Partitioning behavior of trace elements between dacitic melt and plagioclase, orthopyroxene, and clinopyroxene based on laser ablation ICPMS analysis of silicate melt inclusions

Partitioning behavior of Sc, Ti, V, Mn, Sr, Y, Zr, Nb, Ba, La, Nd, Sm, Eu, Gd, Dy, Ho, Yb, Hf, and Pb between dacitic silicate melt and clinopyroxene, orthopyroxene, and plagioclase has been determined based on laser ablation-inductively coupled plasma mass spectrometric (LA-ICPMS) analysis of melt inclusions and the immediately adjacent host mineral. Samples from the 1988 eruption of White Island, New Zealand were selected because petrographic evidence suggests that all three mineral phases are in equilibrium with each other and with the melt inclusions. All three phenocryst types are found as mineral inclusions within each of the other phases, and mineral inclusions often coexist with melt inclusions in growth-zone assemblages. Compositions of melt inclusions do not vary between the different host minerals, suggesting that boundary layer processes did not affect compositions of melt inclusions and that post-trapping modifications have not occurred.Partition coefficients were calculated from the host and melt inclusion compositions and results were compared to published values. All trace elements examined in this study except Sr are incompatible in plagioclase, and all measured trace elements except for Mn are incompatible in orthopyroxene. In clinopyroxene, Sc, V, and Mn are compatible, and Y, Ti, HREE, and the MREE are only slightly incompatible. Most partition coefficients overlap the wide range of values reported in the literature, but the White Island data are consistently at the lower end of the range in published values. Results from the literature obtained using modern microanalytical techniques such as secondary ion mass spectrometry (SIMS) or proton induced X-ray emission spectroscopy (PIXE) also fall at the lower end of the published values, whereas partition coefficients determined from bulk analysis of glass and crystals separated from volcanic rocks typically extend to higher values. Rapid crystal growth-rates, crystal zonation, or the presence of accessory mineral inclusions in phenocrysts likely accounts for the wide range and generally higher partition coefficients obtained using bulk sampling techniques. The results for 3+ cations from this study are consistent with theoretical predictions based on a lattice strain model for site occupancy. The results also confirm that the melt inclusion-mineral (MIM) technique is a reliable method for determining partition coefficients, as long as the melt inclusions have not experienced post-entrapment reequilibration.     

The influence of melt composition on the partitioning of REEs, Y, Sc, Zr and Al between forsterite and melt in the system CMAS

Partition coefficients for a range of Rare Earth Elements (REEs), Y, Sc, Al and Zr were determined between forsteritic olivine (nearly end-member Mg₂SiO₄) and ten melt compositions in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS) at 1 bar and 1400 °C, with concentrations of the trace elements in the olivine and the melt measured by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The REEs and Sc were added at levels sufficient to ensure that concentrations in the olivine were well above the detection limits. The REE partition coefficients decrease with increasing silica in the melt, indicating strong bonding between REEO_1.5 and SiO₂ in the melt. The variation of as a function of ionic radius is well described by the Brice equation for each composition, although a small proportion of this variation is due to the increase in the strength of the REEO_1.5-SiO₂ interactions in the melt with ionic radius. Scandium behaves very similarly to the REEs, but a global fit of the data from all ten melt compositions suggests that deviates somewhat from the parabolas established by the REE and Y, implying that Sc may substitute into olivine differently to that of the REEs. In contrast to the behaviour of the large trivalent cations, the concentration of Al in olivine is proportional to the square root of its concentration in the melt, indicating a coupled substitution in olivine with a high degree of short-range order. The lack of any correlation of REE partition coefficients with Al in olivine or melt suggests that the REE substitution in olivine is charge-balanced by cation vacancies. The partition coefficient of the tetravalent trace element Zr, which is highly incompatible in olivine, depends on the CaO content of the melt.     

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.     

Laser-ablation ICP-MS analysis of silicate and sulfide melt inclusions in an andesitic complex I: analytical approach and data evaluation

Quantitative microanalysis of entire silicate and sulfide melt inclusions by Excimer Laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICPMS) has been applied to extrusive and shallow intrusive rocks from the andesitic Farallón Negro Volcanic Complex (northwestern Argentina). Silicate melts are trapped in pyroxene, amphibole, plagioclase and quartz, and sulfide melts are trapped in amphibole. Details of the analytical approach and the quantification procedure are given and the results are evaluated to test the accuracy of the technique and the validity of the interpretation of analytical signals. Similar compositions of silicate melt inclusions trapped in truly co-precipitating minerals show that the quantification approach of melt inclusion compositions from LA-ICPMS signals through an internal standard is valid. This correspondence also shows that melt inclusions investigated in this study are not significantly influenced by the boundary layer around a growing crystal or by post-entrapment modifications. Post-entrapment diffusive re-equilibration only affected the Fe and Mg content of melt inclusions in mafic phases. Thus, melt inclusions are representative samples of the melt from which the host mineral crystallized, with regard to most major and trace elements. Sulfide melt inclusions (present as pyrrhotite with exsolution of Au and Cu in phases separated during cooling) were analyzed for their bulk Fe, Cu and Au content, and the abundance of these elements was quantified using a silicate glass as external standard. The validity of this calibration was tested by comparing electron microprobe analyses of Fe, Cu, Ni and Co in homogeneous sulfide minerals with LA-ICPMS results. Identical results within calculated uncertainty (one standard deviation of five to nine analyses, mostly between 1 and 5 wt% RSD) demonstrate that for these elements, measured element ratios are independent of the matrix using our analytical setup.Editorial responsibility: T.L. Grove     

Evidence for heterogeneous enriched shergottite mantle sources in Mars from olivine-hosted melt inclusions in Larkman Nunatak 06319

Larkman Nunatak (LAR) 06319 is an olivine-phyric shergottite whose olivine crystals contain abundant crystallized melt inclusions. In this study, three types of melt inclusion were distinguished, based on their occurrence and the composition of their olivine host: Type-I inclusions occur in phenocryst cores (Fo_77-73); Type-II inclusions occur in phenocryst mantles (Fo_71-66); Type-III inclusions occur in phenocryst rims (Fo_61-51) and within groundmass olivine. The sizes of the melt inclusions decrease significantly from Type-I (∼150-250 μm diameter) to Type-II (∼100 μm diameter) to Type-III (∼25-75 μm diameter). Present bulk compositions (PBC) of the crystallized melt inclusions were calculated for each of the three melt inclusion types based on average modal abundances and analyzed compositions of constituent phases. Primary trapped liquid compositions were then reconstructed by addition of olivine and adjustment of the Fe/Mg ratio to equilibrium with the host olivine (to account for crystallization of wall olivine and the effects of Fe/Mg re-equilibration). The present bulk composition of Type-I inclusions (PBC1) plots on a tie-line that passes through olivine and the LAR 06319 whole-rock composition. The parent magma composition can be reconstructed by addition of 29 mol% olivine to PBC1, and adjustment of Fe/Mg for equilibrium with olivine of Fo₇₇ composition. The resulting parent magma composition has a predicted crystallization sequence that is consistent with that determined from petrographic observations, and differs significantly from the whole-rock only in an accumulated olivine component (∼10 wt%). This is consistent with a calculation indicating that ∼10 wt% magnesian (Fo_77-73) olivine must be subtracted from the whole-rock to yield a melt in equilibrium with Fo₇₇. Thus, two independent estimates indicate that LAR 06319 contains ∼10 wt% cumulate olivine.The rare earth element (REE) patterns of Type-I melt inclusions are similar to that of the LAR 06319 whole-rock. The REE patterns of Type-II and Type-III melt inclusions are also broadly parallel to that of the whole-rock, but at higher absolute abundances. These results are consistent with an LAR 06319 parent magma that crystallized as a closed-system, with its incompatible-element enrichment being inherited from its mantle source region. However, fractional crystallization of the reconstructed LAR 06319 parent magma cannot reproduce the major and trace element characteristics of all enriched basaltic shergottites, indicating local-to-large scale major- and trace-element variations in the mantle source of enriched shergottites. Therefore, LAR 06319 cannot be parental to the enriched basaltic shergottites.     

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

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

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.     

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.     

The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic 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] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

Constraints on clinopyroxene/melt partitioning of REE, Rb, Sr, Ti, Cr, Zr, and Nb during mantle melting: First insights from direct peridotite melting experiments at 1.0 GPa

Earlier piston-cylinder experiments in our laboratory produced a collection of mantle melting run products at 1.0 GPa that have now been analyzed by ion probe for selected REE, Ti, Cr, Rb, Sr, Y, Zr, and Nb. Natural starting materials were used and experiments were run in graphite-lined Pt capsules with the melt separated from the residual minerals into a layer of vitreous carbon spheres (VCS) to circumvent quench modification. The glass phase in 18 run products, representing melt percentages of ∼2-20 wt%, yielded excellent data that were inverted to yield the first estimates ever of clinopyroxene/melt distribution coefficients, Ds, derived from direct peridotite partial melting experiments. Uncertainties were estimated with a Monte Carlo method.For the REE and Y, these Ds were then compared to Ds calculated with the widely-used model of Wood and Blundy (1997) and the two sets overlap at the ±2σ level in 123 of 128 cases (∼96%). This indicates to us that: 1) the experiments analyzed here are well equilibrated with respect to major and trace element distributions, thus supporting the efficacy of the VCS technique and its variation involving diamond (e.g., Baker and Stolper, “Determining the composition of high-pressure mantle melts using diamond aggregates” [1994], Geochim. Cosmochim. Acta58, 2811-2827); 2) the model of Wood and Blundy (1997), calibrated largely on the basis of large melt fraction, inverse- or sandwich-type experiments, describes REE and Y partitioning during peridotite melting well, even very near the solidus; and it suggests that the cpx/melt Ds derived here for other elements, not modeled by the Wood and Blundy formulation, are probably also correct for peridotite melting to within their ±2σ uncertainties. D^sp/liq and D^cpx/liq values for Cr calculated directly from electron microprobe data decrease by about a factor of five with increasing temperature and melt percentage.The degree to which our experiments appear to have equilibrated seems at odds with recent measurements of the diffusivities of REE in diopside which suggest that relatively small percentages of our starting mineral grains should have equilibrated diffusively. Instead, we suggest that equilibration occurs much more rapidly through the processes of recrystallization and grain coarsening, accomplished through dissolution and reprecipitation. This suggestion is supported by the observation that our final grain sizes are typically 5-10 times larger than the ∼10 μm starting sizes, indicating that substantial mass transfer occurred in our experiments, probably mediated by the melt phase in which diffusion is faster.     

Trace element partitioning in the granulite facies

Analyses of trace elements in the mineral phases of granulites provide important information about the trace element distribution in the lower crust. Since granulites are often considered residues of partial melting processes, trace element characteristics of their mineral phases may record mineral/melt equilibria thus giving an opportunity to understand the nature and composition of melts in the lower continental crust. This study provides an extensive set of mineral trace element data obtained by LA-ICP-MS analyses of mafic and intermediate granulites from Central Finland. Mass balance calculations using the analytical data indicate a pronounced contribution of the accessory minerals apatite for the REE and ilmenite for the HFSE. Coherent mineral/mineral ratios between samples point to a close approach to equilibrium except for minerals intergrown with garnet porphyroblasts. Mineral trace element data were used for the formulation of a set of D ^mineral/melt partition coefficients that is applicable for trace element modelling under lower crustal conditions. D ^mineral/melt were derived by the application of predictive models and using observed constant mineral/mineral ratios. The comparison of the calculated D ^mineral/melt with experimental data as well as the relationship between mineral trace element contents and a leucosome with a composition close to an equilibrium melt provides additional constraints on mineral/melt partitioning. The D values derived in this study are broadly similar to magmatic partition coefficients for intermediate melt compositions. They provide a first coherent set of D values for Sc, V, Cr and Ni between clinopyroxene, amphibole, garnet, orthopyroxene, ilmenite and melt. In addition, they emphasize the strong impact that ilmenite exerts on the distribution of Nb and Ta.     

A possible effect of melt structure on the Mg-Fe partitioning between olivine and melt

Partitioning of Mg and Fe²⁺ between olivine and mafic melts has been determined experimentally for eight different synthetic compositions in the temperature range between 1335 and 1425°C at 0.1 MPa pressure and at fo₂ ∼1 log unit below the quartz-fayalite-magnetite buffer. The partition coefficient [K_D = (Fe²⁺/Mg)^ol/(Fe²⁺/Mg)^melt] increases from 0.25 to 0.34 with increasing depolymerization of melt (NBO/T of melt from 0.25-1.2), and then decreases with further depolymerization of melt (NBO/T from 1.2-2.8). These variations are similar to those observed in natural basalt-peridotite systems. In particular, the variation in NBO/T ranges for basaltic-picritic melts (0.4-1.5) is nearly identical to that obtained in the present experiments. Because the present experiments were carried out at constant pressure (0.1 MPa) and in a relatively small temperature range (90°C), the observed variations of Mg and Fe²⁺ partitioning between olivine and melt must depend primarily on the composition or structure of melt. Such variations of K_D may depend on the relative proportions of four-, five-, and six-coordinated Mg²⁺ and Fe²⁺ in melt as a function of degree of NBO/T.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using 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], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Petrogenesis of Tholeiitic Lavas from the Submarine Hana Ridge, Haleakala Volcano, Hawaii

Hana Ridge, the longest submarine rift zone in the Hawaiianisland chain, extending from Maui 140 km to the ESE, has a complexmorphology compared with other Hawaiian rift zones. A totalof 108 rock specimens have been collected from the submarineHana Ridge by six submersible dives. All of the rocks (76 bulkrocks analyzed) are tholeiitic basalts or picrites. Their majorelement compositions, together with distinctively low Zr/Nb,Sr/Nb, and Ba/Nb, overlap those of Kilauea lavas. In contrast,the lavas forming the subaerial Honomanu shield are intermediatein composition between those of Kilauea and Mauna Loa. The compositionalcharacteristics of the lavas imply that clinopyroxene and garnetwere important residual phases during partial melting. The compositionsof olivine and glass (formerly melt) inclusions imply that regardlessof textural type (euhedral, subhedral–undeformed, deformed)olivine crystallized from host magmas. Using the most forsteriticolivine (Fo_90·6) and partition coefficients     

Thin intergranular melt films and melt pockets in spinel peridotite xenoliths from the Rhön area (Germany): early stage of melt generation by grain boundary melting

Optical microscopy and transmission electron microscopy (TEM) on a porphyroclastic high temperature spinel peridotite from the Rhön area reveal fine, irregular glass layers and pockets along mineral interfaces, cracks in olivine, inside olivine crystals and in spongy rims of clinopyroxene. The chemical composition of the glass deviates significantly from the composition of the host basanite. Electron diffraction technique confirms the amorphous nature of the glass, thus classifying it as a former melt. Every grain or phase boundary shows amorphous intergranular glass layers of variable thickness and characteristic chemical composition with distinct chemical inhomogeneities. Olivine grain boundaries, as the most common type of interfaces, exhibit two different types of melt glasses: (1) Type I melt at olivine grain boundaries, which is characterized by low contents of SiO₂ (～37?wt%) and Al₂O₃ (～5?wt%) and elevated contents of MgO (～31?wt%) and FeO (～22?wt%), is supposed to have formed prior to or during the thermal overprint and the dynamic recrystallisation of the xenolith in the mantle. Melt inclusions inside olivine grains with an average composition of type I melt are suggested to be earlier melt droplets at olivine interfaces, overgrown by migrating olivine grain boundaries during recrystallization in the mantle prior to the uplift of the xenolith. (2) Type II melt, the most common type of melt in the xenolith, shows higher contents of SiO₂ (～48?wt%) and Al₂O₃ (～17?wt%) but lower contents of MgO (～20?wt%) and FeO (～11?wt%). The observation of different types of glass within a single xenolith indicates the development of different chemical melt equilibria at interfaces or triple junctions in the xenolith. The absence of geochemical trends in bivariate plots excludes a unifying process for the genesis of these glasses. Melt inclusions in the spongy rims of clinopyroxene are interpreted to be the product of a potassium-rich metasomatism. The formation of most amorphous intergranular melt layers and pockets at the mineral interfaces including type II melt at olivine grain boundaries is suggested to result from decompression melting during the uplift with the basalt magma. We suggest that these glasses were produced by grain boundary melting due to lattice mismatch and impurity segregation. The observed intergranular amorphous layers or melts represent the very beginning of mineral melting by grain boundary melting.     

Chemical zonation in olivine-hosted melt inclusions

Significant zonation in major, minor, trace, and volatile elements has been documented in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (e.g., MgO, FeO, Cr₂O₃, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H₂O, and F, components with a lower concentration in the host olivine than in the melt (e.g., Al₂O₃, SiO₂, Na₂O, K₂O, TiO₂, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions, concurrent with diffusive propagation of the boundary layer toward the inclusion center. Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na₂O, K₂O) by coupling to slow diffusing components such as SiO₂ and Al₂O₃. Concentrations of H₂O and F decrease toward the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects. A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C h^?1 from the liquidus down to ~1,000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1,000 °C ranges from 40 s to just over 1 h. Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization. All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.     

Chemical evolution of basalts from 23°N along the mid-Atlantic ridge: evidence from melt inclusions

The chemical compositions of melt inclusions in a primitive and an evolved basalt recovered from the mid-Atlantic ridge south of the Kane Fracture Zone (23°–24°N) are determined. The melt inclusions are primitive in composition (0.633–0.747 molar Mg/(Mg+Fe²⁺), 1.01–0.68 wt% TiO₂) and are comparable to other proposed parental magmas except in having higher Al₂O₃ and lower CaO. The primitive melt inclusion compositions indicate that the most primitive magmas erupted in this region are not near primary magma compositions. Olivine and plagioclase microphenocrysts are close to exchange equilibrium with their respective basalt glasses, whose compositions are displaced toward olivine from 1 atm three phase saturation. The most primitive melt inclusion compositions are close to exchange equilibrium with the anorthitic cores of zoned plagioclases (An_78.3-An_83.1; the hosts for the melt inclusions in plagioclase) and with olivines more forsteritic (Fo₈₉-Fo₉₁) than the olivine microphenocrysts (the hosts for the melt inclusions in olivine). Xenocrystic olivine analyzed is Fo₈₉ but contains no melt inclusions. These observations indicate that olivines have exchanged components with the melt after melt inclusion entrapment, whereas plagioclase compositions have remained the same since melt inclusion entrapment. Common denominator element ratio diagrams and oxide versus oxide variation diagrams show that the melt inclusion compositions, which represent liquids higher along the liquid line of descent, are related to the glass compositions by the fractionation of olivine, plagioclase and clinopyroxene (absent from the mincral assemblage), probably occurring at elevated pressures. A model is proposed whereby clinopyroxene segregates from the melt at elevated pressures (to account for its absence in the erupted lavas that have the chemical imprint of clinopyroxene fractionation). Zoned plagioclases in the erupted lavas are thought to be survivors of decompressional melting during magma ascent. Since similar primitive melt inclusions occur in olivine microphenocrysts and in the cores of zoned plagioclases, any model must account for all phases present.     

Rare earth and high field strength element partitioning between iron-rich clinopyroxenes and felsic liquids

Rare earth elements are commonly assumed to substitute only for Ca in clinopyroxene because of the similarity of ionic radii for REE³⁺ and Ca²⁺ in eightfold coordination. The assumption is valid for Mg-rich clinopyroxenes for which observed mineral/melt partition coefficients are readily predicted by the lattice strain model for substitution onto a single site (e.g., Wood and Blundy 1997). We show that natural Fe-rich pyroxenes in both silica-undersaturated and silica-oversaturated magmatic systems deviate from this behavior. Salites (Mg# 48–59) in phonolites from Tenerife, ferrohedenbergites (Mg# 14.2–16.2) from the rhyolitic Bandelier Tuff, and ferroaugites (Mg# 9.6–32) from the rhyolitic Rattlesnake Tuff have higher heavy REE contents than predicted by single-site substitution. The ionic radius of Fe²⁺ in sixfold coordination is substantially greater than that of Mg²⁺; hence, we propose that, in Fe-rich clinopyroxenes, heavy REE are significantly partitioned between eightfold Ca sites and sixfold Fe and Mg sites such that Yb and Lu exist dominantly in sixfold coordination. We also outline a REE-based method of identifying pyroxene/melt pairs in systems with multiple liquid and crystal populations, based upon the assumption that LREE and MREE reside exclusively in eightfold coordination in pyroxene. Contrary to expectations, interpolation of mineral/melt partition coefficient data for heavy REE does not predict the behavior of Y. We speculate that mass fractionation effects play a role in mineral/melt lithophile trace element partitioning that is detectable among pairs of isovalent elements with near-identical radii, such as Y and Ho, Zr and Hf, and Nb and Ta.     

Determination of melt influence on divalent element partitioning between anorthite and CMAS melts

We propose a theory for crystal-melt trace element partitioning that considers the energetic consequences of crystal-lattice strain, of multi-component major-element silicate liquid mixing, and of trace-element activity coefficients in melts. We demonstrate application of the theory using newly determined partition coefficients for Ca, Mg, Sr, and Ba between pure anorthite and seven CMAS liquid compositions at 1330 °C and 1 atm. By selecting a range of melt compositions in equilibrium with a common crystal composition at equal liquidus temperature and pressure, we have isolated the contribution of melt composition to divalent trace element partitioning in this simple system. The partitioning data are fit to Onuma curves with parameterizations that can be thermodynamically rationalized in terms of the melt major element activity product (a_Al2O3)(a_SiO2)² and lattice strain theory modeling. Residuals between observed partition coefficients and the lattice strain plus major oxide melt activity model are then attributed to non-ideality of trace constituents in the liquids. The activity coefficients of the trace species in the melt are found to vary systematically with composition. Accounting for the major and trace element thermodynamics in the melt allows a good fit in which the parameters of the crystal-lattice strain model are independent of melt composition.