and solute-rich aqueous fluid converge at high pressure, the hydrous data presented here are particularly pertinent to modelling processes in subduction zones, where aqueous fluids may have an important metasomatic role.     

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 cpx/melt partitioning of 24 trace elements

Cpx/melt partition coefficients have been determined by ion probe for 24 trace elements at natural levels in an alkali basalt experimentally equilibrated at 1,380°C and 3 GPa. One goal was to intercompare Ds for both high-field-strength elements and rare earth elements (REE) in a single experiment. Relative to the REE spidergram, Hf and Ti show virtually no anomaly, whereas Zr exhibits a major negative anomaly. Other incompatible elements (Ba, K, Nb) fall in the range of published values, as do elements such as Sr, Y, Sc, Cr and V. Pb shows a value intermediate between La and Ce. Values for Be, Li and Ga are reported for the first time, and show that Be is as incompatible as the light REEs whereas Li and Ga are somewhat more compatible than the heavy REE.     

Zirconolite-bearing ultra-potassic veins in a mantle-xenolith from Mt. Melbourne Volcanic Field,Victoria Land,Antarctica

One mantle xenolith from a basanite host of the Mt. Melbourne Volcanic Field (Ross Sea Rift) is extraordinary in containing veins filled with leucite, plagioclase, clinopyroxene, nepheline, Mg-ilmenite, apatite, titaniferous mica, and the rare mineral zirconolite. These veins show extensive reaction with the dunitic or lherzolitic host (olivine+spinel+orthopyroxene+clinopyroxene). The reaction areas contain skeletal olivine and diopside crystals, plagioclase, phlogopite, aluminous spinel and ilmenite in a fine grained groundmass of aluminous spinel, clinopyroxene, olivine, plagioclase and interstitial leucite. The vein composition estimated from modal abundances and microprobe analyses is a mafic leucite-phonolite with high amounts of K, Al, Ti, Zr and Nb but low volatile contents. The melt is unrelated to the host basanite and was probably derived by smallscale melting of incompatible element-enriched phlogopite-bearing mantle material and must have lost most of its volatile content during migration, crystallization and reaction with the host dunite. While the veins are completely undeformed the dunitic host shows slight deformation. Vein minerals crystallized at high temperatures above 1000°C and pressures below 5 kbar according to the phase assemblage including leucite, nepheline and K-feldspar. Spinel/olivine geothermometry yielded 800–920°C for the re-equilibration of the host peridotite. Thus the xenolith must have been at shallow depth prior to and during the late veining event. Mantle material at shallow depths is consistent with rifting and the regional extreme displacement at the transition from the rifted Victoria Land Basin in the Ross Sea to the uplifted Trans-Antarctic Mountains.     

Mantle metasomatism and magma formation in continental lithosphere: Data on xenoliths in alkali basalts from the Makhtesh Ramon,Negev desert,Israel

Mantle xenoliths (lherzolites, clinopyroxene dunites, wehrlites, and clinopyroxenites) in the Early Cretaceous volcanic rocks of Makhtesh Ramon (alkali olivine basalts, basanites, and nephelinites) represent metasomatized mantle, which served as a source of basaltic melts. The xenoliths bear signs of partial melting and previous metasomatic transformations. The latter include the replacement of orthopyroxene by clinopyroxene in the lherzolites and, respectively, the wide development of wehrlites and olivine clinopyoroxenites. Metasomatic alteration of the peridotites is accompanied by a sharp decrease in Mg, Cr, and Ni, and increase of Ti, Al, Ca contents and ³⁺Fe/²⁺Fe ratio, as well as the growth of trace V, Sc, Zr, Nb, and Y contents. The compositional features of the rocks such as the growth of ³⁺Fe/²⁺Fe and the wide development of Ti-magnetite in combination with the complete absence of sulfides indicate the high oxygen fugacity during metasomatism and the low sulfur concentration, which is a distinctive signature of fluid mode during formation of the Makhtesh Ramon alkali basaltic magma. Partial melting of peridotites and clinopyroxenites is accompanied by the formation of basanite or alkali basaltic melt. Clino- and orthopyroxenes are subjected to melting. The crystallization products of melt preserved in the mantle rock are localized in the interstices and consist mainly of fine-grained clinopyroxene, which together with Ti-magnetite, ilmenite, amphibole, rhenite, feldspar, and nepheline, is cemented by glass corresponding to quartz–orthopyroxene, olivine–orthopyroxene, quartz–feldspar, or nepheline–feldspar mixtures of the corresponding normative minerals. The mineral assemblages of xenoliths correspond to high temperatures. The high-Al and high-Ti clinopyroxene, calcium olivine, feldspar, and feldspathoids, amphibole, Ti-magnetite, and ilmenite are formed at 900–1000°. The study of melt and fluid inclusions in minerals from xenoliths indicate liquidus temperatures of 1200–1250°C, solidus temperatures of 1000–1100°C, and pressure of 5.9–9.5 kbar. Based on the amphibole–plagioclase barometer, amphibole and coexisting plagioclase were crystallized in clinopyroxenites at 6.5–7.0 kbar.     

OUTLINE OF THE GEOLOGY OF KOREA

A database on a number of elements in oceanic volcanic rocks is presented, including the principal major-element oxides-SiO₂, TiO₂, Al₂O₃, Fe₂O₃(T), MnO, MgO, CaO, Na₂O, K₂O, and P₂O₅ (where T refers to total iron)–and the trace elements–Ba, Ce, Cr, Cu, Ni, Sc, Sr, V, Pb (mainly by isotope dilution), Yb, Zn, and Zr. Interpretations are given for transition metals, with emphasis on Mn, Sc, and V, in order to determine the concentration of the elements in primitive melts and assess their trends in magmatic differentiation. Transition metals are not enriched in plagioclase, so all are incompatible with pure plagioclase removal–that is, they become enriched in the melt. Both Cr and Ni are known to be highly compatible with olivine separation-i.e., they are depleted in the melt early in differentiation. Also, Sc is compatible with clinopyroxene (Cpx) removal from the melt and is depleted by separation of Cpx. Copper does not fit well in any of the principal silicates, but Cu, like Ni, is greatly enriched in sulfides that may remain in the source or separate from the magma. Decreasing Ni abundances and increasing Cu contents during differentiation are a sign of olivine separation. In the analysis presented herein, V–in the absence of Cpx separation–is found to behave remarkably like the moderately incompatible element Zn, and these two elements add to the list of element pairs of similar incompatibility whose ratios are insensitive to differentiation and to submarine weathering as well. Both are enhanced in titanomagnetite, so both would be compatible during titanomagnetite separation. When Cpx separates, however, V becomes compatible like Sc, but Zn remains incompatible. Thus, decreasing V (and Sc) contents and increasing Zn contents during differentiation are a sign of Cpx separation. Manganese often behaves much like Zn and therefore is moderately incompatible, but Mn is less compatible than Zn and V in titanomagnetite. Thus, decreasing Zn and V with increasing Mn is an indication of titanomagnetite removal. Dual compatible and incompatible trends with differentiation are found chiefly for Cu, Sc, and Sr. Distinguishing mid-ocean ridge basalts (MORB), oceanic-island volcanic rocks (OIV), and island-arc volcanic rocks (IAV) may be accomplished by plots of Ce/Yb versus Ba/Ce, where OIV plot to higher values of Ce/Yb than do MORB, and IAV data plot to higher values of Ba/Ce than do those of MORB. These ratios do not seem to be significantly affected by submarine weathering.     

Subsolidus reactions monitored by trace element partitioning: the spinel- to plagioclase-facies transition in mantle peridotites

Mantle peridotites of the External Liguride (EL) Units (Northern Apennines) mainly consist of fertile spinel-lherzolites partially recrystallized to plagioclase-facies assemblages, and are consequently appropriate to investigate the interphase element partitioning related to the transition from spinel- to plagioclase-facies stability field. Evidence for the development of the plagioclase-facies assemblage is mainly given by: (1) large exsolution lamellae of orthopyroxene and plagioclase within spinel-facies clinopyroxene; (2) plagioclase rims around spinel; (3) granoblastic domains made up of olivine+plagioclase±clino-and orthopyroxene. In situ major and trace [REE (rare-earth elements), Ti, Sc, V, Cr, Sr, Y, Zr and Ba] element mineral analyses have been performed, by electron and ion probe, on selected samples which show the progressive development of the plagioclase-bearing assemblage. The main compositional variations observed during the change from spinel- to plagioclase-facies minerals are as follows: (1) clinopyroxenes decrease in Al, Na, Sr, Eu/Eu^* and increase in Y, V, Sc, Cr, Zr and Ti; (2) amphiboles decrease in Eu/Eu^*, Sr, Ba and increase in Zr and V; (3) spinels decrease in Al and increase in Cr and Ti. The most striking feature is the decoupling in the behaviour of similarly incompatible elements (D about 0.1) in clinopyroxene, e.g. Sr decrease is mirrored by Zr increase. Massbalance calculations indicate that the trace element interphase redistribution documented in the EL peridotites occurred in a closed system and in response to the metamorphic reaction governing the transition from the spinel- to the plagioclase-facies stability field. The observed element partitioning reveals, moreover, that subsolidus re-equilibration processes in the upper mantle produce HFSE (high-field-strength element)/REE fractionation in minerals, which must be evaluated for a reliable determination of mineral-melt distribution coefficients. The results of this study furnish evidence for subsolidus metamorphic evolution during decompression, without concomitant partial melting processes. This is consistent with the interpretation that the EL peridotites represent subcontinental lithospheric mantle emplaced at the surface in response to lithospheric thinning and tectonic denudation mechanisms related to the Triassic-Jurassic rifting of the Ligure-Piedmontese basin.     

Experimental determination of F and Cl partitioning between lherzolite and basaltic melt

We experimentally determined F and Cl partition coefficients together with that of 19 trace elements (including REE, U-Th, HFSE and LILE) between basaltic melt and lherzolite minerals: olivine, orthopyroxene, clinopyroxene, plagioclase and garnet. Under conditions from 8 to 25 kbars and from 1,265 to 1,430°C, compatibilities of F and Cl are globally ordered as D ^Cpx/melt > D ^Opx/melt > D ^Grt/melt > D ^Ol/melt > D ^Plag/melt, and D _F ^mineral/melt is larger than D _Cl^mineral/melt. Four other major results were brought to light. (1) Chlorine partition coefficients positively correlate with the jadeite component in orthopyroxene, and increase of the CaTs component promotes Cl incorporation in clinopyroxene. (2) Variations of fluorine partition coefficients correlate strongly with melt viscosity. (3) F and Cl partition coefficients correlate with the Young’s modulus (E ₀) of pyroxene octahedral sites (M sites) and with Raman vibrational modes of pyroxenes. This demonstrates a fundamental interaction between the M site of pyroxenes and the incorporation of F and Cl. (4) We also determined the parameters of the lattice-strain model applied to 3+ cation trace elements for the two M sites in orthopyroxene and clinopyroxene: D ₀^M1, D ₀^M2, r ₀^M1, r ₀^M2, E ₀^M1 and E ₀^M2.