Trace element chemistry of Apollo 14 lunar soil from Fra Mauro

Analytical data are presented for Apollo 14 fines ( < 1 mm) sample 14163,136 for 31 trace elements. The heavy REE are enriched monotonically by factors of 105 ± 10 over chondrites. Eu shows a large depletion (30 × chondrites) and the light REE show a smooth progressive enrichment with a slight fall at La. Ba, Cs, Th, U, Nb, Zr and Hf are strongly enriched, relative to chondritic abundances. Thus the outer portions of the moon sampled by the Imbrium event, and now represented by the Fra Mauro Formation, possessed high concentrations (100–200 × chondrites) for many elements, prior to the excavation of the mare basins. A correlation may exist between Gd/Eu and Zr/Hf ratios in lunar materials.     

Geochemical constraints on cumulate textured Ti-rich Al-depleted Komatiites from Chotanagpur Gneissic Complex,Eastern India

For the first time occurrence of Ti rich Al depleted ultramafic cumulates having komatiitic signature in the northwestern fringe of Chotanagpur Gneissic Complex is presented. These rocks exhibit intrusive relationship with metasedimentary rocks and metaultramafites. Geochemically they are characterized by Mg# 79.1–91.60, high TiO₂ (1.29–1.54 wt%), significantly low Al₂O₃/TiO₂ and (Gd/Yb)_n >1. Major oxides, trace and REE content suggest low degree of fractional crystallization and lesser degree of partial melting. These Al depleted komatiites are characterized by high concentration of incompatible elements than most suites of Barberton type komatiites. High Ti content suggests less degree of majorite garnet melting, leaving behind garnet in the restite. The rock shows higher Ti/Sc (190),Ti/V (22), Zr/Y (3), Zr/Sc (4), V/Sc (8), Zr/Sm (28) and Zr/Hf (47) ratios than primitive mantle and REE distribution pattern shows gentle slope from LREE to HREE in most samples pointing towards mantle metasomatism and crustal contamination during emplacement. The observed chemical characteristics indicate derivation of komatiite from an enriched mantle source and represent plume activity in an extensional tectonic regime of intracratonic setting.     

Bizarre geochemistry of komatiites from the Crixás greenstone belt,Brazil

Komatiite lava flows in the Crixás greenstone belt, Goiás, Brazil, have textures and volcanic structures typical of Archean komatiites, but are geochemically most unusual. The flows are porphyritic and massive, or layered with spinifex upper parts and olivine cumulate lower parts. MgO contents range from 18 to 40%. In such lavas, only olivine (and minor chromite) can have crystallized, but neither major nor trace elements fall on olivine control lines. In MgO variation diagrams, CaO and Sr fall on lines with slopes steeper than olivine control lines; SiO₂, FeO, Na₂O, K₂O and Y show little systematic variation; Zr shows a large variation that does not correlate with MgO; and Al₂O₃ decreases markedly with decreasing MgO. The aberrant behaviour is highlighted by the REE (rare earth elements) in spinifex and olivine cumulate layers from three flows: in the spinifex layers, chondrite-normalized REE patterns are hump-shaped with maxima at Nd or Sm ((La/Sm)_N=0.6, (Gd/Yb)_N=1.6–2.3), whereas cumulate zones in the same flows have steadily sloping patterns, with LREE enriched relative to HREE ((La/Sm)_N=1.3, (Gd/Yb)_N=1.4). Neither normal magmatic processes acting during emplacement of the komatiites, nor thermal erosion and wall-rock assimilation can explain these effects, and we speculate that elements commonly thought of as “immobile” (e.g. Al, Zr, REE) migrated during hydrothermal alteration or metamorphism. A Pb-Pb whole rock isochron gave an age of 2,728±140 Ma and selected Sm-Nd analyses an apparent isochron age of 2,825±98 Ma (ɛ_Nd≈0). The Pb-Pb age is believed to be the approximate time of emplacement. Interpretation of the Sm-Nd data is complicated by the evidence of mobility of REE.     

Integrated Models of Basalt Petrogenesis: A Study of Quartz Tholeiites to Olivine Melilitites from South Eastern Australia Utilizing Geochemical and Experimental Petrological Data

The Tertiary to Recent basalts of Victoria and Tasmania havemineralogical and major element characteristics of magmas encompassingthe range from quartz tholeiites to olivine melilitites. Abundancesof trace elements such as incompatible elements, including therare earth elements (REE), and the compatible elements Ni, Coand Sc, vary systematically through this compositional spectrum.On the basis of included mantle xenoliths, appropriate 100 Mg/Mg+ Fe₊₂ (68–72) and high Ni contents many of these basaltsrepresent primary magmas (i.e., unmodified partial melts ofmantle peridotite). For fractionated basalts we have derivedmodel primary magma compositions by estimating the compositionalchanges caused by fractional crystallization of olivine andpyroxene at low or moderate pressure. A pyrolite model mantlecomposition has been used to establish and evaluate partialmelting models for these primary magmas. By definition and experimentaltesting the specific pyrolite composition yields parental olivinetholeiite magma similar to that of KilaeauIki, Hawaii (1959–60)and residual harzburgite by 33 per cent melting. It is shownthat a source pyrolite composition differing only in having0.3–0.4 per cent TiO₂ rather than 0.7 per cent TiO₂, isable to yield the spectrum of primary basalts for the Victorian-Tasmanianprovince by 4 per cent to 25 per cent partial melting. The mineralogiesof residual peridotites are consistent with known liquidus phaserelationships of the primary magmas at high pressures and thechemical compositions of residual peridotite are similar tonatural depleted or refractory lherzolites and harzburgites.For low degrees of melting the nature of the liquid and of theresidual peridotite are sensitively dependent on the contentof H₂O, CO₂ and the CO₂/H₂O in the source pyrolite. The melting models have been tested for their ability to accountfor the minor and trace element, particularly the distinctivelyfractionated REE, contents of the primary magmas. A single sourcepyrolite composition can yield the observed minor and traceelement abundances (within at most a factor of 2 and commonlymuch closer) for olivine melilitite (4–6 per cent melt),olivine nephelinite, basanite (5–7 per cent melt), alkaliolivine basalt (11–15 per cent melt), olivine basalt andolivine tholeiite (20–25 per cent melt) provided thatthe source pyrolite was already enriched in strongly incompatibleelements (Ba, Sr, Th, U, LREE) at 6–9 x chondritic abundancesand less enriched (2.5–3 x chondrites) in moderately incompatible(Ti, Zr, Hf, Y, HREE) prior to the partial melting event. Thesources regions for S.E. Australian basalts are similar to thosefor oceanic island basalts (Hawaii, Comores, Iceland, Azores)or for continental and rift-valley basaltic provinces and verydifferent in trace element abundances from the model sourceregions for most mid-ocean ridge basalts. We infer that thismantle heterogeneity has resulted from migration within theupper mantle (LVZ or below the LVZ) of a melt or fluid (H₂O,CO₂-enriched) with incompatible element concentrations similarto those of olivine melilitite, kimberlite or carbonatite. Asa result of this migration, some mantle regions are enrichedin incompatible elements and other areas are depleted. Although it is possible, within the general framework of a lherzolitesource composition, to derive the basanites, olivine nephelinitesand olivine melilitites from a source rock with chondritic relativeREE abundances at 2–5 x chondritic levels, these modelsrequire extremely small degrees of melting (0.4 per cent forolivine melilitite to 1 per cent for basanite). Furthermore,it is not possible to derive the olivine tholeiite magmas fromsource regions with chondritic relative REE abundances withoutconflicting with major element and experimental petrology argumentsrequiring high degrees (15 per cent) of melting and the absenceof residual garnet. If these arguments are disregarded, andpartial melting models are constrained to source regions withchondritic relative REE abundances, then magmas from olivinemelilitites to olivine tholeiites can be modelled if degreesof melting are sufficiently small, e.g., 7 per cent meltingfor olivine tholeiite. However, the source regions must be heterogenousfrom 1 to 5 x chondritic in absolute REE abundances and heterogerieousin other trace elements as well. This model is rejected in favorof the model requiring variation in degree of melting from 4per cent to 25 per cent and mantle source regions ranging fromLREE-enriched to LREE-depleted relative to chondritic REE abundances.     

Glasses in the D'Orbigny angrite

The angrites are a small and heterogeneous group of achondritic meteorites with highly unusual chemical and mineralogical features. The abundant presence of glasses in D'Orbigny makes this rock a unique member of the angrite group. Glasses fill open spaces, form pockets, and occur as inclusions in olivines. Their physical settings exclude an incorporation from an external source. Major and trace element (rare earth elements [REE], Li, B, Be, transition elements, N and C) contents of these glasses and host olivines were measured combining laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), secondary-ion mass spectrometry (SIMS), Nuclear Reaction Analysis (NRA), and EMP techniques. Based on the major element composition, glasses filling voids could represent either a melt formed by melting an angritic rock or a melt from which angrites could have crystallized. Trace element contents of these glasses strongly indicate a direct link to the D'Orbigny bulk meteorite. They are incompatible with the formation of the glasses by partial melting of a chondritic source rock or by shock melting. The refractory elements (e.g., Al, Ti, Ca) have about 10 × CI abundances with CaO/TiO₂ and FeO/MnO ratios being approximately chondritic. Trace element abundances in the glasses appear to be governed by volatility and suggest that the refractory elements in the source had chondritic relative abundances. Although the glasses (and the whole rock) lack volatile elements such as Na and K, they are rich in some moderately volatile elements such as B, V, Mn, Fe (all with close to CI abundances), and Li (about 3-5 × CI). These elements likely were added to the glass in a sub-solidus metasomatic elemental exchange event. We have identified a novel mechanism for alteration of glass and rock compositions based on an exchange of Al and Sc for Fe and other moderately volatile elements in addition to the well-known metasomatic exchange reactions (e.g., Ca-Na and Mg-Fe).Because glass inclusions in olivine were partly shielded from the metasomatic events by the host crystal, their chemical composition is believed to be closer to the original composition than that of any other glasses. The relative trace element abundances in glasses of glass inclusions in olivine and glass pockets are also unfractionated and at the 10 to 20 × CI level. These glasses are chemically similar to the common void-filling glasses but show a much wider compositional variation. Inclusion glasses demonstrate that at least olivine grew with the help of a liquid. In analogy to olivines in carbonaceous chondrites, initial formation could also have been a vapor-liquid-solid condensation process. At that time, the glass had a purely refractory composition. This composition, however, was severely altered by the metasomatic addition of large amounts of FeO and other moderately volatile elements. The presence of volatile elements such as carbon and nitrogen in glasses of glass inclusions is another feature that appears to give these glasses a link with those hosted by olivines of carbonaceous chondrites. All these features point to an origin from a vapor with relative abundances of condensable elements similar to those in the solar nebula.     

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.     

陕西商州地区丹凤变质火山岩的地球化学特征

陕西商州地区丹凤变质火山岩具有洋内岛弧火山岩地球化学特征,它们是分别来自不同源区的拉斑玄武和钙碱性2个系列共存的一套变质火山岩。其Th/Ta比值高及Ni、Ta、Ti、Y和Yb含量低,表明岩石受到消减带组分的影响。种种证据表明,丹凤变质火山岩是早古生代华北地块南缘消减带之上洋内岛弧环境的产物。     

Trace elements in the Allende meteorite—IV. Amoeboid olivine aggregates

INAA data for Ca, Sc, Hf, La, Ce, Sm, Eu, Tb, Yb, Lu, Os, Ir, Ru, Na, Cl, Br, Fe, Mn, Cr, Co, Au, As, and Sb are presented for ten amoeboid aggregates from the Allende meteorite. Only one lacks olivine. Seven of the remainder, as a group, have cosmic proportions of refractory lithophile and siderophile elements and appear to have formed when coarse-grained Allende inclusion material underwent partial reaction with a low-temperature nebular gas and mixture with FeO-rich olivine. The other two have highly fractionated abundances of refractory elements relative to one another compared to Cl chondrites, including Group II REE patterns, and probably formed by the mixing of fine-grained Allende inclusion material with FeO-rich olivine. Non-refractory siderophile components are also different in composition in each type of amoeboid olivine aggregate.     

黄河和长江沉积角闪石亲石元素地球化学特征对比与物源辨识

为辨识黄河和长江入海沉积物中角闪石的物源差异,对采自黄河口段、长江口段以及废黄河口和苏北沿岸,共26个样点、38组粒度粗细不同的碎屑角闪石进行了矿物元素地球化学测试,获得了这些角闪石群体的50种常量和微量元素含量值.结果表明:不同粒级测量的同源角闪石元素含量除少数大离子活泼元素相对偏差较大之外,大部分元素含量差异性较小...     

Experimental cpx/melt partitioning of 24 trace elements

Cpx/melt partition coefficients have been determined by ion probe for 24 trace elements at natural levels in an alkali basalt experimentally equilibrated at 1,380°C and 3 GPa. One goal was to intercompare Ds for both high-field-strength elements and rare earth elements (REE) in a single experiment. Relative to the REE spidergram, Hf and Ti show virtually no anomaly, whereas Zr exhibits a major negative anomaly. Other incompatible elements (Ba, K, Nb) fall in the range of published values, as do elements such as Sr, Y, Sc, Cr and V. Pb shows a value intermediate between La and Ce. Values for Be, Li and Ga are reported for the first time, and show that Be is as incompatible as the light REEs whereas Li and Ga are somewhat more compatible than the heavy REE.     

The abundances of titanium,zirconium and hafnium in stony meteorites

The concentrations of Ti, Zr and Hf have been determined, by a stable isotope dilution method, in 27 chondrites, seven achondrites and standard rock samples BCR-1 and W-1.Among all chondrites investigated, enstatite chondrite Abee is lowest in Ti atomic ratio compared with Si while all carbonaceous chondrites show higher values. The Zr contents are higher in CII and CIII chondrites, relative to the other groups of chondrites. There is a clustering of Ti and Zr within each group. The $\text{Zr}\text{Hf}$ ratios in CII, CIII. E and H chondrites are essentially the same, while that in the CI chondrite is lower and in L, LL and unequilibrated chondrites are higher.The concentrations of Ti, Zr, Hf and $\text{Ti}\text{Zr}$, $\text{Zr}\text{Hf}$ ratios in achondrites are variable, even among members of the same group.Based on these results, condensation models for these elements are discussed. The variable results for Ti, Zr and Hf in achondrites may be due to the reheating recrystallization and metamorphic processes.‘Cosmic atomic abundances’ of Ti, Zr and Hf are calculated as 2470, 11.2 and 0.185. respectively for Si = 10⁶ atoms.     

REE fractionation and Ce anomalies in weathered Karoo dolerite

Analyses of samples from a weathering profile on Karoo dolerite allow elements to be divided into three groups depending on their behaviour. Si, K, Na, Mg, Ca, Sr, Ba and V are mobilized and removed from weathered products. Fe, Al. Ti, Zr, Hf, Zn, Cu, Sc, Co and Ni are immobile. REE, Y, and to a lesser extent Cr, are mobile and redistributed within the profile without a net loss of these elements from the profile. Large positive Ce anomalies are developed in oxidized weathered products by preferential leaching of the other REE's. Negative Ce anomalies and REE enrichment is a feature of less altered dolerite.     

Compositions of Formosan basalts and aspects of their petrogeneses

Twenty-three basalts from northwestern Formosa were analyzed for Si, Ti, Al, Fe, Mg, Ca, Na, K, Rb, Sr, Hf, Co, Sc, Cr, Th, and 7 REE. Formosan alkalic basalts are generally similar to most alkalic basalts, and Formosan tholeiites are somewhat similar to island arc and continental tholeiites in terms of trends in K/Rb, Rb/Sr, K/Sr, and Ca/Sr ratios. Compared to most submarine tholeiites, Formosan tholeiites are enriched in Rb relative to K and Sr, and enriched in Sr relative to K and Ca. Both types of Formosan basalts show, relative to chondritic proportions, enrichments in light REE which smoothly decrease through the heavy REE. Their REE patterns are similar to those observed in Dogo-Oki alkalic basalts, Hawaiian basalts, and Deccan Plateau basalt, but differ strikingly from those of Japanese tholeiites and oceanic ridge basalts. These relationships and contrasts suggest that Formosan basalts originated in a plagioclase-free portion of the upper mantle and at greater depths that did Japanese tholeiites and oceanic ridge basalts.     

LA-ICP-MS study of apatite- and K feldspar-hosted primary carbonatite melt inclusions in clinopyroxenite xenoliths from lamprophyres, Hungary: Implications for significance of carbonatite melts in the Earth’s mantle

We report the results of LA-ICP-MS analyses of rock forming minerals in clinopyroxene-apatite-K feldspar-phlogopite (CAKP) metasomatic xenoliths and primary carbonatite melt inclusions (CMI) hosted in apatite (Ap) and K feldspar (Kfs). The xenoliths are from the Cretaceous lamprophyre dikes of the Transdanubian Central Range, Hungary. The CMI in Ap have phosphorus dolomitic composition as opposed to CMI in Kfs, which display dolomitic alkali-aluminosiliceous character. The melts found in CMI in Ap and in Kfs likely formed by liquid-liquid separation from an originally carbonate- and phosphorous-rich melt. Primitive mantle (PM) normalized trace element distributions of both Ap- and Kfs-hosted CMI (n = 60 and 20, respectively) reveal a strong negative Ti-anomaly, and an extreme enrichment in incompatible elements (U, Th, LILE and LREE) relative to HREE, Sc, V, Ni and Cr. Rarely, apatites contain unique CMI, which show major- and trace-element signature transitional to K feldspar-hosted CMI. This is due to heterogeneous entrapment of an immiscible phosphorous-bearing carbonatite melt and a carbonate-bearing alkali aluminosiliceous melt, which is a further evidence for their co-existence. CMI reveal that U, Th, Pb, Nb, Ta, P, Sr, Y and REE partitioned into the phosphorous-bearing carbonatite melt, whereas Cs, Rb, Na, K, B, Al, Zr and Hf preferred the silicate-bearing liquid.PM normalized REE pattern (high LREE/HREE), elevated Zr and Hf contents and negative Ti anomaly of clinopyroxene (Cpx) indicate that its formation is genetically linked to carbonatite metasomatism attested by CMI. Trace element partitioning between the studied Cpx and CMI is in accordance with experimentally determined trace element distributions between Cpx and carbonatite melt. Cpx, which occur in samples with high modal proportion of apatite represent mantle section, which interacted with a higher amount of “initial” carbonatite melt than Cpx from apatite-poor xenoliths. This is confirmed by higher Cr, Ni, V, Sc, Ti and lower Zr, as well as Hf concentration in Cpx from xenoliths with low modal abundance of Ap. CMI reveal that Ti, V, Ni and Cr were in lower concentration in the “initial” carbonatite melt than in PM. Contrarily, Zr and Hf were more abundant in this melt than in PM. Consequently, a continuously migrating “initial” carbonatite melt, increased Zr and Hf concentration, and decreased Ti, Sc, V, Ni and especially Cr in the clinopyroxenes. Our findings suggest that the studied CAKP rocks were formed by carbonatite melt metasomatism, which occurred in an open system in the upper mantle.     

橄榄石微量元素原位分析的现状及其应用

随着高精度EMPA和LA-ICP-MS分析技术的发展和矿物微量元素测试精度的提高,利用橄榄石中的微量元素示踪地幔部分熔融、地幔交代作用、岩浆早期结晶过程等地质问题成为近年来一个新兴的研究方向。一系列开拓性的研究发现也被陆续的发表,主要涉及橄榄石中Ni、Co、Al、Cr、Zn、Ti、Li、V、Sc、Mn、Ca和P等元素的示踪使用。一些卓有成效的示踪方法为:Ca、Al、Ti、Ni及Mn能够很好的用于区分橄榄石捕掳晶和斑晶;橄榄石-尖晶石地幔演化趋势线(OSMA:olivine-spinel mantle array)图解可以用于表征岩浆源区的亏损程度;玄武岩中橄榄石斑晶的Li同位素及Li含量可以很有效地指示岩浆源区是否存在地壳物质再循环及地幔交代作用;橄榄石斑晶中Ni、Ca、Mn、Cr和Al协变关系图解可以识别岩浆的辉石岩源区;利用橄榄石捕掳晶中Zr和Sc的含量差异特征可将橄榄岩中三种最主要的类型(尖晶石橄榄岩、石榴石橄榄岩以及尖晶石-石榴石橄榄岩)区分开来;一些元素的比值或组合(例如Ni/Co、Fe/Mn、V/Sc、Zr和Sc、Ca和Ti)可以指示源区交代作用、岩浆作用过程及氧化状态;基于橄榄石中Al、Cr及Ca的地质温度计可以为推算地幔热状态提供新方法;基于橄榄石分离结晶Fo-NiO演化线的原始岩浆计算模型可以较好的推算原始岩浆成分;利用橄榄石的环带及微量元素的扩散机制可以判别更多岩石成因信息,如识别交代介质、熔体类型以及地质构造背景等。基于上述最新研究的相关资料和已有成果,本文对橄榄石微量元素的地球化学示踪方法做系统性的归纳整理,并对橄榄石微量元素赋存状况、橄榄石微量元素测试方法、橄榄石微量元素的使用条件及需注意的问题等进行讨论,为读者在做相关研究时提供参考。     

APPLICATION OF THE ICP-MS TECHNIQUE TO TRACE ELEMENT ANALYSIS OF PERIDOTITES AND THEIR MINERALS

Inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of Rb, Sr, Ba, Zr, Hf, Nb, Ta, Th, U, Pb, Sc and 14 REE in peridotites and their constituent minerals: garnet, clinopyroxene, orthopyroxene and olivine. Determination limits for most elements are 1–10 ppb (in the solid sample), with accuracy and precision comparable to those of thermal ionisation and spark-source mass spectrometry. New data on international standards PCC-1, DTS-1, UB-N and JP-1 are reported.     

Ti-rich komatiites from northern Norway

Komatiites of the Karasjok Greenstone Belt, northern Norway, show two unusual features: they have certain compositional differences compared with other komatiites, and they are largely volcaniclastic in origin. Their geological setting suggests that the komatiites were crupted into shallow water, thus permitting phreatomagmatic eruption, in a small ocean basin that opened in the Baltic Shield. The major oxides (except for TiO₂), the trace elements Y, Sc, V, heavy rare earth elements (HREE), Cr, Co, Ni and the platinum group elements (PGE) cover similar ranges to those observed in other komatiites, but TiO₂, Sm, Zr and Hf (Ti-associated elements, TAE) are enriched compared with abundances commonly reported for komatiites. Thus, the Karasjok komatiites have interelement ratios 2 to 3 times greater than chondritic between the TAE and the HREE, PGE, Sc, V, Y, Al (HRE-associated elements, HAE). The light rare earth elements (LREE), Ta and Th are enriched in some samples relative to Ti, Sm, Zr, and Hf, but are depleted in others. One group of rocks that is similar to the Karasjok komatiites both in terms of geological setting and geochemistry is the Baffin Bay picrites. The reason for the high concentrations of TAE in the Karasjok komatiites could be that they formed at lower degrees of partial melting than most komatiites. The greater-than-chondritic TAE/HAE ratios indicate that garnet was a residual phase during their formation, requiring that the melt formed at a pressure greater than 40 kb. A model involving decompression melting of a mantle plume rising in a rifting environment, can explain the main features of the Karasjok komatiites.     

Subsolidus reactions monitored by trace element partitioning: the spinel- to plagioclase-facies transition in mantle peridotites

Mantle peridotites of the External Liguride (EL) Units (Northern Apennines) mainly consist of fertile spinel-lherzolites partially recrystallized to plagioclase-facies assemblages, and are consequently appropriate to investigate the interphase element partitioning related to the transition from spinel- to plagioclase-facies stability field. Evidence for the development of the plagioclase-facies assemblage is mainly given by: (1) large exsolution lamellae of orthopyroxene and plagioclase within spinel-facies clinopyroxene; (2) plagioclase rims around spinel; (3) granoblastic domains made up of olivine+plagioclase±clino-and orthopyroxene. In situ major and trace [REE (rare-earth elements), Ti, Sc, V, Cr, Sr, Y, Zr and Ba] element mineral analyses have been performed, by electron and ion probe, on selected samples which show the progressive development of the plagioclase-bearing assemblage. The main compositional variations observed during the change from spinel- to plagioclase-facies minerals are as follows: (1) clinopyroxenes decrease in Al, Na, Sr, Eu/Eu^* and increase in Y, V, Sc, Cr, Zr and Ti; (2) amphiboles decrease in Eu/Eu^*, Sr, Ba and increase in Zr and V; (3) spinels decrease in Al and increase in Cr and Ti. The most striking feature is the decoupling in the behaviour of similarly incompatible elements (D about 0.1) in clinopyroxene, e.g. Sr decrease is mirrored by Zr increase. Massbalance calculations indicate that the trace element interphase redistribution documented in the EL peridotites occurred in a closed system and in response to the metamorphic reaction governing the transition from the spinel- to the plagioclase-facies stability field. The observed element partitioning reveals, moreover, that subsolidus re-equilibration processes in the upper mantle produce HFSE (high-field-strength element)/REE fractionation in minerals, which must be evaluated for a reliable determination of mineral-melt distribution coefficients. The results of this study furnish evidence for subsolidus metamorphic evolution during decompression, without concomitant partial melting processes. This is consistent with the interpretation that the EL peridotites represent subcontinental lithospheric mantle emplaced at the surface in response to lithospheric thinning and tectonic denudation mechanisms related to the Triassic-Jurassic rifting of the Ligure-Piedmontese basin.     

Chemical composition and origin of the earth's primitive mantle

An attempt has been made to estimate the chemical composition of the earth's primitive mantle by a critical evaluation of data derived from ultramafic mantle samples and partial melting model calculations for mafic and ultramafic magmas of various ages.Compatible (Al, Ca, Si, Mg, Fe) and moderately incompatible (Ti, Zr, heavy and middle rare earth) elements in basaltic magma sources have not changed significantly since the early Archaean (~3.5 Byr). Estimated abundances for refractory lithophile elements (such as Al, Ca, Ti, Zr, Y, Se, REE etc.) in the primitive mantle are about 2.0 times ordinary chondrites (~ 1.1 times Cl chondrites relative to Mg). Highly incompatible volatile elements (K, Rb, Cs, Tl, Pb etc.) are depleted in the mantle throughout geological time. Abundances of Fe, Ni and Co are obtained on the basis of values for ultramafic nodules and model calculations using komatiites of various ages. The results show little (? 20%?) dispersion and there is no obvious secular variation since 3.5 Byr. Noble metals show similar effects. These data permit constraints to be placed on the timing of core formation.The estimated elemental abundances for the primitive mantle are normalized to Cl chondrites relative to Mg and plotted against the solar condensation temperature at 10^?4 atm. Above 700 K there are two parallel trends which are defined by lithophile elements (Al, Ca, REE, Ti, Mg, Si, Cr, Mn, Na, K, Rb, F, Zn etc.) and siderophile elements (W, Ni, Co, P, As, Ag, Sb and Ge) respectively. The depletion factor for the siderophile trend relative to the lithophile trend is about 0.085. Within each trend there is a continuous depletion towards lower temperature. A third trend is defined by noble metals (Ir, Os, Re, Pd, Pt and Au) with a depletion factor of about 0.003 relative to Cl chondrites. These trends are interpreted in terms of core-mantle differentiation and volatility-controlled processes operating before and during earth accretion.     

Efremovka 101.1: a CAI with ultrarefractory REE patterns and enormous enrichments of Sc, Zr, and Y in Fassaite and Perovskite

Inclusion 101.1 from the CV3 carbonaceous chondrite Efremovka is a compact Type A Ca-Al-rich inclusion (CAI) highly enriched in ultrarefractory (UR) oxides. It is the first complete CAI with a UR rare earth element (REE) pattern found in a CV3 chondrite. The inclusion is petrographically complex and was formed in a multistage process. It consists of several lithologically unrelated units.The core contains abundant Y- and Zr-perovskite, Sc- and Zr-rich fassaite, and metallic FeNi enclosed in melilite. All mineral species (except spinel) in all lithological units exhibit the same basic UR REE pattern. Four different populations of perovskites are distinguished by different Y/Zr ratios. A few of the perovskites have Y/Zr ratios similar to those obtained from crystal/liquid fractionation experiments. Perovskites from the other three populations have either chondritic, lower than chondritic Y/Zr ratios or extremely low Zr contents. Ca isotopic ratios differ among three perovskites from different populations, demonstrating a variety of sources and formational processes. Most fassaites crystallized in situ through reaction between the CAI liquid and preexisting perovskites. This process induced redistribution of Zr, Y, Sc, and V between perovskite and fassaite, thus overprinting the original abundances in perovskite. Fassaite reaction rims around FeNi metals are also encountered. They are enriched in V, which was gained from the metal through oxidation of V in metal during fassaite crystallization. The relative abundances of Zr, Y, and Sc in perovskites are complementary to the abundances of these elements in Sc- and Zr-fassaite, indicating subsolidus partitioning of these elements between the two phases. Perovskites are enriched in Y and depleted in Sc and Zr in comparison to fassaites.The core contains two complete captured CAIs, several sinuous fragments, and fine-grained polygonal refractory fragments. An assemblage of andradite-wollastonite-hedenbergite and pure metallic iron is encountered as enclaves in the interior of some sinuous fragments. Metallic Fe and wollastonite formed by reduction of preexisting andradite and hedenbergite nebular alteration products upon inclusion in the highly reduced CAI melt. Numerous spinel clusters and framboids with varying V₂O₃ and Cr₂O₃ concentrations are enclosed in individual melilite crystals in the host CAI and captured CAIs. The rim sequence of the host consists of six layers (from the inside outward): (a) FeO-poor spinel, (b) Sc-bearing fassaite, (c) Al-diopside, (d) Al- and Ca-bearing olivine, (e) pure diopside, and (f) Ca-poor olivine. Like the constituents of the CAI core, all mineral layers of the rim sequence, except spinel, have the same UR REE pattern. However, the total REE abundances decrease systematically by 1 order of magnitude from layer 2 to layer 6. This feature strongly suggests formation of the rim sequence by successive condensation from a unique reservoir enriched in UR elements and excludes formation by flash heating. Petrography, mineral chemistry, REE, refractory lithophile element abundances, and Ca isotopic compositions demonstrate the complex multistage formation history of a CAI that on the surface looks like a regular Type A inclusion.