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.     

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.     

南极格罗夫山陨石GRV 020043—一个特殊的E/H过渡型球粒陨石

南极格罗夫山陨石GRV 020043是一块特殊的球粒陨石,虽与普通球粒陨石有着相似的矿物组合,但矿物成分超出普通球粒陨石范围.主要矿物组合及其模式含量(vol%)是:斜方辉石40、橄榄石24、透辉石8、斜长石10、 Fe-Ni合金14、陨硫铁4 vol%、及少量铬铁矿和磷灰石.主要组成矿物成分均一,如斜方辉石(Fs10...     

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.     

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.     

Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998     

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].     

Partition coefficients of Hf,Zr, and REE between zircon,apatite, and liquid

Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10–100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite.     

Trace element distribution coefficients in alkaline series

Mineral/groundmass partition coefficients for U, Th, Zr, Hf, Ta, Rb, REE, Co and Sc have been systematically measured in olivine, clinopyroxene, amphibole, biotite, Ti-magnetites, titanite, zircon and feldspars, in basaltic to trachytic lavas from alkaline series (Velay, Chaîne des Puys: Massif Central, France and Fayal: Azores). Average partition coefficients are denned within the experimental uncertainty for limited compositional ranges (basalt-hawaiite, mugearites, benmoreite-trachyte), and are useful for trace element modelling. The new results for U, Th, Ta, Zr and Hf partition coefficients show contrasting behaviour. They can thus be used as “key elements” for identifying fractionating mineral phases in differentiation processes (e.g. Ta and Th for amphibole and mica).Partition coefficient may be calculated using the two-lattice model suggested by Nielsen (1985). Such values show a considerably reduced chemical dependence in natural systems, relative to weight per cent D values. The residual variations may be accounted for by temperature or volatile influence. This calculation greatly enhances modelling possibilities using trace elements for comparing differentiation series as well as for predicting the behaviour of elements during magmatic differentiation.     

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.     

Experimental investigations of trace element fractionation in iron meteorites,II: The influence of sulfur

We have investigated the partitioning of Ir. Ge, Ga, W, Cr, Au, P, and Ni between solid metal and metallic liquid as a function of temperature and S-concentration of the metallic liquid. Partition coefficients for siderophile elements such as Ir, W, Ga and Ge increase by factors of 10–100 as the Sconcentration of the metallic liquid increases from 0–30 wt%. Partition coefficients for other siderophile elements such as Ni, Au and P increase by only factors of 2–3. In contrast, partition coefficients for the more chalcophile element Cr decrease. These experimentally-determined partition coefficients have been used in conjunction with a fractional crystallization model to reproduce the geochemical behavior of Ni, P, Au and Ir during the magmatic evolution of groups IIAB, IIIAB, IVA and IVB iron meteorites. The mean S-concentration for each group increases in the order IVB, IVA, IIIAB, IIAB, in accord with cosmochemical prediction. However, we are unable to reproduce the geochemical behavior of Ge, Ga, W and Cr in an internally consistent way. We conclude that the magmatic histories of these iron meteorite groups are more complex than has been generally assumed.     

Trace elements in minerals as indicators of the evolution of alkaline ultrabasic dike series: LA-ICP-MS data for the magmatic provinces of northeastern Fennoscandia and Germany

In this paper we report the results of the analysis of rare earth (REE), large-ion lithophile (LILE), and high field strength (HFSE) elements in minerals from the alkaline lamprophyre dikes of the Kola region and the Kaiserstuhl province by the local method of laser ablation inductively coupled plasma mass spectrometry. The contents of Y, Li, Rb, Ba, Th, U, Ta, Nb, Sr, Hf, Zr, Pb, Be, Sc, V, Cr, Ni, Co, Cu, Zn, Ga, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu were measured in olivine, melilite, clinopyroxene, amphibole, phlogopite, nepheline, apatite, perovskite, and the host fine-grained groundmass. The obtained data on trace element partitioning among the mineral phases of the alkaline ultrabasic rocks of the dike series indicate that the main mineral hosts for the HFSEs and REEs in alkaline picrites, olivine melanephelinites, and melilitites are perovskite and apatite comprising more than 90% of these elements. Among major rock-forming minerals, melilite, clinopyroxene, and highly magnesian amphibole make a significant contribution to the balance of REEs during the evolution of melanephelinite melts. The partition coefficients of Ni, Co, Cu, Zn, Sc, V, Cr, Ga, Y, Li, Rb, Ba, Th, U, Ta, Nb, Sr, Hf, Zr, Pb, Be, and all of the REEs were calculated for olivine, clinopyroxene, amphibole, phlogopite, nepheline, perovskite, and apatite on the basis of mineral/groundmass ratios. Variations in the composition of complex zoned clinopyroxene phenocrysts reflect the conditions of polybaric crystallization of melanephelinite melt, which began when the magmas arrived at the base of the lower crust and continued during the whole period of their ascent to the surface. The formation of green cores in clinopyroxene is an indicator of mixing between primary melanephelinite melts and phonolite magmas under upper mantle conditions. The estimation of the composition of primary melts for the rocks of the alkaline ultrabasic series of the Kola province indicated a single primary magma for the whole series. This magma produced pyroxene cumulates and complementary melilitolites, foidolites, and nepheline syenites.     

Clinopyroxene-matrix partitioning of K,Rb, Cs,Sr and Ba

Extremely pure samples of clinopyroxene phenocrysts from two volcanic rocks have been analyzed for K, Rb, Cs, Sr and Ba. In conjunction with matrix concentrations, partition coefficients are obtained which are in the range 0.001–0.004 for K, Rb, Cs and Ba. These values are lower than those in the literature by factors of 6–100 but are in good agreement with values determined experimentally at pressures of 15–30 kb by Shimizu (Geochim. Cosmochim. Acta38, 1974). Values for partition coefficients measured on separates of impure or cloudy pyroxenes from these same rocks were higher and similar to those in the literature. We suggest this effect is related to ‘trapping,’ during crystal growth, of liquid which is enriched in the larger ions (such as Rb and Cs) due to lack of diffusion equilibrium in the liquid. Partition coefficient values for olivine and plagioclase from one of these same rocks were also determined.     

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.     

Sc,Cr, Co and Ni partitioning between minerals from spinel peridotite xenoliths

The partitioning of divalent (Co, Ni) and trivalent (Sc, Cr) trace elements between olivine, ortho- and clinopyroxene and spinel from spinel peridotite xenoliths has been investigated. These peridotites cover a wide range in modal composition from dunite to primitive lherzolites and have equilibrated in the upper mantle between >900° C and <1,200° C.The distribution of Co and Ni shows only minor variation through the whole sequence. In contrast, Sc partitioning between ortho- and clinopyroxene and olivine and clinopyroxene as well as Cr partitioning between olivine and clinopyroxene or olivine and orthopyroxene display high but systematic variations which can be assigned to dependences upon equilibration temperatues. Empirical temperature calibrations are given for Sc-orthopyroxene/clinopyroxene, Sc-olivine/clinopyroxene and Cr-olivine/clinopyroxene which, in principle, may permit to estimate equilibration temperatures not only for lherzolites or harzburgites but for orthopyroxene-free peridotites, too.Sc and Ni partition coefficients between spinel and mantle silicate minerals are primarily dependent upon the major element composition of spinel (e.g. Cr and Al) although a temperature dependence can still be identified. Probably such compositional effects are not observed for trace element partitioning between pyroxenes and olivine or ortho- and clinopyroxene only for the reason that in normal spinel peridotites these minerals show much less variation in major element composition than their coexisting spinels.     

The production of iron oxide during peridotite serpentinization: Influence of pyroxene

Serpentinization produces molecular hydrogen(H2)that can support communities of microorganisms in hydrothermal fields;H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron,and consequently iron oxide(magnetite or hematite)forms.However,the mechanisms that control H2 and iron oxide formation are poorly constrained.In this study,we performed serpentinization experiments at 311℃ and 3.0 kbar on olivine(with 5% pyroxene),orthopyroxene,and peridotite.The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution.Olivine-derived serpentine had a significantly lower FeO content(6.57±1.30 wt.%)than primary olivine(9.86 wt.%),whereas orthopyroxene-derived serpentine had a comparable FeO content(6.26±0.58 wt.%)to that of primary orthopyroxene(6.24 wt.%).In experiments on peridotite,olivine was replaced by serpentine and iron oxide.However,pyroxene transformed solely to serpentine.After 20 days,olivine-derived serpentine had a FeO content of 8.18±1.56 wt.%,which was significantly higher than that of serpentine produced in olivine-only experiments.By contrast,serpentine after orthopyroxene had a slightly higher FeO content(6.53±1.01 wt.%)than primary orthopyroxene.Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral.After 120 days,the FeO content of olivine-derived serpentine decreased significantly(5.71±0.35 wt.%),whereas the FeO content of orthopyroxene-derived serpentine increased(6.85±0.63 wt.%)over the same period.This suggests that iron oxide preferentially formed after olivine serpentinization.Pyroxene in peridotite gained some Fe from olivine during the serpentinization process,which may have led to a decrease in iron oxide production.The correlation between FeO content and SiO_2 or AI_2 O_3 content in olivine-and orthopyroxene-derived serpentine indicates that aluminum and silica greatly control the production of iron oxide.Based on our results and data from natural serpentinites reported by other workers,we propose that aluminum may be more influential at the early stages of peridotite serpentinization when the production of iron oxide is very low,whereas silica may have a greater control on iron oxide production during the late stages instead.     

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     

Crystallisation sequence and magma evolution of the De Beers dyke (Kimberley,South Africa)

We present petrographic and mineral chemical data for a suite of samples derived from the De Beers dyke, a contemporaneous, composite intrusion bordering the De Beers pipe (Kimberley, South Africa). Petrographic features and mineral compositions indicate the following stages in the evolution of this dyke: (1) production of antecrystic material by kimberlite-related metasomatism in the mantle (i.e., high Cr-Ti phlogopite); (2) entrainment of wall-rock material during ascent through the lithospheric mantle, including antecrysts; (3) early magmatic crystallisation of olivine (internal zones and subsequently rims), Cr-rich spinel, rutile, and magnesian ilmenite, probably on ascent to the surface; and (4) crystallisation of groundmass phases (i.e., olivine rinds, Fe-Ti-rich spinels, perovskite, apatite, monticellite, calcite micro-phenocrysts, kinoshitalite-phlogopite, barite, and baddeleyite) and the mesostasis (calcite, dolomite, and serpentine) on emplacement in the upper crust. Groundmass and mesostasis crystallisation likely forms a continuous sequence with deuteric/hydrothermal modification. The petrographic features, mineralogy, and mineral compositions of different units within the De Beers dyke are indistinguishable from one another, indicating a common petrogenesis. The compositions of antecrysts (i.e., high Cr-Ti phlogopite) and magmatic phases (e.g., olivine rims, magnesian ilmenite, and spinel) overlap those from the root zone intrusions of the main Kimberley pipes (i.e., Wesselton, De Beers, Bultfontein). However, the composition of these magmatic phases is distinct from those in ‘evolved’ intrusions of the Kimberley cluster (e.g., Benfontein, Wesselton water tunnel sills). Although the effects of syn-emplacement flow processes are evident (e.g., alignment of phases parallel to contacts), there is no evidence that the De Beers dyke has undergone significant pre-emplacement crystal fractionation (e.g., olivine, spinel, ilmenite). This study demonstrates the requirement for detailed petrographic and mineral chemical studies to assess whether individual intrusions are in fact ‘evolved’; and that dykes are not necessarily produced by differentiated magmas.

     

Gough Island: Evaluation of a fractional crystallization model

Gough Island is composed of an alkaline olivine basalt-trachyte series. A fractional crystallization model for the development of these rocks has been evaluated by correlating the geochemical trends of major and trace elements. Beginning with an alkali olivine basalt parent the major element abundances were used to determine the varying proportions of crystallizing minerals required to generate the various residual liquids. A least-squares computer model was used for this calculation. The modal proportions of cumulative minerals and trace element distribution coefficients were used to predict the trace element abundances in each rock type.Three significant trace element trends are observed in Gough Island rocks: (1) increasing rare earth (RE) abundance and relative light RE enrichment with increasing major element differentiation, (2) marked Eu, Sr, and Ba depletions in late stage trachytes, (3) Cr and M enrichment in picrite basalt.The trace element abundances predicted by the fractional crystallization model are in good agreement with these observed trends. A fractional crystallization process involving olivine, pyroxene, feldspar, and apatite accounts for all the significant major and trace element trends observed in Gough Island rocks.