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

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

Partition 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.     

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.     

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon

Partition coefficients (^zircon/meltD_M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D_REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D_REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D_REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques.D_REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce⁴⁺ in the melt results in elevated D_Ce compared to neighboring REE due to the similar valence and size of Ce⁴⁺ and Zr⁴⁺. Predicted ^zircon/meltD values for Ce⁴⁺ and Ce³⁺ indicate that the Ce⁴⁺/Ce³⁺ ratios of the melt ranged from about 10⁻³ to 10⁻². Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D_M < 1.0), and Ti, Y and Nb showing compatible behavior (D_M > 1.0).The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D_REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D_Yb from this study. Using D_Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.     

Partitioning of rare earth and high field strength elements between titanite and phonolitic liquid

We present the results of a LA–ICPMS study of titanites and associated glasses from the mixed-magma phonolitic Fasnia Member of the Diego Hernández Formation, Tenerife, Canary Islands. We employ a method of identifying equilibrium mineral–melt pairs from natural samples using REE contents and a linear form of the lattice strain model equation (Blundy and Wood, 1994), where the Young's modulus (E_M) for the 7-fold coordinated site is an output variable. For felsic magmas that contain crystals potentially derived from a variety of environments within the system, this approach is more rigorous than the use of solely textural criteria such as mineral–glass proximity. We then estimate titanite/melt partition coefficients for Y, Zr, Nb, REE, Hf, Ta, U and Th. In common with prior studies, we find that middle REE partition more strongly into titanite than either light or heavy REE, and that REE partitioning behavior in titanite is reasonably predicted by the lattice strain model. Titanite also fractionates Y from Ho, Zr from Hf, and Nb from Ta. Comparison with experimental data indicates that melt structure effects on partitioning are significant, most particularly in very highly polymerized melts. We use the data to estimate 7-fold coordination radii for trivalent Pr, Nd, Ho, Tm and Lu, and to make approximate predictions of titanite/melt partitioning of Ra, Ac and Pa. Interpolation of data for heavy REE does not predict the behavior of Y, indicating that factors other than charge and radius are involved in partitioning. Variations in Y/Ho induced by magmatic processes appear to be negatively correlated with temperature, and are expected to be greatest in near-minimum melts.     

Mineralogical and chemical changes of soil and stream sediment formed by intense weathering of the Danburg granite, Georgia, U.S.A.

A series of soil and stream sediments developed during intense weathering on the metaluminous Danburg granite, northeastern Georgia, U.S.A., have been analyzed mineralogically and chemically. The concentrations of Ba, Na, Rb and Cs in the silt and coarser fractions are controlled mainly by feldspars and biotite. Hf is controlled by zircon, and the REE (rare-earth elements) and Th are largely controlled by sphene. Variations in feldspar, sphene and zircon may produce small variations in Eu/Sm and La/Lu ratios. Ferromagnesian minerals control Ta, Fe, Co, Sc and Cr concentrations.

The mineralogical and chemical composition of the Danburg granite is more closely reflected in the silt than in the sand or gravel fractions of stream sediments. In the silt, the contents of Rb, REE, Th, Ta, Fe, Co and Sc and the ratios of La/Sc, Th/Sc, La/Co, Th/Co, Eu/Sm and La/Lu are similar to those in the unweathered granite. In contrast, these element contents or ratios in the sands and gravels are 0.05−3× the concentration in the unweathered granite. Ta and Ba contents are an exception to the above. The Ta and Ba contents of the sands and gravels are similar to those of the granite.

In the kaolinite-halloysite clays, the content of Na is depleted relative to the source. Rb, Cs, Ba, Hf and Ta are depleted or enriched in the clays relative to the source, while the REE, Th, Fe, Co, Sc and Cr are enriched. The Eu/Sm (Eu anomaly size) and La/Lu ratios, and the REE patterns of the clays are similar to those of the source.

Thus, the mineralogy and element contents of a siltstone developed from metaluminous, granitic sources during intense weathering would be expected to be more similar to the source rock than the sandstones and conglomerates. Claystones should contain similar REE patterns and Eu/Sm ratios as the source rock, but such fine-grained sediments might represent much larger areas of source rocks than the more locally derived sandstones or conglomerates.     

1kbar、800℃下REE在富磷过铝质熔体/流体相间分配的实验研究

利用"RQV-快速内冷淬火"(或称之为"外加热冷封式")高温高压实验装置,实验研究了1kbar、800℃条件下12个REE+Y在富磷过铝质熔体/含水流体相间的分配,并利用EMP、LA-ICPMS和ICP-MS分析技术分别测定了实验初始物、实验产物玻璃中主要化学组成以及熔体相和流体相中REE含量。实验结果表明,REE元素(La,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb和Lu)在流体/熔体相间的分配系数(Dfluid/melt)在(0.1～19.9)×10-4范围,DfYluid/melt在(0.2～7.8)×10-4范围,指示REE和Y强烈趋向于在熔体中富集。REE在流体/熔体相间的分配系数(Dfluid/melt)与体系中P2O5含量变化呈近抛物线状分布,其最大值对应于残余熔体中w(P2O5)为1.44%处。REE在流体/熔体相间的分配系数(Dfluid/melt)随REE的原子序数增大而逐渐降低,构成右倾的平滑曲线,总体上显示出DLREE>DMREE>DHREE的趋势。Y与Ho在流体/熔体相间分配系数的比值(DY/DHo)约为1(0.91～1.28),不随体系中P2O5变化而变化的特征。上述特征表明熔体-流体作用不会导致Y-Ho及REE间的分异,因此,可推断熔体-流体作用过程不可能是过铝质岩浆体系中产生稀土"四重效应"机制。     

Rare earth element fractionation in magmatic Ca-rich garnets

Igneous garnets have the potential to strongly fractionate rare earth elements (REE). Yet informations on partition coefficients are very scant, and criteria for distinguishing between hydrothermal and magmatic garnets are ambiguous. To fill this gap, we present trace element and isotopic data for two types of Ca-rich garnets from phonolites (Mt. Somma-Vesuvius). Both Ca-garnet populations are different in their style and dynamics of fractionation: one population is progressively strongly depleted in HREE from core to rim, reflecting REE fractionation in the host phonolite via earlier-crystallized garnets. Such examples for extreme changes in HREE in garnets are only known for hydrothermal grandites by REE-bearing fluids. The second garnet population is homogeneous and formed in a closed system. Near-flat patterns between Sm and Lu confirm experimental data indicating lower D(Sm)/D(Lu) for Ca-rich garnets than for e.g. pyrope-rich garnets. It follows: D ^Grt/PhMelt for La = 0.5, Sm = 48 and Yb = 110.     

Trace-element composition of hydrothermal zircon and the alteration of Hadean zircon from the Jack Hills,Australia

Hydrothermal zircon can be used to date fluid-infiltration events and water/rock interaction. At the Boggy Plain zoned pluton (BPZP), eastern Australia, hydrothermal zircon occurs with hydrothermal scheelite, molybdenite, thorite and rutile in incipiently altered aplite and monzogranite. The hydrothermal zircon is texturally distinct from magmatic zircon in the same rocks, occurring as murky-brown translucent 20–50 μm-thick mantles on magmatic cores and less commonly as individual crystals. The hydrothermal mantles are internally textureless in back-scatter electron and cathodoluminescence images whereas magmatic zircon is oscillatory zoned. The age of the hydrothermal zircon is indistinguishable from magmatic zircon, indicating precipitation from a fluid evolved from the magma during the final stages of crystallization. Despite indistinguishable U-Pb isotopic compositions, the trace-element compositions of the hydrothermal and magmatic zircon are distinct. Hydrothermal zircon is enriched in all measured trace-elements relative to magmatic zircon in the same rock, including V, Ti, Nb, Hf, Sc, Mn, U, Y, Th and the rare-earth elements (REE). Chondrite-normalized REE abundances form two distinct pattern groupings: type-1 (magmatic) patterns increase steeply from La to Lu and have Ce and Eu anomalies—these are patterns typical for unaltered magmatic zircon in continental crust rock types; type-2 (hydrothermal) patterns generally have higher abundances of the REE, flatter light-REE patterns [(Sm/La)_N = 1.5–4.4 vs. 22–110 for magmatic zircon] and smaller Ce anomalies (Ce/Ce* = 1.8–3.5 vs. 32–49 for magmatic zircon). Type-2 patterns have also been described for hydrothermally-altered zircon from the Gabel Hamradom granite, Egypt, and a granitic dyke from the Acasta Gneiss Complex, Canada.Hadean (∼4.5–4.0 Ga) zircon from the Jack Hills, Western Australia, have variable normalized REE patterns. In particular, the oldest piece of Earth—zircon crystal W74/2-36 (dated at 4.4 Ga)—contains both type-1 and type-2 patterns on a 50 μm scale, a phenomenon not yet reported for unaltered magmatic zircon. In the context of documented magmatic and hydrothermal zircon compositions from constrained samples from the BPZP and the literature, the type-2 patterns in crystal W74/2-36 and other Jack Hills Hadean (JHH) zircon are interpreted as hydrothermally-altered magmatic compositions. An alteration scenario, constrained by isotope and trace-element data, as well as α-decay event calculations, involving fluid/zircon cation and oxygen isotope exchange within partially metamict zones and minor dissolution/reprecipitation, may have occurred episodically for some JHH zircon and at ∼4.27 Ga for zircon W74/2-36. Type-2 compositions in JHH zircon are interpreted to represent localized exchange with a light-REE-bearing, high δ¹⁸O (∼6–10‰ or higher) fluid. Thus, a complex explanation involving “permanent” liquid water oceans, large-scale water/rock interaction and plate tectonics in the very early Archean is not necessary as the zircon textures and compositions are simply explained by exchange between partially metamict zircon and a low volume ephemeral fluid.     

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

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

Rare earth element mobility at constant inter-REE ratios in the alteration zone at the Phelps Dodge massive sulphide deposit,Matagami, Quebec

Rare earth elements (REE) from La to Ho were mobile and enriched in hydrothermally altered rocks below the Archean Phelps Dodge Cu-Zn volcanogenic massive sulphide deposit in northwestern Quebec. Largest net enrichment was in the moderately altered quartz-chlorite zone where La concentration increased six-fold and La_NYb_N steepened from 1.9 to 13.0; the intensely altered chloritite zone had both minor net REE enrichment and depletion. Yb and Lu were immobile throughout both zones. The mobile REE were added and subtracted in constant chondrite-normalized inter-REE proportions: 1.0 La, 0.79 Ce, 0.57 Nd, 0.49 Sm, 0.01 Eu, 0.10 Tb and 0.02 Hb. Small additions of Eu relative to generally larger additions of LREE and Tb produced enhanced negative Eu-anomalies. The REE were mobilized at the hot (>300 C) core of the alteration system and deposited at the cooler periphery. Other sites of intense alteration and water/rock interaction display similar REE changes, indicating that selective REE enrichment at constant inter-REE ratios is a widespread phenomenon.     

Rare-earths in size fractions and sedimentary rocks of Pennsylvanian-Permian age from the mid-continent of the U.S.A.

The REE (rare-earth) contents of sixty-three <2 μ fractions of Pennsylvanian and Permian platform sediment from the mid-continent of the U.S.A. vary considerably (ΣREE = 46–439 ppm;La/ Lu = 5.2–15.7; correlation coefficient of REE with La/Lu = 0.89), but the Eu/Sm ratios are nearly constant even in reducing environments that concentrate U (0.16–0.22). There is no correlation of REE content to clay mineralogy.Lower Permian <2 μ fractions from continental to nearshore marine sediment in Oklahoma have higher REE content (244–261 ppm) than marine facies in Kansas (46–140ppm), but <2μ Upper Permian fractions in an evaporite basin have constant but high REE content (288–281 ppm; one = 153—ppm). All Pennsylvanian <2 μ fractions from Oklahoma have high REE content (209–439 ppm), and fractions from Kansas cyclothems have variable REE content (86–438 ppm). REE content in the <2 μ fractions is inherited from the provenance, but is modified by ion exchange during weathering, transportation, or deposition. Exchangable REE tend to be concentrated in clay minerals in basic environments, but removed in acid environments.Sand and gravel-size fractions consist mostly of quartz or chert so their REE content is low (7.9–40.6 ppm) although heavy minerals may contribute a large fraction of the REE content. Unexpectedly, silt-size fractions have REE contents (74–355 ppm) that are usually lower but similar to their <2 μ fractions, and the REE contents do not correlate to clay mineral/quartz ratios. The interpretation of REE content in sedimentary rocks needs to be done cautiously due to the above factors.     

内蒙古大石寨地区稀土元素的区域分布特征

总结了内蒙古大石寨地区1∶25万区域地球化学调查获得的1点/4km2的水系沉积物组合样品中的La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y等15种稀土元素的区域地球化学分布特征。稀土元素分布与研究区中部的黑云母花岗岩密切相关,轻稀土主要分布在该岩体外围的二叠系地层中,重稀土主要分布在该岩体上方。该岩体上方和外围地层的稀土元素分布、稀土元素总量、轻重稀土比及δCe、δEu、(La/Sm)N、(La/Tb)N、(La/Lu)N、(Ce/Yb)N、(Gd/Lu)N等稀土元素分馏特征的差异明显。利用区域地球化学调查水系沉积物样品中的稀土元素含量,可获得研究区可靠的稀土元素区域地球化学分布特征,也可反映研究区地质特点,并为区域地球化学异常解译提供参考资料。     

Determination of the Rare-Earth Elements and Yttrium In 37 International Silicate Reference Materials By Inductively Coupled Plasma-Atomic Emission Spectrometry

The rare-earth elements (REE) and yttrium have been determined in 37 international rock and mineral reference materials. Samples were prepared using conventional rock-dissolution techniques, and the REE and yttrium were separated from the other constituents using cation-exchange chromatography. The REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) and yttrium were determined simultaneously by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Results for four well-characterised USGS standard rocks agree favourably with "recommended" values and with REE determinations made previously by workers using ICP-AES, isotope dilution mass spectrometry, instrumental neutron activaton analysis and X-ray fluorescence spectrometry.
Les éléments de terres rares (TR) et yttrium ont été dosés dans 37 échantillons internationaux de réféence. Les échantillons ont été décomposés par dissolution acide et les TR séparés par résine échangeuse de cations. Les TR (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) et yttrium ont été dosés simultanément par la spectrométrie d'émission-plasma inductif. Les résultats obtenus pour quatre échantillons de référence bien charactérisés de I'USGS se comparent favorablement avec ceux obtenus par la spectrométrie d'émission-plasma, la dilution isotopique, I'activation neutronique et par la spectrométrie d'é fluorescence-X.     

Experimental rare earth element partition coefficients for garnet,clinopyroxene and amphibole coexisting with andesitic and basaltic liquids

The partitioning of La, Sm, Dy, Ho and Yb between garnet, calcic clinopyroxene, calcic amphibole and andesitic and basaltic liquids has been studied experimentally. Glasses containing one or more REE in concentrations of 500–2000 ppm were crystallized at pressures of 10–35 kbar, and temperatures of 900–1520°C. Water was added to stabilize amphibole and to allow study of partition coefficients over wide temperature ranges. Major element and REE contents of crystal rims and adjacent glass were determined by EPMA, with limits of detection for individual REE of 100–180 ppm. Measured partition coefficients, D_REE^Cryst-liq, are independent of REE concentration over the concentration ranges used.D-values show an inverse dependence on temperature, best illustrated for garnet. At a given temperature, they are almost always higher for equilibria involving andesitic liquid. Garnet shows by far the greatest range of D-values, with e.g. D_La < 0.05 and D_Yb ~ 44 for andesitic liquid at 940°C. D_Yb falls to ~ 12 at 1420°C. D_Sm^Ga-liq also correlates negatively with temperature and positively with the grossular content of garnet. Patterns of D_ree^Cryst-Liq for calcic clinopyroxenes and amphiboles are sub-parallel, with D-values for amphibole generally higher. Both individual D-values and patterns for the crystalline phases studied are comparable with those determined for phenocryst-matrix pairs in natural dacites, andesites and basalts.D-values and patterns are interpreted in terms of the entry of REE³⁺ cations into mineral structures and liquids of contrasted major element compositions. The significance of the partition coefficients for models of the genesis of andesitic and Hy-normative basaltic magmas is assessed. Most magmas of these types in island arcs are unlikely to be produced by melting of garnet-bearing sources such as eclogite or garnet lherzolite.     

Ion-microprobe zircon geochemistry as an indicator of mineral genesis during geochronological studies

This paper considers the distribution of trace elements (including rare earth elements) in zircons dated by the ion-microprobe U-Th-Pb isotope method and its genetic implications. Two problems were addressed on the basis of the investigation of trace element compositions of zircons: (1) genesis of zircons from subalkaline magmatic rocks, sysenites, and sanukitoids and their comparison with tonalites as exemplified by the rocks of the Karelian region, and (2) determination of trace element signatures of zircons from the oldest granulite-facies rocks of the Ukrainian shield. It was shown that the REE distribution patterns of the tonalites, which crystallized in equilibrium with melt, are strictly governed by crystal-chemical laws. The REE distribution patterns show a positive slope with an increase from La to Lu, a positive Ce anomaly, and a negative Eu anomaly. Similar patterns were observed in zircons from the syenites. The trace element contents of zircons are related to those of melts through partition coefficients. Zircons from the sanukitoids show a considerable LREE enrichment, which is inconsistent with the calculated zircon/melt partition coefficients and presumably related to the inherently imperfect zircon structure. Such a structure was formed during zircon crystallization from melt at high temperatures and the anomalous fluid regime that is characteristic, in particular, of sanukitoid melts. The REE distribution patterns of zircons that crystallized under granulite-facies conditions are sharply different from typical distributions in HREE depletion, which was caused by the competitive growth of garnet during zircon crystallization.     

Successive Eruption of Alkaline and Tholeiite Magmas in a Japanese Palaeozoic Geosynclinal Basalt Body with Special Reference to Rare Earth Element Features

Rare-earth element (REE) abundances and major chemical compositionsof six late Palaeozoic geosynclinal basalts at Nakaoku, theKii peninsula, southwest Japan are discussed from the generalviewpoint of geosynclinal basalt magma. The REE patterns ofbasalt samples are smoothly and progressively enriched relativeto Leedey chondrite. The lighter REE are considerably fractionated,whereas concentrations of heaviest REE remain approximatelyconstant. Each fractionation pattern probably corresponds toresidual liquid at different stages during the solidificationof magma in depth. The partition coefficients of REE betweenmagma (i.e. liquid) and crystallizing solid can be calculated,assuming that the partition coefficient of Lu is nearly unity,because the Lu contents show little change among samples. Byusing the REE contents and partition coefficients, solidifiedpercentages for various stages of the magmatic process werecalculated; the percentage shows a good correlation with thesolidification index calculated from major chemical compositions.Some major compositions are also correlative with the solidifiedpercentage calculated from REE data. The Nakaoku basalts when plotted on a silica-alkali diagramshow a change of type from tholeiitic to alkali basalt duringthe solidifying process in depth. These petrochemical aspectsof the Nakaoku basaltic body are compatible with the resultsof experimental melting study at moderate pressures of about10 kb carried out by Green & Ringwood (1967). The spatialcoexistence of tholeiitic and alkali basalt in the Japaneselate Palaeozoic geosyncline found by Sugisaki & Tanaka (1971b)and disclosed here in the Nakaoku basalts, is not uncommon phenomenon.     

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

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

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.