新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。     

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.     

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

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

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

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

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

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

变基性岩部分熔融过程中榍石的微量元素效应:以南迦巴瓦混合岩为例

南迦巴瓦地区广泛出露的中下地壳变基性岩部分熔融形成的层状混合岩和淡色花岗岩,为研究部分熔融过程中榍石的地球化学行为对熔体的微量元素组成的影响提供了良好的机会。相对于源岩或熔融残留体,淡色体亏损Ti、V、REE、Y、Nb、Ta、U等元素,与混合岩中榍石的微量元素特征互补。混合岩、淡色体和榍石微量元素特征表明南迦巴瓦角闪岩部分熔融形成的淡色体的微量元素特征主要受控于榍石的地球化学行为。角闪岩脱水部分熔融过程中,由于长英质熔体的低Ti溶解度,榍石以未熔残留体形式存在于暗色体中,导致熔体亏损Ti、REE、Nb、Ta、V、U等元素和Sr/Y比值相对升高。关键元素在榍石和熔体之间的配分系数受熔体成分影响明显。角闪岩中变质榍石D_Nb/Ta<1,因此变质榍石残留导致熔体Nb/Ta相对于源岩升高;而高Si-Al花岗质熔体中榍石D_Nb/Ta>1,因此与高Si-Al熔体平衡的榍石的分离（转熔或结晶分异）将导致熔体Nb/Ta比值相对源岩降低。榍石在部分熔融过程中的微量元素效应为理解变基性岩部分熔融产生熔体的地球化学特征提供新的认识。     

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.     

Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: evidence from Y/Ho,Zr/Hf,and lanthanide tetrad effect

 The parameters which control the behaviour of isovalent trace elements in magmatic and aqueous systems have been investigated by studying the distribution of yttrium, rare-earth elements (REEs), zirconium, and hafnium. If a geochemical system is characterized by CHArge-and-RAdius-Controlled (CHARAC) trace element behaviour, elements of similar charge and radius, such as the Y-Ho and Zr-Hf twin pairs, should display extremely coherent behaviour, and retain their respective chondritic ratio. Moreover, normalized patterns of REE(III) should be smooth functions of ionic radius and atomic number. Basic to intermediate igneous rocks show Y/Ho and Zr/Hf ratios which are close to the chondritic ratios, indicating CHARAC behaviour of these elements in pure silicate melts. In contrast, aqueous solutions and their precipitates show non-chondritic Y/Ho and Zr/Hf ratios. An important process that causes trace element fractionation in aqueous media is chemical complexation. The complexation behaviour of a trace element, however, does not exclusively depend on its ionic charge and radius, but is additionally controlled by its electron configuration and by the type of complexing ligand, since the latter two determine the character of the chemical bonding (covalent vs electrostatic) in the various complexes. Hence, in contrast to pure melt systems, aqueous systems are characterized by non-CHARAC trace element behaviour, and electron structure must be considered as an important additional parameter. Unlike other magmatic rocks, highly evolved magmas rich in components such as H₂O, Li, B, F, P, and/or Cl often show non-chondritic Y/Ho and Zr/Hf ratios, and “irregular” REE patterns which are sub-divided into four concave-upward segments referred to as “tetrads”. The combination of non-chondritic Y/Ho and Zr/Hf ratios and lanthanide tetrad effect, which cannot be adequately modelled with current mineral/melt partition coefficients which are smooth functions of ionic radius, reveals that non-CHARAC trace element behaviour prevails in highly evolved magmatic systems. The behaviour of high field strength elements in this environment is distinctly different from that in basic to intermediate magmas (i.e. pure silicate melts), but closely resembles trace element behaviour in aqueous media. “Anomalous” behaviour of Y and REEs, and of Zr and Hf, which are hosted by different minerals, and the fact that these minerals show “anomalous” trace element distributions only if they crystallized from highly evolved magmas, indicate that non-CHARAC behaviour is a reflection of specific physicochemical properties of the magma. This supports models which suggest that high-silica magmatic systems which are rich in H₂O, Li, B, F, P, and/or Cl, are transitional between pure silicate melts and hydrothermal fluids. In such a transitional system non-CHARAC behaviour of high field strength elements may be due to chemical complexation with a wide variety of ligands such as non-bridging oxygen, F, B, P, etc., leading to absolute and relative mineral/melt or mineral/aqueous-fluid partition coefficients that are extremely sensitive to the composition and structure of this magma. Hence, any petrogenetic modelling of such magmatic rocks, which utilizes partition coefficients that have not been determined for the specific igneous suite under investigation, may be questionable. But Y/Ho and Zr/Hf ratios provide information on whether or not the evolution of felsic igneous rocks can be quantitatively modelled: samples showing non-chondritic Y/Ho and Zr/Hf ratios or even the lanthanide tetrad effect should not be considered for modelling. However, the most important result of this study is that Y/Ho and Zr/Hf ratios may be used to verify whether Y, REEs, Zr, and Hf in rocks or minerals have been deposited from or modified by silicate melts or aqueous fluids. Received: 4 September 1995 / Accepted: 30 October 1995     

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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With 1 Figure     

Fractionation of Nb and Ta from Zr and Hf at Mantle Depths: the Role of Titanian Pargasite and Kaersutite

Selective enrichment or depletion in either Zr and Hf (HFSE⁴⁺)or Nb and Ta (HFSE⁵⁺) is a feature commonly observed in manymantle-derived melts and amphiboles occurring as either disseminatedminerals in mantle xenoliths and peridotite massifs or in veinassemblages cutting these rocks. The fractionation of Nb fromZr seen in natural mantle amphiboles suggests that their incorporationis governed by different crystal-chemical mechanisms. An extensiveset of new partitioning experiments between pargasite–kaersutiteand melt under upper-mantle conditions shows that HFSE incorporationand fractionation depends on amphibole major-element compositionand the presence or absence of dehydrogenation. Multiple regressionanalysis shows that ^Amph/LD_Nb/Zr is strongly dependent on themg-number of the amphibole as a result of a combination of amphiboleand melt structure effects, so that the following generalizationsapply: (1) high-mg-number amphiboles crystallized from unmodifiedmantle melts more easily incorporate Zr relative to Nb leadingto an increase of the Nb/Zr ratio in the residual melt; (2)low-mg-number amphiboles, such as those found in veins cuttingperidotites, may strongly deplete the residual melt in Nb andcause very low Nb/Zr in residual melts. Implications and applicationsto mantle environments are discussed. KEY WORDS: trace elements; high field strength elements; partition coefficients; amphibole; upper mantle     

Geochemical and Sm–Nd isotopic study of titanite from granitoid rocks of the eastern Dharwar craton,southern India

Titanite occurs as an accessory phase in a variety of igneous rocks, and is known to concentrate geologically important elements such as U, Th, rare earth element (REE), Y and Nb. The differences in the abundances of the REEs contained in titanite from granitoid rocks could reflect its response to changes in petrogenetic variables such as temperature of crystallization, pressure, composition, etc. Widespread migmatization in the granodiorite gneisses occurring to the east of Kolar and Ramagiri schist belts of the eastern Dharwar craton resulted in the enrichment of the REEs in titanite relative to their respective host rocks. A compositional influence on the partitioning of REEs between titanite and the host rock/magma is also noticed. The relative enrichment of REEs in titanite from quartz monzodiorite is lower than that found in the granodioritic gneiss. Depletion of REE and HFSE (high field-strength elements) abundances in granitic magmas that have equilibrated with titanite during fractional crystallization or partial melting has been modelled. As little as 1% of titanite present in residual phases during partial melting or in residual melts during fractional crystallization can significantly lower the abundances of trace elements such as Nb, Y, Zr and REE which implies the significance of this accessory mineral as a controlling factor in trace element distribution in granitoid rocks. Sm–Nd isotope studies on titanite, hornblende and whole rock yield isochron ages comparable to the precise U–Pb titanite ages, invoking the usefulness of Sm–Nd isochron ages involving minerals like titanite.     

Genesis and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif,Mongolia: Evidence from melt inclusions

Melt inclusions were studied by various methods, including electron and ion microprobe analysis, to determine the compositions of melts and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif in Mongolia. Primary crystalline and coexisting melt inclusions were found in quartz from the rare-metal granites of intrusive phase V. Among the crystalline inclusions, we identified potassium feldspar, albite, tuhualite, titanite, fluorite, and diverse rare-metal phases, including minerals of zirconium (zircon and gittinsite), niobium (pyrochlore), and rare earth elements (parisite). The observed crystalline inclusions reproduce almost the whole suite of major and accessory minerals of the rare-metal granites, which supports the possibility of their crystallization from a magmatic melt. Melt inclusions in quartz from these rocks are completely crystallized. Their daughter mineral assemblage includes quartz, microcline, aegirine, arfvedsonite, polylithionite, a zirconosilicate, pyrochlore, and a rare-earth fluorocarbonate. The melt inclusions were homogenized in an internally heated gas vessel at a temperature of 850°C and a pressure of 3 kbar. After the experiments, many inclusions were homogeneous and consisted of silicate glass. In addition to silicate glass, some inclusions contained tiny quench zircon crystals confined to the boundary of inclusions, which indicates that the melts were saturated in zircon. In a few inclusions, glass coexisted with a CO₂ phase. This allowed us to estimate the content of CO₂ in the inclusion as 1.5 wt %. The composition of glasses from the homogeneous melt inclusions is similar to the composition of the rare-metal granites, in particular, with respect to SiO₂ (68–74 wt %), TiO₂ (0.5–0.9 wt %), FeO (2.2–4.6 wt %), MgO (0.02 wt %), and Na₂O + K₂O (up to 8.5 wt %). On the other hand, the glasses of melt inclusions appeared to be strongly depleted compared with the rocks in CaO (0.22 and 4 wt %, respectively) and Al₂O₃ (5.5–7.0 and 9.6 wt %, respectively). The agpaitic index is 1.1–1.7. The melts contain up to 3 wt % H₂O and 2–4 wt % F. The trace element analysis of glasses from homogenized melt inclusions in quartz showed that the rare-metal granites were formed from extensively evolved rare-metal alkaline melts with high contents of Zr, Nb, Th, U, Ta, Hf, Rb, Pb, Y, and REE, which reflects the metallogenic signature of the Khaldzan Buregtey deposit. The development of unique rare metal Zr–Nb–REE mineralization in these rocks is related to the prolonged crystallization differentiation of melts and assimilation of enclosing carbonate rocks.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Kinetically induced compositional zoning in titanite: implications for accessory-phase/melt partitioning of trace elements

Usually it is assumed that the partitioning of trace elements into titanite in metaluminous granitoid plutonic environments takes place under equilibrium conditions and that compositional zoning is due solely to progressive changes in melt chemistry and/or mineral/melt partition coefficients. Examination of titanites from a variety of Caledonian metaluminous granitoids and related rocks has revealed that sector zoning is present, indicating disequilibrium partitioning. The sector zoning in titanites is defined principally by the distribution of the rare earth elements (REE), Y, Nb, Al and Fe. The REE, Y and Nb preferentially occur within the minor (100) sectors relative to the morphologically important (111) sectors. The reverse is true of Al and Fe which preferentially occur within the (111) sectors relative to the (100) sectors. The patterns of sector zoning are complicated by the fact that the relative growth rates of the various crystal faces fluctuated during growth. Sector zoning indicates that crystal-interface kinetics are responsible for the observed patterns of element partitioning. It is concluded that differences in the lateral-layerspreading rates of crystal faces bring about the sector zoning. The results have implications for the use of trace element partition coefficients in the modelling of fractionation processes.     

Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in igneous rocks

Some F-rich granitic rocks show anomalous, nonchondritic ratios of Y/Ho, extreme negative Eu anomalies, and unusual, discontinuous, segmented chondrite-normalised plots of rare earth elements (REE). The effects of F-rich fluids have been proposed as one of the explanations for the geochemical anomalies in the evolved granitic systems, as the stability of nonsilicate complexes of individual rare earths may affect the fluid-melt element partitioning. The lanthanide tetrad effect, related to different configurations of 4f-electron subshells of the lanthanide elements, is one of the factors affecting such complexing behaviour. We present the first experimental demonstration of the decoupling of Y and Ho, and the tetrad effect in the partitioning of rare earths between immiscible silicate and fluoride melts. Two types of experiments were performed: dry runs at atmospheric pressure in a high-temperature centrifuge at 1100 to 1200°C, and experiments with the addition of H₂O at 700 to 800°C and 100 MPa in rapid-quench cold-seal pressure vessels. Run products were analysed by electron microprobe (major components), solution-based inductively coupled plasma mass spectrometry (ICP-MS) (REE in the centrifuged runs), and laser ablation ICP-MS (REE and Li in the products of rapid-quench runs). All the dry centrifuge runs were performed at super-liquidus, two-phase conditions. In the experiments with water-bearing mixtures, minor amounts of aqueous vapour were present in addition to the melts. We found that lanthanides and Y concentrated strongly in the fluoride liquids, with two-melt partition coefficients reaching values as high as 100-220 in water-bearing compositions. In all the experimental samples, two-melt partition coefficients of lanthanides show subtle periodicity consistent with the tetrad effect, and the partition coefficient of Y is greater than that of Ho. One of the mixtures also produced abundant fluorite (CaF₂) and cryolite (Na₃AlF₆) crystals, which enabled us to study fluorite-melt and cryolite-melt REE partitioning. REE concentrations in fluorite are high and comparable to those in the fluoride melt. However, fluorite-melt partition coefficients appear to depend mostly on ionic radii and show neither significant tetrad anomalies, nor differences in Y and Ho partitioning. In contrast, REE concentrations in cryolite are low (∼5-10 times lower than in the silicate melt), and cryolite-melt REE partitioning shows very strong tetrad and Y-Ho anomalies. Our results imply that Y-Ho and lanthanide tetrad anomalies are likely to be caused mainly by aluminofluoride complexes, and the tetrad REE patterns in natural igneous rocks can result from fractionation of F-rich magmatic fluids.     

Trace and rare earth elements as indicators of provenance and depositional environments of Lias cherts in Gumushane,NE Turkey

Trace elements and rare earth elements (REEs) of Lias-aged cherts in the Gumushane area were studied in order to understand their origin and depositional environment. Twenty three chert samples from five stratigraphic sections were analysed by inductively coupled plasma-mass spectrometry, X-ray diffraction, and mineralogical investigation. Lias cherts in the study area are microcrystalline, cryptocrystalline quartz, and megaquartz depending on mineralogical content. Trace elements of the cherts were compared with PAAS, Co, Y, and Th had stronger depletions in the five sections, whereas V, Ni, Zr, Nb, and Hf had smaller depletions. The distribution of Zr, Hf, and Ta yields Zr/Hf, Zr/Ta and Hf/Ta ratios (25/645, 37/665, and 0.18/3, respectively) that differ from those of chondrites and average upper continental crust, suggesting that these elements are likely non-detrital but are sourced from seawater. Th/U ratios range from 0.04 to 0.45 and are lower than those of the upper continental crust (average: 3.9). Lias-aged cherts have low total REE abundances and stronger depletions in five sections of the PAAS and chondrite-normalised plots. The cherts are characterised by a positive Eu anomaly (average: 4.9) and LREE-enrichment (La_N/Yb_N = average: 3.5). In addition, about one-half of the cherts exhibit positive Ce anomaly (range: 0.25–2.58), chondritic Y/Ho values (range: 3.3–60), and low (La/Ce)_N values (average: 1.8). REE and trace element abundance in Lias cherts indicate that these elements were likely derived from hydrothermal solutions, terrigenous sources, and seawater. The REE patterns of the cherts show that they were probably deposited close to a continental margin.     

Contrasting origin of two A-type rhyolite series from the Early Permian Nomgon bimodal volcanic association (Southern Mongolia)

A-type rhyolites of contrasting compositions and eruption characters were revealed among two volcanic series of the Early Permian bimodal association in the Nomgon graben. Rhyolites of the lower volcanic series formed extrusions, lava domes, and tuff horizons. They had low FeO_t, Zr, Hf, Nb, Ta, Y, and REE concentrations and also a moderately depleted Nd isotope composition (ε_Nd(Т) = 6.7–7.1). Their formation was related to anatexis of the juvenile continental crust, triggered by the thermal effect of mafic magmas. Rhyolites of the upper volcanic series formed extensive lava flows and dikes. Their composition was characterized by high FeO_t, Zr, Hf, Nb, Ta, Y, and REE concentrations, and also depleted Nd isotope characteristics (ε_Nd(Т) = 7.7–9.0). These rhyolite melts formed under long-term crystallizational differentiation of basaltoids in the intracrustal magmatic chambers, with limited participation of crustal contamination. The source of magmas for the upper volcanic series was the sublithospheric mantle.     

佛冈高分异I型花岗岩的成因:来自Nb-Ta-Zr-Hf等元素的制约

华南南岭地区发育有大面积的与钨锡成矿相关的侏罗纪花岗岩,然而其中有些花岗岩的成因类型却难以确定。本文以佛冈岩体为例,结合前人已发表数据,对佛冈花岗岩体中Nb、Ta、Zr和Hf等元素的迁移特征及其原理进行探讨,并对佛冈花岗岩的成因类型进行了厘定。随着分异程度增加,佛冈花岗岩Nb和Ta含量增加,Nb/Ta(3.6~15.3)和Zr/Hf(17.3~38.9)比值降低并发生分异。随着Zr含量的降低,佛冈花岗岩的Zr/Hf比值降低,这一特征表明锆石的分离结晶作用使得佛冈花岗岩的Zr/Hf比值分异。Nb/Ta比值分异可能与角闪石和黑云母的分离结晶作用有关。随着Nb/Ta比值降低,Y/Ho比值增加,这一特征表明佛冈花岗岩Nb/Ta比值的分异也和岩浆演化后期的流体有关。佛冈花岗岩不含原生的富铝矿物,为准铝质到弱过铝质岩石。随着分异程度增加,佛冈花岗岩P2O5含量降低,表明它不是S型花岗岩。随着Y/Ho比值增加和Nb/Ta和Zr/Hf比值降低,佛岗花岗岩Ga/Al和Fe OT/Mg O比值增加,从典型I型花岗岩特征演化到类似A型花岗岩的地球化学特征。因此,我们认为佛冈花岗岩不是A型花岗岩而是高分异的I型花岗岩。区域上与成矿相关的流体和花岗质岩浆的相互作用和分离结晶作用,使得华南南岭地区的花岗岩地球化学特征复杂,所以其成因类型也变的难以确定。     

Major and trace element variation in ilmenite in the Skaergaard Intrusion: petrologic implications

Ilmenite separates from the floor (LS), roof (UBS), and wall (MBS) sequences of the Skaergaard Intrusion were analyzed for major and trace elements using DCP-AES and ICP-MS techniques. In all three sequences, FeO progressively increases, and MgO and Al₂O₃ progressively decrease with differentiation. Although trace element abundances are, in general, higher in UBS ilmenite than in MBS and LS ilmenite, all three sequences have similar trends for trace element abundance vs. crystallization. Ba, Cs, Rb, Sr, Th, U, Y, and the REEs are excluded elements in ilmenite, and remained at low abundances during differentiation. Cr, Ni, Sc, and V are included elements in ilmenite and other mafic phases, and decreased during differentiation. V contents in ilmenite, however, do not decrease significantly until the upper part of the middle zone, suggesting that magnetite did not begin to affect the magma differentiation trend until much later than when it first appears in the intrusion. Hf, Nb, Ta, and Zr, which are strongly excluded elements in silicates, are included elements in ilmenite. The element ratios Zr/Hf, Y/Ho, Nb/Ta, and U/Th are relatively constant in Skaergaard ilmenite from different parts of the intrusion, suggesting that fluid transport did not significantly effect these elements during differentiation or post-solidification cooling. Calculated partition coefficients for ilmenite in the Skaergaard Intrusion are similar to those reported from previous studies of lunar and terrestrial basalts and kimberlites, and for most elements are significantly lower than those reported for ilmenite in rhyolitic magma. Similar D_i's for Zr, Hf, Nb, and Ta suggest that ilmenite crystallization did not significantly affect Zr/Nb or Hf/Ta in the Skaergaard magma, but the ratios of Zr, Hf, Nb, or Ta to other high field strength elements, such as Th, U, Y, or the REEs, may have been altered by ilmenite fractionation.     

LA-ICP-MS mineral chemistry of titanite and the geological implications for exploration of porphyry Cu deposits in the Jinshajiang – Red River alkaline igneous belt,SW China

The Jinshajiang–Red River alkaline igneous belt in the eastern Indian–Asian collision zone, of southwestern China, hosts abundant, economically important Cu–Mo–Au mineralization of Cenozoic age. Major- and trace-element compositions of titanites from representative Cu-mineralized intrusions determined by LA-ICP-MS show higher values for Fe₂O₃/Al₂O₃, ΣREE?+?Y, LREE/HREE, Ce/Ce*, (Ce/Ce*)/(Eu/Eu*), U, Th, Ta, Nb and Ga, and lower values for Al₂O₃, CaO, Eu/Eu*, Zr/Hf, Nb/Ta and Sr than those for titanites from barren intrusions. Different ΣREE?+?Y, LREE/HREE, U, Th, Ta and Nb values of titanites between Cu-mineralized and barren intrusions were controlled mainly by the coexisting melt compositions. However, different Sr concentrations and negative Eu anomalies of titanites between Cu-mineralized and barren intrusions were most probably caused by different degrees of crystallization of feldspar from melts. In addition, different Ga concentrations and positive Ce anomalies of titanites between Cu-mineralized and barren intrusions were most likely caused by different magmatic fO₂ conditions. Pronounced compositional differences of titanites between Cu-mineralized and barren intrusions can provide a useful tool to help discriminate between ore-bearing and barren intrusions at an early stage of exploration, and, thus, have a potential application in exploration for porphyry Cu deposits in the Jinshajiang – Red River alkaline igneous belt, and to other areas.     

Evolution of melts of the Changbaishan Tianchi volcano (China–North Korea) as a model of ore–magmatic system formation: Data from melt inclusions studies

The composition and evolution of the melts of trachytes from the volcano were studied based on examining the inclusions of mineral-forming media by means of X-ray and ion microanalysis. A correlation was shown between the degree of enrichment of these melts in rare elements and the processes of magmatic differentiation. It was found that trachytes of the volcano were generated in highly differentiated alkaline melts enriched in Hf, Nb, Zr, Ta, U, Th, Rb, Y, and REEs under 1020–1060°C. The evolution of melts was determined by the processes of crystal fractionation. The main volatile components in the melts are water, fluorine, and chlorine with the concentrations of 0.1–0.5, 0.2–0.5, and 0.2–0.3 wt %, respectively. The melt crystallization was accompanied by degassing caused by the decrease in the outer pressure. The low concentrations of water and fluorine represent the melt composition by these components exclusively at the time of the melt movement towards the Earth’s surface just before the eruption.