Redox equilibria of iron and silicate melt structure: Implications for olivine/melt element partitioning

Olivine/melt partitioning of ΣFe, Fe²⁺, Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, and Ni²⁺ has been determined in the systems CaO-MgO-FeO-Fe₂O₃-SiO₂ (FD) and CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂ (FDA3) as a function of oxygen fugacity (f_O2) at 0.1 MPa pressure. Total iron oxide content of the starting materials was ∼20 wt%. The f_O2 was to used to control the Fe³⁺/ΣFe (ΣFe: total iron) of the melts. The Fe³⁺/ΣFe and structural roles of Fe²⁺ and Fe³⁺ were determined with ⁵⁷Fe resonant absorption Mössbauer spectroscopy. Changes in melt polymerization, NBO/T, as a function of f_O2 was estimated from the Mössbauer data and existing melt structure information. It varies by ∼100% in melts coexisting with olivine in the FDA3 system and by about 300% in the FD system in the Fe³⁺/ΣFe range of the experiments (0.805-0.092). The partition coefficients ( in olivine/wt% in melt) are systematic functions of f_O2 and, therefore, NBO/T of the melt. There is a -minimum in the FDA3 system at NBO/T-values corresponding to intermediate Fe³⁺/ΣFe (0.34-0.44). In the Al-free system, FD, where the NBO/T values of melts range between ∼1 and ∼2.9, the partition coefficients are positively correlated with NBO/T (decreasing Fe³⁺/ΣFe). These relationships are explained by consideration of solution behavior in the melts governed by Qⁿ-unit distribution and structural changes of the divalent cations in the melts (coordination number, complexing with Fe³⁺, and distortion of the polyhedra).     

Trace element partitioning between mica- and amphibole-bearing garnet lherzolite and hydrous basanitic melt: 1. Experimental results and the investigation of controls on partitioning behaviour

Thirty five minor and trace elements (Li, Be, B, Sc, Cu, Zn, Ga, Ge, As, Rb, Nb, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ce, Nd, Sm, Tb, Ho, Tm, Lu, Hf, Ta, W, Tl, Pb, Bi, Th and U) in experimentally produced near-liquidus phases, from a primitive nelpheline basanite from Bow Hill in Tasmania (Australia), were analysed by LAM ICP-MS. A number of halogens (F, Cl and I) were also analysed by electron microprobe. The analyses were used to determine mineral/melt partition coefficients for mica, amphibole, garnet, clinopyroxene, orthopyroxene and olivine for conditions close to multiple saturation of the basanite liquidus with garnet lherzolite (approximately 2.6 GPa and 1,200°C with 7.5 wt% of added H₂O). A broader range of conditions was also investigated from 1.0 GPa and 1,025°C to 3.5 GPa and 1,190°C with 5–10 wt% of added H₂O. The scope and comprehensiveness of the data allow them to be used for two purposes, these include the following: an investigation of some of the controlling influences on partition coefficients; and the compilation of a set partition coefficients that are directly relevant to the formation of the Bow Hill basanite magma by partial melting of mantle peridotite. Considering clinopyroxene, the mineral phase for which the most data were obtained, systematic correlations were found between pressure and temperature, mineral composition, cation radius and valence, and ΔG ^coulb (the coulombic potential energy produced by substituting a cation of mismatched valence into a crystallographic site). ΔG ^coulb is distinctly different for different crystallographic sites, including the M2 and M1 sites in clinopyroxene. These differences can be modelled as a function of variations in optimum valence (expressed as 1 sigma standard deviations) within individual M1 and M2 site populations.     

An experimental study of partitioning of fluorine between K-richterite,apatite, phlogopite,and melt at 20 kbar

Phase relations have been determined at 20 kbar and primarily under suprasolidus conditions in the Fe−Ti-free F-bearing K-richterite—phlogopite and K-richterite—apatite systems in order to assess the partitioning of F among phlogopite, K-richterite, apatite, and melt under upper-mantle conditions. Both systems are pseudoternary because they contain forsterite, enstatite and a diopside-rich clinopyroxene from the breakdown of the mica and K-richterite. The F-bearing K-richterite systems have lower minimum melting temperatures than the F-bearing phlogopite —apatite system at the same pressure. However in the systems studied, F in phlogopite appears the most effective component in altering minimum liquid compositions whereas comparison between the present study and previous systems suggests that the presence of P₂O₅ during melting may result in more K-enriched melts. Variations in the compositions of the F-bearing phases are primarily controlled by the bulk compositions of the end-member minerals and by temperature, although buffering by non-F bearing minerals (e.g. clinopyroxene) may be effective. Distribution coefficients (as wt% ratios) between F-bearing minerals and coexisting liquids have been determined as functions of bulk composition and temperature for products of experiments. Distribution coefficients between K-richterite—liquid, apatite—liquid, and phlogopite—liquid are ≥1 to slightly <1 for most bulk compositions, indicating thatF is generally a compatible element. This conclusion is in agreement with the sequence ofF distribution for similar phases in ultrapotassic rocks. These results preclude F-bearing mineral reservoirs in the mantle, at depths corresponding to 20 kbar, being capable of producing F-enrichment in ultrapotassic magmas, or being effective in redox melting processes. Editorial responsibility: K. Hodges     

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.     

An experimental study of rare earth element partitioning between a shergottite melt and pigeonite: implications for the oxygen fugacity of the mart ian interior

A series of experiments on a synthetic, pigeonite-saturated, basaltic shergottite were carried out to constrain the variation of D(Eu/Gd)_{pigeonite/melt} and D(Eu/Sm)_{pigeonite/melt} with oxygen fugacity (f_O2). The experiments have been run under both dry and hydrous conditions. The shergottite was doped with 0.1, 0.5, and 1.0 wt.% Eu, Gd, and Sm oxides in different experiments and was equilibrated at liquidus conditions for 24 hours. D(Eu/Gd)_{pigeonite/melt} in dry melts ranges from 0.156 ± 0.014 (f_O2 = IW − 1) to 0.630 ± 0.102 (IW + 3.5). D(Eu/Sm)_{pigeonite/melt} in dry melts ranges from 0.279 ± 0.021 (IW − 1) to 1.114 ± 0.072 (IW + 3.5). Due to difficulties with low-f_O2 experiments, hydrous distribution coefficients were measured, but were not used in the calibration of the Eu-oxybarometers. These two Eu-oxybarometers provide an accurate way to measure f_O2 recorded during pigeonite crystallization, thereby yielding a record of f_O2 during the earliest period of Martian meteorite parent magma crystallization history.Using this new calibration, Martian meteorite pigeonite cores record f_O2 values of IW − 0.6 (±0.3) (QUE94201) to IW + 1.9 (±0.6) (Shergotty). These new values differ in magnitude, but not trend, from previously published data. The pigeonite Eu-oxybarometer yields an f_O2 range in the basaltic shergottites of 2 to 3 orders of magnitude. Several processes have been proposed to explain the origin of this f_O2 range, the majority of which rely on assimilation of an oxidized source. A potential correlation between this new pigeonite data and recent Fe-Ti oxide data, however, is consistent with intrinsic f_O2 differences in the magma source region being responsible for the measured f_O2 variations. This implies that the Martian meteorite source region, the mantle or lithosphere, may be heterogeneous in nature. However, the process of assimilation cannot be completely ruled out in that an assimilation event that took place before crystallization commenced would result in the overprinting of the source region f_O2 signature.     

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 partitioning between apatite and silicate melts

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

Fractionation of pyroxene-phyric MORB at low pressure: An experimental study

Contributions to Mineralogy and Petrology - One-atmosphere melting experiments are used to assess the role of clinopyroxene in producing the compositional variations observed in mid-ocean-ridge...     

Trace element partitioning between ilmenite, armalcolite and anhydrous silicate melt: Implications for the formation of lunar high-Ti mare basalts

We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300-1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO-FeO-MgO-Al₂O₃-TiO₂-SiO₂ system. Ilmenite-melt and armalcolite-melt partition coefficients (D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( 0.0020 ± 0.0010 to 0.069 ± 0.010 for ilmenite; 0.0048 ± 0.0023 to 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: 0.0013 ± 0.0008, 0.0035 ± 0.0015 and 0.039 ± 0.005, and for armalcolite 0.008 ± 0.003, 0.0048 ± 0.0022 and 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. 0.28 ± 0.05 and : 0.76 ± 0.07). Both minerals fractionate the high field strength elements with D_Ta/D_Nb and D_Hf/D_Zr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with D_Hf/D_W = 12-13 compared to 6.7-7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite (D ∼ 7.5) and V in armalcolite (D ∼ 8.1). D values show no clear variation with pressure in the small range covered.Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals.Our results are used to model the Lu-Hf-Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO₂ contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.     

Trace element partitioning and substitution mechanisms in calcium perovskites

We have determined the partition coefficients of a large number of trace elements between CaTiO₃ perovskite and anhydrous silicate melts at atmospheric pressure and 3 GPa. Determination of the concentration limits of Henrys law behaviour in the CaO-Al₂O₃–SiO₂–TiO₂ system reveals that the incorporation of rare earth elements (REE) and tetravalent large ion lithophile elements (LILE⁴⁺ such as U and Th) at the Ca-site of CaTiO₃ perovskite occurs with charge compensation through Ca-vacancy formation rather than by coupled substitution of Al for Ti. When melt composition is varied, we find that partition coefficients for REE and Th are strong functions of the CaO content of the melt. The observed trends are in excellent agreement with those predicted from the Ca-vacancy model. Given that they adopt the same crystal structure and have similar trace element partitioning behaviour, CaTiO₃ perovskite and the deep mantle phase CaSiO₃ perovskite can be considered analogous to one another. When the analogy is pursued in detail, we find that partitioning into both phases follows the composition-dependence predicted by the Ca-vacancy model. Thus, substitution of REE, U⁴⁺ and Th into CaSiO₃ in the lower mantle also occurs with Ca-vacancy formation to balance charge. Furthermore when 2+, 3+ and 4+ partition coefficients for both phases are plotted as functions of CaO melt content, the trends for CaSiO₃ and CaTiO₃ appear to be continuous. This surprising result means that partitioning into Ca-perovskite is independent of pressure and temperature and also of whether or not the host is CaSiO₃ or CaTiO₃. One implication is that CaSiO₃ crystallising from a peridotitic magma ocean may have partition coefficients for Th and U up to about 400. Crystallisation and sequestration of as little as 0.25 volume% of this phase in the lower mantle early in earth history would make a significant contribution to current mantle heat production.Electronic Supplementary Material Supplementary material is available for this article at     

Element partitioning between olivine and silicate melt under high pressure

Element partitioning between olivine and silicate melt has been investigated at pressures 1–14 GPa, by using a 6–8 type multi-anvil high pressure apparatus. In order to observe systematics in the partitioning of trivalent ions, Li was added to the starting materials in order to increase the concentration of trivalent ions in olivine. With increasing pressure, it was found that partition coefficients of most of the elements gradually decreased. Trivalent ions generally showed parabolic pattern on partition coefficient — ionic radius diagram. When pyrolite-like material was used as the starting material, partition coefficient of Al, D_Al, gradually increased with increase in pressure while the partition coefficients of the other elements decreased, and the D_Al deviated from the parabolic pattern of other trivalent ions. The deviation of D_Al from the D pattern of the other trivalent ions was also found when olivine was employed as main component of the starting material. This result may be ascribed to the compositional change of coexisting silicate melt with increase in pressure.     

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.     

Trace element partitioning between silicate minerals and carbonatite at 25 kbar and application to mantle metasomatism

Summary Experiments at 25 kbar and 1000°C, on a model trace element-enriched carbonatite-eridotite mix, produced augite + pargasite ± garnet ± dolomite coexisting with a carbonatite melt. Proton microprobe analysis of the phases showed that key trace elements (Rb, Ba, Sr, Nb, Ta, Zr, Y and REE) all partitioned strongly into the melt (with the exception of Y, Ho and Lu in garnet), verifying that carbonatite is potentially a highly effective metasomatizing agent. The data also indicate that carbonatitic metasomatism will impart higher Ba/Rb, Ba/Nb, Nb/Ta, Sr/Ta, La/Ta, and lower Zr/Y, with little change to Sr/Nb, in affected mantle.

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Spurenelementverteilung zwischen Silikatmineralen und Karbonatit bei 25 kbar: Anwendung für die Mantel-Metasomatose

Zusammenfassung Experimente mit einer Modell-mischung von Karbonatit-Peridotit, angereichert mit Spurenelementen, produzierten bei 25 kbar und 1000°C Augit + Pargasit ± Granat ±Dolomit coexistierend mit einer Karbonatitschmelze. Protonmikrosonden-Analyse der Phasen zeigte, dass alle Schlüsselspurenelemente (Rb, Ba, Sr, Nb, Ta, Zr, Y and REE) stark in der Schmelze angereichert werden (mit der Ausnahme von Y, Ho und Lu in Granat), was beweist, dass Karbonatit potentiell ein sehr effektives Agens für Metasomatose ist. Die Daten zeigen weiterhin, dass karbonatitische Metasomatose in betroffenen Mantel höhere Ba/Rb, Ba/Nb, Nb/Ta, Sr/Ta, La/Ta und niedrigere Zr/Y produziert, mit geringen Äderungen für Sr/Nb.

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Rare earth element partitioning between clinopyroxene and silicate liquid at moderate to high pressure

Experimental determination of over seventy sets of clinopyroxene/silicate liquid (glass) partitition coefficients (D) for four rare earth elements (REE — La, Sm, Ho, Lu) in a range of REE-enriched natural rock compositions (basalt, basaltic andesite, andesite and rhyodacite) demonstrate a convex upward pattern, favouring the heavy REE (Ho, Lu) and markedly discriminating against the light REE (La). These patterns are consistent with previously documented clinopyroxene D values reported from natural phenocryst/matrix pairs and from experimental work using either REE-enriched compositions and electron microprobe analytical techniques (as in the present study) or natural or synthetic undoped compositions and mass spectrometric, ion probe or X-ray autoradiographic analytical techniques. However, the large data base in the present study allows evaluation of the effect of compositional and physical parameters on REE partitioning relationships. Considering D_Ho, it is shown that (1) D increases 6-fold with increasing SiO₂ content of the coexisting liquid from 50 to 70 wt% SiO₂ (2) D increases 4-fold with decreasing temperature from 1,120°C to 900° C (3) D increases 2-fold with increasing pressure from 2.5 to 20 kb. (4) D increases 2-fold fO₂ increases from approximately that of the MW buffer to the HM buffer (5) D remains unchanged within experimental error as the water content of the melt changes from 0.3 to 10% by weight H₂O.The absolute REE content of the clinopyroxene shows no consistent trend with temperature, but decreases slightly with increasing pressure, paralleling an increase in the jadeite component of the pyroxene. Thus the increase in D with increasing pressure is attributed to changes in the silicate liquid structure, which discriminate against accommodation of REE with increasing pressure. The clinopyroxene REE content increases with increasing fO₂, and in this case the increase in D with increasing fO₂ may be attributed mainly to this change in the clinopyroxene composition. Application of the present results to geochemical modelling allows a more appropriate choice of D values, according to the liquid composition and physical conditions applicable in the modelled system. They may also be used to evaluate cognate or xenocrystic relationships between clinopyroxene megacrysts and their host matrix.     

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.     

Trace element partitioning between mica- and amphibole-bearing garnet lherzolite and hydrous basanitic melt: 2. Tasmanian Cainozoic basalts and the origins of intraplate basaltic magmas

Oligocene volcanics from Oatlands in Tasmania, Australia, include olivine tholeiites, alkali olivine basalts, nepheline basanites and olivine nephelinites. They have compositional characteristics that are typical of intraplate basalts worldwide. They are generally enriched in incompatible elements relative to the primitive mantle and are strongly enriched in Nb, Ta and light rare earths, but not heavy rare earths. At the same time, they have Sr and Nd isotope compositions that are similar to those in some incompatible-element-depleted mid-ocean ridge basalts (E-type MORB). Experimentally obtained mineral/melt partition coefficients for an Oatlands basanite allow the relative concentrations of incompatible elements in the volcanics to be produced by small degrees of melting (≤1%) of a source similar to the E-type MORB source of Workman and Hart (2005). However, the absolute concentrations that can be achieved in this way are much less than present in the most incompatible-element-enriched basanites and nephelinites at Oatlands. This contradiction can be explained by open-system melting under the influence of a conductive geotherm. This would have involved upwardly migrating near-solidus melts from the asthenosphere cooling along a sub-adiabatic geotherm. Cooling of the melts would have caused them to re-crystallize and accumulate in the overlying mantle, thereby enriching both the new host rocks and any residual melts in incompatible elements. This would also have increased the buoyancy of the host rocks leading to upwelling and further (decompression) melting of incompatible-element-enriched peridotite. We were able to use our partition coefficients to quantitatively model the development of incompatible-element enrichments in the Oatlands magmas by these processes. Our explanation is consistent with the characteristically scattered but widespread distributions and long time scales of intraplate volcanism in a broad variety of tectonic settings. This is because the conditions required to initiate volcanism (i.e. those of near-solidus melting of the asthenosphere) are relatively easy to produce and can therefore be caused by both near-surface tectonics and deeper mantle processes. Furthermore, the super-enrichments of incompatible elements in some intraplate volcanics can be attributed to the influence of normal geothermal gradients on melting processes. Without the very strong fractionation imposed by this combination of factors, the Oatlands volcanics would more closely resemble mid-ocean-ridge basalts.