Platinum-group element abundances in the upper mantle: new constraints from in situ and whole-rock analyses of Massif Central xenoliths (France)

Fourteen peridotite xenoliths collected in the Massif Central neogene volcanic province (France) have been analyzed for platinum-group elements (PGE), Au, Cu, S, and Se. Their total PGE contents range between 3 and 30 ppb and their PGE relative abundances from 0.01 to 0.001 × CI-chondrites, respectively. Positive correlations between total PGE contents and Se suggest that all of the PGE are hosted mainly in base metal sulfides (monosulfide solid solution [Mss], pentlandite, and Cu-rich sulfides [chalcopyrite/isocubanite]). Laser ablation microprobe-inductively coupled plasma mass spectrometry analyses support this conclusion while suggesting that, as observed in experiments on the Cu-Fe-Ni-S system, the Mss preferentially accommodate refractory PGEs (Os, Ir, Ru, and Rh) and Cu-rich sulfides concentrate Pd and Au. Poikiloblastic peridotites pervasively percolated by large silicate melt fractions at high temperature (1200°C) display the lowest Se (<2.3 ppb) and the lowest PGE contents (0.001 × CI-chondrites). In these rocks, the total PGE budget inherited from the primitive mantle was reduced by 80%, probably because intergranular sulfides were completely removed by the silicate melt. In contrast, protogranular peridotites metasomatized by small fractions of volatile-rich melts are enriched in Pt, Pd, and Au and display suprachondritic Pd/Ir ratios (1.9). The palladium-group PGE (PPGE) enrichment is consistent with precipitation of Cu-Ni-rich sulfides from the metasomatic melts. In spite of strong light rare earth element (LREE) enrichments (Ce/Yb_N < 10), the three harzburgites analyzed still display chondrite-normalized PGE patterns typical of partial melting residues, i.e., depleted in Pd and Pt relative to Ir and Ru. Likewise, coarse-granular lherzolites, a common rock type in Massif Central xenoliths, display Pd/Ir, Ru/Ir, Rh/Ir, and Pt/Ir within the 15% uncertainty range of chondritic meteorites. These rocks do not contradict the late-veneer hypothesis that ascribes the PGE budget of the Earth to a late-accreting chondritic component; however, speculations about this component from the Pd/Ir and Pt/Ir ratios of basalt-borne xenoliths may be premature.     

Insights into Petrological Characteristics of the Lithosphere of Mantle Wedge beneath Arcs through Peridotite Xenoliths: a Review

The petrological characteristics of peridotite xenoliths exhumedfrom the lithospheric mantle below the Western Pacific arcs(Kamchatka, NE Japan, SW Japan, Luzon–Taiwan, New Irelandand Vanuatu) are reviewed to obtain an overview of the supra-subductionzone mantle in mature subduction systems. These data are thencompared with those for peridotite xenoliths from recent orolder arcs described in the literature (e.g. New Britain, WesternCanada to USA, Central Mexico, Patagonia, Lesser Antilles andPannonian Basin) to establish a petrological model of the lithosphericmantle beneath the arc. In currently active volcanic arcs, thedegree of partial melting recorded in the peridotites appearsto decrease away from the fore-arc towards the back-arc region.Highly depleted harzburgites, more depleted than abyssal harzburgites,occur only in the frontal arc to fore-arc region. The degreeof depletion increases again to a degree similar to that ofthe most depleted abyssal harzburgites within the back-arc extensionalregion, whether or not a back-arc basin is developed. Metasomatismis most prominent beneath the volcanic front, where the magmaproduction rate is highest; silica enrichment, involving themetasomatic formation of secondary orthopyroxene at the expenseof olivine, is important in this region because of the additionof slab-derived siliceous fluids. Some apparently primary orthopyroxenes,such as those in harzburgites from the Lesser Antilles arc,could possibly be of this secondary paragenesis but have beenrecrystallized such that the replacement texture is lost. TheTi content of hydrous minerals is relatively low in the sub-arclithospheric mantle peridotites. The K/Na ratio of the metasomatichydrous minerals decreases rearward from the fore-arc mantleas well as downward within the lithospheric mantle. The lithosphericmantle wedge peridotites, especially metasomatized ones frombelow the volcanic front, are highly oxidized. Shearing of themantle wedge is expected beneath the volcanic front, and isrepresented by fine-grained peridotite xenoliths. KEY WORDS: mantle wedge; lithospheric mantle; peridotite xenoliths; melting; metasomatism     

Platinum-group element geochemistry of peridotite xenoliths from the Sierra Nevada and the Basin and Range, California

The nature of PGE-Re (PGE = Pt, Pd, Os, Ir, Ru) behavior in subcontinental lithospheric mantle was investigated using new, high precision PGE-Re abundance measurements and previously published Re-Os isotopic analyses of peridotite xenoliths from the Sierra Nevada and Mojave Province, California. Ru/Ir ratios and Ir concentrations are constant over a wide range in S content and major-element fertility indices (e.g., Mg/(Mg+Fe)), indicating that Ru and Ir are not only compatible during partial melting, but also that their partitioning behaviors may not be controlled entirely by sulfide. Pt/Ir, Pd/Ir, Os/Ir, and Re/Ir ratios range from slightly superchondritic to distinctly subchondritic for all xenoliths except for one anomalous sample (1026V), which is characterized by radiogenic ¹⁸⁷Os/¹⁸⁸Os, low Re/Os ratio, and large enrichments in Cu, Os, Pt, Pd, and S relative to Ir (COPPS metasomatism). Assuming chondritic initial relative abundances, the magnitudes of some of the depletions in Pt, Pd, Os, and Re relative to Ir and Ru require incompatible behavior or substantial secondary loss. In detail, some samples, which are otherwise characterized by fertile major-element indices, exhibit low S contents and subchondritic Os/Ir and Pd/Ir ratios, indicating that depletions in Pd and Os relative to Ir are not simple functions of the degree of melting as inferred from major elements. Possible mechanisms for depleting Pt, Pd, Os, and Re relative to Ir and Ru include partitioning into chromian spinels and alloys, partitioning between sulfide and sulfide liquids, mobilization by aqueous fluids, or secondary loss associated with late-stage sulfide breakdown. However, it is not possible to explain all of the depletions in Pt, Pd, Os, and Re by any single mechanism.The preferential enrichment in Os over Re and Ir in sample 1026V is somewhat paradoxical because this sample’s radiogenic ¹⁸⁷Os/¹⁸⁸Os requires a metasomatic agent, originating from a source with a high time-integrated Re/Os ratio. The abundant garnet websterite xenoliths may be a suitable source because they have high Re/Os ratios, radiogenic Os, and abundant garnet, which may sequester Re over Os during partial melting. However, their extremely low Os contents require the processing of large amounts of garnet websterite to concentrate enough Os into the metasomatic sulfides needed to enrich sample 1026V in Os. The homogeneity in ¹⁸⁷Os/¹⁸⁸Os ratio in the remaining xenoliths suggest that their Os isotopic compositions were not significantly affected by PGE metasomatism. The singular nature of 1026V’s composition emphasizes the rarity of COPPS metasomatism.     

ABUNDANCE AND DISTRIBUTION OF PLATINUM-GROUP ELEMENTS (PGE) IN PERIDOTITE FROM THE DAGZHUKA OPHIOLITE IN TIBET:IMPLICATIONS FOR MANTLE METASOMATISM

ABUNDANCE AND DISTRIBUTION OF PLATINUM-GROUP ELEMENTS (PGE) IN PERIDOTITE FROM THE DAGZHUKA OPHIOLITE IN TIBET:IMPLICATIONS FOR MANTLE METASOMATISM     

Rhodium,gold and other highly siderophile elements in orogenic peridotites and peridotite xenoliths

The concentrations of Rh, Au and other highly siderophile elements (HSE: Re, Os, Ir, Ru, Pt, Rh, Pd and Au), and ¹⁸⁷Os/¹⁸⁸Os isotope ratios have been determined for samples from peridotite massifs and xenoliths in order to further constrain HSE abundances in the Earth's mantle and to place constraints on the distributions processes accounting for observed HSE variations between fertile and depleted mantle lithologies. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS. The monoisotopic elements Rh and Au were quantified by standardization relative to the concentrations of Ru and Ir, respectively, and were determined from the same digestion aliquot as other HSE. The measurement precision of the concentration data under intermediate precision conditions, as inferred from repeated analyses of 2 g test portions of powdered samples, is estimated to be better than 10% for Rh and better than 15% for Au (1 s).Fertile lherzolites display non-systematic variation of Rh concentrations and constant Rh/Ir of 0.34 ± 0.03 (1 s, n = 57), indicating a Rh abundance for the primitive mantle of 1.2 ± 0.2 ng/g. The data also suggest that Rh behaves as a compatible element during low to moderate degrees of partial melting in the mantle or melt–mantle interaction, but may be depleted at higher degrees of melting. In contrast, Au concentrations and Au/Ir correlate with peridotite fertility, indicating incompatible behaviour of Au during magmatic processes in the mantle. Fertile lherzolites display Au/Ir ranging from 0.20 to 0.65, whereas residual harzburgites have Au/Ir < 0.20. Concentrations of Au and Re are correlated with each other and suggest similar compatibility of both elements. The primitive mantle abundance of Au calculated from correlations displayed by Au/Ir with Al₂O₃ and Au with Re is 1.7 ± 0.5 ng/g (1 s).The depletion of Pt, Pd, Re and Au relative to Os, Ir, Ru and Rh displayed by residual harzburgites, suggests HSE fractionation during partial melting. However, the HSE abundance variations of fertile and depleted peridotites cannot be explained by a simple fractionation process. Correlations displayed by Pd/Ir, Re/Ir and Au/Ir with Al₂O₃ may reflect refertilization of previously melt depleted mantle rocks due to reactive infiltration of silicate melts.Relative concentrations of Rh and Au inferred for the primitive mantle model composition are similar to values of ordinary and enstatite chondrites, but distinct from carbonaceous chondrites. The HSE pattern of the primitive mantle is inconsistent with compositions of known chondrite groups. The primitive mantle composition may be explained by late accretion of a mixture of chondritic with slightly suprachondritic materials, or alternatively, by meteoritic materials mixed into mantle with a HSE signature inherited from core formation.     

Insights into Li and Li isotope cycling and sub-arc metasomatism from veined mantle xenoliths,Kamchatka

Harzburgitic xenoliths cut by pyroxenite veins from Avachinsky volcano, Kamchatka, are derived from the sub-arc mantle and record element transfer from the slab to the arc. Olivine and orthopyroxene in the harzburgites have Li isotopic compositions (δ⁷Li = +2.8 to +5.6) comparable to estimates of the upper mantle (δ⁷Li ~ +4 ± 2). The pyroxenite veins, which represent modal metasomatism and may therefore provide information about the metasomatic agent, have mantle-normalized trace element characteristics that suggest overprinting of their mantle source by an aqueous, slab-derived fluid. These include relative enrichments of Pb over Ce, U over Th and Sr over Nd. Li is enriched relative to the HREE, and ortho- and clinopyroxene from the veins are in Li elemental and isotopic equilibrium with each other and the surrounding harzburgite. Vein samples (δ⁷Li = +3.0 to +5.0) do not record a significant slab-derived δ⁷Li signature. These observations can be reconciled if slab Li diffusively re-equilibrates in the mantle wedge. Modeling demonstrates that Li equilibration of small (1–2 cm width) veins or melt conduits is achieved at mantle wedge temperatures within 10¹–10⁵ years. We conclude that strongly fractionated Li isotopic signatures cannot be sustained for long periods in the sub-arc mantle, at least at shallow (<70 km) depths. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Enrichment of Platinum-group Elements (PGE) and Re-Os Isotopic Tracing for Porphyry Copper (Gold) Deposits

Platinum-group elements （PGE） in PGE-rich porphyry copper （gold） deposits are mainly Pt and Pd, whereas the concentrations of other PGE （Ru, Rh, Os, Ir） are significantly low. Moreover, Pt and Pd mainly exist in sulfides in the forms of crystal lattice or tiny platinum-group mineral （PGM） inclusions. The present data show that there is a positive relationship between Pt and Pd concentrations and Cu （Au） in porphyry copper （gold） deposits. The comparison of chondrite-normalized PGE distribution patterns between the ore-bearing porphyry intrusions and ore-barren porphyry intrusions in arc setting, 187^Os/188^Os, 87^Sr/86^Sr and S isotopes for porphyry copper （gold） deposits shows that PGEs were mainly derived from the mantle, and fluids from subduction zones devoted trivial PGE to the magma. The porphyry copper （gold） deposits associated with subducted events are most probably enriched in PGE, whereas those related to crustal thickening, lithospheric delamination or underplating rarely concentrate PGE. The osmium isotopic compositions in porphyry copper （gold） deposits reveal that （187^Os/188^Os）i values are highly variable and not lower than those of primitive upper mantle （PUM） and mantle peridotite, however, osmium concentrations are commonly lower than mantle peridotite, suggesting that parental magmas of some porphyry intrusions had experienced crustal contamination during magma evolution. Experimental investigations have proved that PGE exist in the forms of Cl^- and HS^- complexes during transportation and migration of the oreforming fluids. This paper summarizes previous studies including crucial controlling factors and mechanisms for PGE enrichment, and points out that the mantle-derived magmas parental to porphyry intrusions are the prerequisite for PGE enrichment in porphyry copper （gold） deposits. Favorable physical and chemical conditions （including salinity, temperature, pressure, pH, and oxygen fugacity） in hydrothermal fluids crucially control the     

地幔富硅交代与大陆岩石圈的演化

富硅交代是弧下地幔中熔体岩石相互作用的主要表现形式 ,是造成古老克拉通陆下岩石圈地幔富硅的主要机制。在弧下地幔捕掳体中 ,橄榄岩被来自俯冲洋壳物质部分熔融生成的含水富硅熔体交代后 ,斜方辉石含量的增加使全岩富集SiO2 ,斜方辉石显示异常低的Al2 O3和Cr2 O3,微量元素上表现为强烈富集LILE ,强烈亏损Nb ,Ta和Ti。在古老克拉通地幔岩样品中 ,方辉橄榄岩具过剩的斜方辉石 ,橄榄石的Ni含量与斜方辉石的组成含量成正比 ,而和橄榄石的x(Mg) /x(Mg +Fe2 +)值没有正比关系 ,被解释为亏损的地幔橄榄岩和来自俯冲板片的富硅熔体相互作用的结果。熔体岩石相互作用最终导致了陆下岩石圈地幔富集SiO2 ,这种被含水富硅熔体改造后的地幔岩石的部分熔融可能是造成陆壳富硅富镁的主要原因。含水富硅熔体对岩石圈地幔的影响程度也可能是大陆岩石圈增生或裂解、增厚或减薄的关键因素之一。     

新疆阿尔泰山南缘泥盆纪弧型苦橄岩铂族元素地球化学特征及其地质意义

全球岛弧火山岩的铂族元素数据非常少。本研究对新疆阿尔泰山南缘中泥盆世北塔山组地层中的苦橄岩的铂族元素进行了分析,结果表明:其铂族元素的含量总体变化不大,其原始地幔标准化曲线总体上和已经报道的大西洋Lesser Antilles岛弧的G renada苦橄岩相似,均以富集钯组铂族元素(PPGE)为特征,但总体含量比后者高,而比大火成岩省的苦橄岩低。一些铂族元素的特征比值指示了苦橄岩和富辉玄武岩起源于软流圈地幔,而高的w(Os)/w(Ir)比值则暗示了源区中有深海沉积物的加入。w(Pd)/w(Ir)-w(N i)/w(Cu)图解说明本区的苦橄岩不是原始岩浆,而是原始的高镁玄武岩中有过剩橄榄石的加入,而w(Pd)-w(Cu)图解则说明原始岩浆硫不饱和。IPGE在俯冲带流体中相对稳定,而PPGE在俯冲带流体中的活动性相对较高。     

The characteristics of automobile catalyst-derived platinum group elements in road dusts and roadside soils: a case study in the Pearl River Delta region,South China

The emission of platinum group elements (PGE) from automobile catalytic converters has led to enrichment of PGE in road dusts and roadside soils in urban areas that are well above the natural background levels. This paper evaluates the source of contamination of all the PGE and Au in road dusts and roadside soils in the Pearl River Delta region, including three major cities, Shenzhen, Guangzhou and Hong Kong, South China. Samples were digested using Carius tube and analyzed by isotope dilution ICP-MS; Os was separated by distillation and other PGE by Te-coprecipitation. All samples have elevated PGE concentrations above the background values of uncontaminated soils and contain higher Pt, Pd and Rh than other PGE. The maximum values are 181 ng/g Pt, 514 ng/g Pd, 53 ng/g Rh and 1345 ng/g Au. There are clear positive correlations between Pt and Pd, Pt and Rh, and Pd and Rh, indicating that the main emitted of PGE from automobile catalyst are Pt, Pd and Rh. High concentrations of Au were also found in road dust samples from Hong Kong and Shenzhen. Dust samples with higher Os contents have lower ¹⁸⁷Os/¹⁸⁸Os ratios. Samples from Hong Kong show relatively high Pt/Rh ratios. Positive correlations between Pt and Ru, and Pt and Ir were found in Shenzhen and Hong Kong, but only positive correlations between Pt and Ir were found in Guangzhou. These different characteristics reflect different automobile catalytic systems used in Hong Kong and mainland China.     

苏北盘石山、练山地幔捕虏体的PGE地球化学

通过锍镍火试金预富集法,分析了位于郯庐断裂带东侧的盘石山、练山地幔橄榄岩包体中铂族元素(PGE)和Au含量.不同于部分熔融残留成因地幔橄榄岩中通常所观察到的负斜率型或平坦型的分布模式,这两地的地幔橄榄岩以Pt、Pd、Ru相对富集,Ir、Rh相对亏损的"燕子型"分布模式为特征.Pt、Pd等不相容元素富集说明上地幔除经历过早期的部分熔融外,还经历了后期富Pt、Pd的高熔/岩比的熔(流)体的层析分离交代作用影响.盘石山地幔橄榄岩的PGE总量比练山高,Os的含量也比原始地幔值高;而练山地幔橄榄岩的Os含量比原始地幔值低,说明交代作用带走了练山地幔橄榄岩中的Os,却没有很大改变盘石山地幔橄榄岩中的Os含量,这可能与交代熔(流)体含硫量饱和程度有关.Rh的负异常可能与部分熔融过程中熔体较低的fo2有关.     

PGE distribution in deformed lherzolites of the Udachnaya kimberlite pipe (Yakutia)

The results of the first study of the PGE distribution in deformed lherzolites of the Udachnaya kimberlite pipe (Yakutia) are presented here. The complex character of evolution of the PGE composition in the Deformed lherzolites is assumed to be the result of silicate metasomatism. At the first stage, growth in the amount of clinopyroxene and garnet in the rock is accompanied by a decrease in the concentration of the compatible PGE (Os, Ir). During the final stage, the rock is enriched with incompatible PGE (Pt, Pd) and Re possible due to precipitation of submicron-sized particles of sulfides in the interstitial space of these mantle rocks.     

Highly siderophile element behaviour accompanying subduction of oceanic crust: Whole rock and mineral-scale insights from a high-pressure terrain

Highly siderophile element concentrations (HSE: Re and platinum-group elements (PGE)) are presented for gabbros, gabbroic eclogites and basaltic eclogites from the high-pressure Zermatt-Saas ophiolite terrain, Switzerland. Rhenium and PGE (Os, Ir, Ru, Rh, Pt, Pd) abundances in gabbro- and eclogite-hosted sulphides, and Re-Os isotopes and elemental concentrations in silicate phases are also reported. This work, therefore, provides whole rock and mineral-scale insights into the PGE budget of gabbroic oceanic crust and the effects of subduction metamorphism on gabbroic and basaltic crust.Chondrite-normalised PGE patterns for the gabbros are similar to published mid-ocean ridge basalts (MORB), but show less inter-element fractionation. Mean Pt and Pd contents of 360 and 530 pg/g, respectively, are broadly comparable to MORB, but gabbros have somewhat higher abundances of Os, Ir and Ru (mean: 64, 57 and 108 pg/g). Transformation to eclogite has not significantly changed the concentrations of the PGE, except Pd which is severely depleted in gabbroic eclogites relative to gabbros (∼75% loss). In contrast, basaltic eclogites display significant depletion of Pt (?60%), Pd (>85%) and Re (50-60%) compared with published MORB, while Os, Ir and Ru abundances are broadly comparable. Thus, these data suggest that only Pt, Pd and Re, and not Os, Ir and Ru, may be significantly fluxed into the mantle wedge from mafic oceanic crust. Re-Os model ages for gabbroic and gabbroic eclogite minerals are close to age estimates for igneous crystallisation and high-pressure metamorphism, respectively, hence the HSE budgets can be related to both igneous and metamorphic behaviour. The gabbroic budget of Os, Ir, Ru and Pd (but not Pt) is dominated by sulphide, which typically hosts >90% of the Os, whereas silicates account for most of the Re (with up to 75% in plagioclase alone). Sulphides in gabbroic eclogites tend to host a smaller proportion of the total Os (10-90%) while silicates are important hosts, probably reflecting Os inheritance from precursor phases. Garnet contains very high Re concentrations and may account for >50% of Re in some samples. The depletion of Pd in gabbroic eclogites appears linked, at least in part, to the loss of Ni-rich sulphide.Both basaltic and gabbroic oceanic crust have elevated Pt/Os ratios, but Pt/Re ratios are not sufficiently high to generate the coupled ¹⁸⁶Os-¹⁸⁷Os enrichments observed in some mantle melts, even without Pt loss from basaltic crust. However, the apparent mobility of Pt and Re in slab fluids provides an alternative mechanism for the generation of Pt- and Re-rich mantle material, recently proposed as a potential source of ¹⁸⁷Os-¹⁸⁶Os enrichment.     

Mantle peridotites from the Western Pacific

We review petrographical and petrological characteristics of mantle peridotite xenoliths from the Western Pacific to construct a petrologic model of the lithospheric mantle beneath the convergent plate boundary. The peridotite varies from highly depleted spinel harzburgite of low-pressure origin at the volcanic front of active arcs (Avacha of Kamchatka arc and Iraya of Luzon–Taiwan arc) to fertile spinel lherzolite of high-pressure origin at the Eurasian continental margin (from Sikhote-Alin through Korea to eastern China) through intermediate lherzolite–harzburgite at backarc side of Japan island arcs. Oxygen fugacity recorded by the peridotite xenoliths decreases from the frontal side of arc to the continental margin. The sub-arc type peridotite is expected to exist beneath the continental margin if accretion of island arc is one of the important processes for continental growth. Its absence suggests replacement by the continental lherzolite at the region of backarc to continental margin. Asthenospheric upwelling beneath the continental region, which has frequently occurred at the Western Pacific, has replaced depleted sub-cratonic peridotite with the fertile spinel lherzolite. Some of these mantle diapirs had opened backarc basins and strongly modified the lithospheric upper mantle by metasomatism and formation of Group II pyroxenites.     

Platinum group element (PGE) geochemistry to understand the chemical evolution of the Earth’s mantle

Platinum group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd) are important geochemical and cosmochemical tracers. Depending on physical and chemical behaviour the PGEs are divided into two subgroups: IPGE (Ir, Os, Ru) and PPGE (Pd, Pt, Rh). Platinum group elements show strong siderophile and chalcophile affinity. Base metal sulfides control the PGE budget of the Earth’s mantle. Mantle xenoliths contain two types of sulfide populations: (1) enclosed within silicate minerals, and (2) interstitial to the silicate minerals. In terms of PGE characters the included variety shows IPGE enriched patterns — similar to the melt-depleted mantle harzburgite, whereas the interstitial variety shows PPGE enriched patterns — resembling the fractionated PGE patterns of the basalt. These PGE characters of the mantle sulfides have been interpreted to be representative of multi-stages melting process of the mantle that helped to shape the chemical evolution of the Earth.     

Na Metasomatism in the Island-Arc Mantle by Slab Melt--Peridotite Interaction: Evidence from Mantle Xenoliths in the North Kamchatka Arc

The Pliocene (7 Ma) Nb-enriched arc basalts of the ValovayamVolcanic Field (VVF) in the northern segment of the Kamchatkaarc, Russia, host abundant mantle xenoliths, including spinelIherzolites. Textural and microstructural evidence for high-temperature,multi-stage, creep-related deformations in spinel Iherzolitessupports a sub-arc mantle derivation. Pyroxene chemistry indicatesthe existence of two compositional suites: (1) a Cr-diopsidesuite with low-Tt, moderate-Al clinopyroxene compositions, and(2) an Al-augite suite with high Al and Tt, and low Cr concentrationsin clinopyroxene. Some spinel lherzolite xenoliths contain metasomaticAl-augite-type clinopyroxene, Al-Tt spinel, and felsic veinssimilar to trondhjemite melt. The Al-augite series xenolithstypically contain high-Na plagioclase, Cr-poor, Al-Fe-Mg andAl-Tt-Fe spinels, with occasional almandine-grossularite garnetand high-Al and -Na pargasitic amphibole. Pyroxene and spinel compositional trends suggest that the Crdiopsideseries xenoliths from the VVF Nb-enriched arc basalts representan island-arc mantle affected by a metasomatic event. Occurrenceof high-Na plagioclase and trondhjemitic veins favors the additionof a metasomatic component with high Na, Al and Si to the northernKamchatka arc mantle. Trondhjemitic veins, representing siliceousslab melts, compositionally exemplify the metasomatic component.Na metasomatism by peridotite-slab melt interaction is an importantmantle hybridization process responsible for arc-related alkalinemagma generation from a veined sub-arc mantle. KEY WORDS: metasomatism; island arc; mantle xenoliths; Kamchatka; mantle     

Os isotopes in mantle xenoliths from the Eifel volcanic field and the Vogelsberg (Germany): age constraints on the lithospheric mantle

The effects of mantle metasomatism on the sulfide phase in mantle xenoliths in general, and on the Os isotopic system in particular, have received increased attention in recent years. Here, we report on Os isotopic systematics of metasomatized mantle xenoliths from the late Quaternary Eifel (Dreiser Weiher and Meerfelder Maar) and neighboring Vogelsberg volcanic fields, which provide insight into the effects of melt extraction and metasomatism on Os isotopes and place constraints on the evolution of the lithospheric mantle component beneath central Europe. Sixteen harzburgite, lherzolite, and pyroxenite xenoliths from the Eifel and two lherzolite xenoliths from the Vogelsberg were analyzed for Os isotopes. Samples from the anhydrous peridotite suite (Ib) are highly variable in their Os isotopes, ranging from subchondritic values (¹⁸⁷Os/¹⁸⁸Os=0.1236) to suprachondritic values (¹⁸⁷Os/¹⁸⁸Os=0.1420), indicating that some of these samples have been overprinted by the addition of radiogenic Os and have lost the primary mantle Os that was presumably present. The suprachondritic values suggest a source for this Os in a reservoir with a time-integrated Re/Os ratio greater than that of the bulk Earth. Eifel samples with Os contents >1.5 ng/g from the hydrous suite (Ia) have relatively unradiogenic Os isotope compositions (¹⁸⁷Os/¹⁸⁸Os=0.1208-0.1237) and Al₂O₃-Os isotopic systematics consistent with ancient melt depletion and isolation from the convecting asthenospheric mantle for time periods similar to the age of the overlying crust (~1.5 Ga) as well with results from peridotite massifs in the European region. The LREE-metasomatism and the enrichment of Os (up to 6.47 ng/g) and As (sulfide metasomatism?) in the hydrous suite is strongly inversely correlated with the Os isotope ratios, demonstrating that mantle processes such as metasomatism can significantly modify the Os isotope chemistry of mantle xenoliths.     

Osmium isotope and highly siderophile element geochemistry of mantle xenoliths from NW Turkey: implications for melt depletion and metasomatic history of the sub-continental lithospheric mantle

Ultramafic xenoliths entrained in the late Miocene alkali basalts and basanites from NW Turkey include refractory spinel-harzburgites and dunites accompanied by subordinate spinel-lherzolites. Whole-rock major and trace element characteristics indicate that the xenoliths are mostly the solid residues of varying degrees of partial melting (～4–～15%), but some have geochemical signatures reflecting the processes of melt/rock interaction. Mantle-normalized trace element patterns for the peridotites vary from LREE-depleted to strongly LREE-enriched, reflecting multistage mantle processes from simple melt extraction to metasomatic enrichment. Rhenium and platinum group element (PGE) abundances and ¹⁸⁷Os/¹⁸⁸Os systematics of peridotites were examined in order to identify the nature of the mantle source and the processes effective during variable stages of melt extraction within the sub-continental lithospheric mantle (SCLM). The peridotites are characterized by chondritic Os/Ir and Pt/Ir ratios and slightly supra-chondritic Pd/Ir and Rh/Ir ratios, representing a mantle region similar in composition to the primitive mantle (PM). Moderate enrichment in PPGE (Pd–Pt–Rh)/IPGE (Ir–Os–Ru) ratios with respect to the PM composition in the metasomatized samples, however, reflects compositional modification by sulphide addition during possible post-melting processes. The ¹⁸⁷Os/¹⁸⁸Os ratios of the peridotites range from 0.11801 to 0.12657. Highly unradiogenic Os isotope compositions (γOs at 10 Ma from –7.0 to –3.2) in the chemically undisturbed mantle residues are accompanied by depletion in Re/Os ratios, suggesting long-term differentiation of SCLM by continuous melt extraction. For the metasomatized peridotites, however, systematic enrichments in PPGE and Re abundances, and the observed positive covariance between ¹⁸⁷Re/¹⁸⁸Os and γOs can most likely be explained by interaction of solid residues with basaltic melts produced by melting of relatively more radiogenic components in the mantle. Significantly, the wide range of ¹⁸⁷Os/¹⁸⁸Os ratios characterizing the entire xenolith suite seems to be consistent with multistage evolution of SCLM and suggests that parts of the lithospheric mantle contain materials that have experienced ancient melt removal (～1.3 Ga) which created time-integrated depletion in Re/Os ratios; in contrast, some other parts display evidence indicative of recent perturbation in the Re–Os system by sulphide addition during interaction with metasomatizing melts.     

Composition and evolution of PGE mineralization in chromite ores from the Il’chir ophiolite complex (Ospa–Kitoi and Khara-Nur areas,East Sayan)

Data are presented on chromitites from the northern and southern sheets of the Il’chir ophiolite complex (Ospa–Kitoi and Khara-Nur (Kharanur) massifs). The new and published data are used to consider similarities and differences between ore chrome-spinel from the chromitites of the northern and southern ophiolite sheets as well as the species diversity of PGE minerals and the evolution of PGE mineralization. Previously unknown PGE minerals have been found in the studied chromitites.Ore chrome-spinel in the chromitites from the northern sheet occurs in medium- and low-alumina forms, whereas the chromitites from the southern sheet contain only medium-alumina chrome-spinel. The PGE minerals in the chromitites from the southern sheet are Os–Ir–Ru solid solutions as well as sulfides and sulfoarsenides of these metals. The chromitites from the northern sheet contain the same PGE minerals and diverse Rh–Pt–Pd mineralization: Pt–Ir–Ru–Os and isoferroplatinum with Ir and Os–Ir–Ru lamellae. Areas of altered chromitites contain a wide variety of low-temperature secondary PGE minerals: Pt–Cu, Pt–Pd–Cu, PdHg, Rh2SnCu, RhNiAs, PtAs2, and PtSb2. The speciation of the PGE minerals is described along with multiphase intergrowths. The relations of Os–Ir–Ru solid solutions with laurite and irarsite are considered along with the microstructure of irarsite–osarsite–ruarsite solid solutions. Zoned Os–Ir–Ru crystals have been found. Zone Os82–99 in these crystals contains Ni3S2 inclusions, which mark off crystal growth zones. Different sources of PGE mineralization are presumed for the chromitites from the northern and southern sheets.The stages of PGE mineralization have been defined for the chromitites from the Il’chir ophiolite belt. The Pt–Ir–Ru–Os and (Os, Ru)S2 inclusions in Os–Ir–Ru solid solutions might be relics of primitive-mantle PGE minerals. During the partial melting of the upper mantle, Os–Ir–Ru and Pt–Fe solid solutions formed syngenetically with the chromitites. During the late-magmatic stage, Os–Ir–Ru solid solutions were replaced by sulfides and sulfarsenides of these metals. Mantle metasomatism under the effect of reduced mantle fluids was accompanied by PGE remobilization and redeposition with the formation of the following assemblage: garutiite (Ni,Fe,Ir), zaccariniite (RhNiAs), (Ir,Ni,Cu)S3, Pt–Cu, Pt–Cu–Fe–Ni, Cu–Pt–Pd, and Rh–Cu–Sn–Sb. The zoned Os–Ir–Ru crystals in the chromitites from the northern sheet suggest dissolution and redeposition of Os–Ir–Ru primary-mantle solid solutions by bisulfide complexes. Most likely, the PGE remobilization took place during early serpentinization at 450–600 ºC and 13–16 kbar.During the crustal metamorphic stage, tectonic movements (obduction) and a change from reducing to oxidizing conditions were accompanied by the successive transformation of chrome-spinel into ferrichromite–chrome-magnetite with the active participation of a metamorphic fluid enriched in crustal components. The orcelite–maucherite–ferrichromite–sperrylite assemblage formed in epidote-amphibolitic facies settings during this stage.The PGE mineral assemblage reflects different stages in the formation of the chromitites and dunite-harzburgite host rocks and their transformation from primitive mantle to crustal metamorphic processes.     

Trace elemental and PGE geochemical constraints of Mesozoic and Cenozoic peridotitic xenoliths on lithospheric evolution of the North China Craton

Whole-rock major, trace, and platinum-group elemental (PGE) data, and major and trace element compositions of diopsides are reported for peridotite xenoliths from (1) early Mesozoic volcanic breccias in Xinyang, located at the southern margin of the North China Craton, and (2) Cenozoic basalts in Hebi and Shanwang, both of which are situated within the craton and lie on the North-South Gravity Line and the Tanlu fault zone, respectively. The early Mesozoic Xinyang xenoliths are harzburgites containing <2% Cpx with high Cr^# and enriched in LREE but depleted in HFSE. These xenoliths have chondritic Pd/Ir (1.9-6.6) and Ru/Ir (3.5-4.0) ratios and high Ni and low CaO, Al₂O₃, and S contents, indicating derivation from a highly refractory mantle that experienced carbonatitic metasomatism. Negative Ce (mean δCe = 0.50) and low Mg/Si ratios of the Xinyang peridotites record the addition of crustal components likely produced from subducted continental material of the Yangtze Craton in the early Mesozoic. The subduction-related modification of the lithospheric mantle was limited to the area close to the collision zone rather than being pervasive throughout the craton. The Cenozoic Hebi peridotite xenoliths are harzburgites with ≤4.5% Cpx and have low CaO and Al₂O₃ but high Ni contents, chondritic Ru/Ir ratios (2.5-5.4), and a wide range of CaO/Al₂O₃, Na₂O/TiO₂, Pt/Ir (0.4-2.3), and Pd/Pt (1.1-8.5) ratios. These peridotites are interpreted as the shallow relics of the cratonic mantle. In contrast, the Cenozoic Shanwang xenoliths are lherzolites (5.6%-19.5% Cpx), which have low Ni contents and low Ni/Cu and Mg/Si ratios, but high CaO, Al₂O₃, S, and HREE contents, and relatively high Ru/Ir and Pd/Ir ratios. The Shanwang peridotites show pronounced positive Ti and Sr, negative Th, and slightly negative Y, Zr, and Hf anomalies. They are believed to represent newly accreted fertile lithospheric mantle derived from cooling of upwelling asthenosphere. The documented temporal and spatial variations in the Mesozoic-Cenozoic mantle support the previous suggestion that the buoyant refractory continental keel in the eastern part of the North China Craton was heterogeneously replaced by younger fertile lithospheric mantle in the late Cretaceous-early Tertiary.