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.     

内蒙古柯单山蛇绿岩地幔橄榄岩铂族元素(PGEs)的分布特征及分异机制探讨

采用Carius管结合MC-ICPMS法分析了内蒙古柯单山蛇绿岩地幔橄榄岩中Ir、Ru、 Pt 和Pd 的含量,与典型的地幔橄榄岩进行对比研究,发现柯单山地幔橄榄岩中Ir和Ru明显亏损,Pt和Pd强烈富集,具有极高的Pd/Ir值,PGEs地幔标准化配分模式具有较陡的正斜率,明显不同于通常观测到的代表部分熔融残留相中铂族元素配分模式(负斜率或平坦型)。柯单山地幔橄榄岩的Ir和Ru与MgO呈正相关关系,表明Ir和Ru的亏损可能与部分熔融过程中硫化物的消耗程度有关,而与PGEs在硫化物/硅酸盐间的能斯特分配系数没有直接关系; Pt、Pd的富集表明本区的地幔橄榄岩不仅仅是经历过部分熔融的残余,而与来自深海的橄榄岩和大陆岩石圈地幔(SCLM)中的方辉橄榄岩相似,因此推测,本区地幔橄榄岩在部分熔融后又经历了富Pd的熔/流体交代,而熔/流体的来源可能是在岩浆分异演化过程中"熔离"出来的硫化物。     

Distribution of siderophile and chalcophile elements in serpentinites of the oceanic lithosphere as an insight into the magmatic and crustal evolution of mantle peridotites

The paper reports result of comparative analysis of the distribution of siderophile (Au, Pt, Pd, Co, Ni, and Cr) and chalcophile (Ag, Cd, Sb, Pb, Zn, Cu, As, and S) elements in ultramafic rock samples of various types of abyssal peridotites. One of the objectives of this research was to obtain reference estimates for the concentrations of siderophile and chalcophile elements in the two end members defining the geochemical evolutionary trends of the material of the suboceanic mantle: a sample of insignificantly depleted mantle material (spinel lherzolite) and extensively carbonated serpentinite after harzburgite, which was formed at the “endpoint” of the ascent of mantle material to the seafloor surface. The distribution of siderophile and chalcophile elements is proved to record information on the whole compositional evolution of abyssal peridotites corresponding to the trajectory of their exhumation from mantle depth levels to seafloor outcrops. These data indicate that the bulk-rock compositional parameters of abyssal peridotites can be utilized to estimate the contribution of magmatic and hydrothermal process to the distribution of siderophile and chalcophile elements.     

Sulfide petrology and highly siderophile element geochemistry of abyssal peridotites: a coupled study of samples from the Kane Fracture Zone (45°W 23°20N, MARK area, Atlantic Ocean)

Nineteen samples from the Kane Fracture Zone have been studied for sulfide mineralogy and analyzed for S, Se, platinum-group elements (PGE), and Au to assess the effect of refertilization processes on the PGE systematics of abyssal peridotites. The lherzolites show broadly chondritic PGE ratios and sulfide modal abundances (0.01 to 0.03 wt%) consistent with partial melting models, although the few pyroxene-hosted sulfide inclusions and in situ LAM-ICPMS analyses provide evidence for in situ mobilization of a Cu-Ni-rich sulfide partial melt. The most refractory harzburgites (spinel Cr# > 29) are almost devoid of magmatic sulfides and show uniformly low Pd_N/Ir_N (<0.5) for variable Pt_N/Ir_N (0.8 to 1.2). The compatible behavior of Os, Ir, Ru, Rh, and Pt reflects the presence of primary Os-Ru alloys. Some harzburgites displaying petrographic evidence for refertilization by incremental melts en route to the surface are enriched in sulfides (up to 0.1 wt%). Some of these sulfides are concentrated in small veinlets of clinopyroxene and spinel crystallized from these melts. These S-rich harzburgites display superchondritic Pd_N/Ir_N (up to 2.04) positively correlated with sulfide modal contents. It is concluded that refertilization processes resulting in precipitation of metasomatic sulfides may significantly enhance Pd concentrations of abyssal peridotites while marginally affecting Pt (Pt_N/Ir_N ≤ 1.24) and Rh (Rh_N/Ir_N ≤ 1.23) as well. When the effects of such processes are screened out, our database suggests PGE relative abundances in the DMM (Depleted MORB Mantle; MORB: Mid-Ocean Ridge) within the uncertainty range of chondritic meteorites, without evidence of superchondritic Pt/Ir and/or Rh/Ir ratios.     

金川超大型铜镍硫化物矿床的铂族元素地球化学特征

对金川超大型铜镍岩浆硫化物矿床岩石、矿石的铂族元素地球化学特征研究表明 ,金川岩体的平均Cu/Pd值远大于原生地幔岩浆的Cu/Pd值 ,说明其岩石为因硫化物析离而失去Pd的岩浆所结晶 ;且岩石的PGE具有部分熔融趋势 ,与地幔橄榄岩接近 ,这些均指示存在岩浆熔离作用。该矿床岩石、矿石的PGE球粒陨石标准化分布模式比较对应 ,均可分为两种类型 ,反映了岩浆多次侵入、熔离分异同时成岩成矿的特征。另外 ,PGE S关系分析表明其成岩成矿过程中有少量地壳物质混染。PGE地球化学特征参数还指示了其高镁拉斑玄武质母岩浆的性质。     

Platinum-group element geochemistry of the Zhuqing Fe-Ti-V oxide ore-bearing mafic intrusions in western Yangtze Block,SW China: control of platinum-group elements by magnetite

Platinum-group element (PGE) geochemistry combined with elemental geochemistry and magnetite compositions are reported for the Mesoproterozoic Zhuqing Fe–Ti–V oxide ore-bearing mafic intrusions in the western Yangtze Block, SW China. All the Zhuqing gabbros display extremely low concentrations of chalcophile elements and PGEs. The oxide-rich gabbros contain relatively higher contents of Cr, Ni, Ir, Ru, Rh, and lower contents of Pt and Pd than the oxide-poor gabbros. The abundances of whole-rock concentrations of Ni, Ir, Ru, and Rh correlate well with V contents in the Zhuqing gabbros, implying that the distributions of these elements are controlled by magnetite. The fractionation between Ir–Ru–Rh and Pt–Pd in the Zhuqing gabbros is mainly attributed to fractional crystallization of chromite and magnetite, whereas Ru anomalies are mainly due to variable degrees of compatibility of PGE in magnetite. The order of relative incompatibility of PGEs is calculated to be Pd?<?Pt?<?Rh?<?Ir?<?Ru. The very low PGE contents and Cu/Zr ratios and high Cu/Pd ratios suggest initially S-saturated magma parents that were highly depleted in PGE, which mainly formed due to low degrees of partial melting leaving sulfides concentrating PGEs behind in the mantle. Moreover, the low MgO, Ni, Ir and Ru contents and high Cu/Ni and Pd/Ir ratios for the gabbros suggest a highly evolved parental magma. Fe–Ti oxides fractionally crystallized from the highly evolved magma and subsequently settled in the lower sections of the magma chamber, where they concentrated and formed Fe–Ti–V oxide ore layers at the base of the lower and upper cycles. Multiple episodes of magma replenishment in the magma chamber may have been involved in the formation of the Zhuqing intrusions.     

Fractionation of Ruthenium from Other Highly Siderophile Elements (HSEs) in Forearc Mantle

The geochemical characteristics and behaviors of highly siderophile elements (HSEs) in forearc peridotites remain poorly constrained due to the scarcity of data. Here, we report HSE abundances of mantle peridotites from the New Caledonia ophiolites, a classical ophiolite generated in a forearc setting. Those peridotites show non‐chondritic, strongly fractionated HSE patterns and can be classified into two distinct types (namely Group I and Group II). Group I peridotites have higher HSE contents than Group II peridotites, which might be because intergranular sulfides were completely removed but sulfide inclusions were retained during partial melting of peridotites in a forearc environment, and meanwhile the distribution of sulfide inclusions are not uniform in mantle. Moreover, Group I peridotites display flat patterns from Os to Pt but strongly depleted in Pd, which resemble those patterns of some mantle wedge xenoliths. The Pt–Pd decoupling can be attributed to high degrees of partial melting. However, Group II peridotites are characterized by strongly positive Ru anomaly with highly super‐chondritic Ru/Os and Ru/Ir ratios. Such characteristics are the first reported cases for forearc peridotites. The fractionation of Ru from other HSEs might reflect the stability of refractory Ru‐rich phases in mantle wedge peridotites during different processes, e.g., partial melting and melt/fluid‐rock reactions.     

A laser ablation ICP-MS study of platinum-group and chalcophile elements in base metal sulfide minerals of the Jinchuan Ni–Cu sulfide deposit,NW China

The paper presents concentrations of the platinum-group and chalcophile elements in the base metal sulfides (BMS) from the Jinchuan Ni–Cu sulfide deposit determined by laser ablation-inductively coupled plasma-mass spectrometry. Mass balance calculations reveal that pentlandite hosts a large proportion of Co, Ni and Pd (> 65%), and that pentlandite and pyrrhotite accommodate significant proportions of Re, Os, Ru, Rh, and Ag (~ 35–90%), whereas chalcopyrite contains a small amount of Ag (~ 10%) but negligible platinum-group elements. Iridium and Pt are not concentrated in the BMS and mostly occur in As-rich platinum-group minerals. The enrichments of Co, Ni, Re, Os, Ru, and Rh in pentlandite and pyrrhotite, and Cu in chalcopyrite are consistent with the fractionation of sulfide liquid and exsolution of pentlandite and pyrrhotite from the mono-sulfide solid solution (MSS). The Ir-bearing minerals exsolved from the MSS, depleting pentlandite and pyrrhotite in Ir, whereas sperrylite exsolved from the residual sulfide liquid on cooling. Diffusion of Pd from residual sulfide liquid into pentlandite during its exsolution from the MSS and crystallization of Pt-bearing minerals in the residual sulfide liquid resulted in the enrichment of Pd in pentlandite and decoupling between Pd and Pt in the Jinchuan net-textured and massive ores.     

GEOCHEMICAL CHARACTERISTICS OF PLATINUM GROUP ELEMENTS IN JINCHUAN SUPER-LARGE SULFIDE COPPER-NICKEL DEPOSIT, JINCHANG CITY, GANSU PROVINCE, CHINA

The platinum-group element geochemistry of rocks and ores from Jinchuan super-large copper-nickel sulfide deposit is systemically studied in this paper. The Cu/Pd mean ratio of Jinchuan intrusion is lower than that of original mantle magma, which indicates that these ultrabasic rocks were crystallized from magma that lost Pd in the form of melting segregation of sulfides. The PGE of the rocks show trend of partial melting, similar to that of mantle peridotite, which shows that magma formation occurs during rock-forming and ore-forming processes. The chondrite normalized PGE patterns of the rocks and ores are well related to each other, which signifies the signatures of multi-episode magmatic intrusion, melting and differentiation in the formation processes of rocks and ores. In addition, analyses about the relation between PGE and S, and study on Re-Os isotopes indicate that few contamination of the crustal substances occurred during the magmatic intrusion and the formation of deposit. However, contamination by crustal substances helps to supply part of the S for the enrichment of PGE. Meanwhile, the hydrothermal process is also advantageous for the enrichment of PGE, especially lbr Pt and Pd, due to deep melting segregation. The characteristic parameters （such as Pt/（Pt＋Pd）, （Pt＋Pd）/（Ru＋Ir＋Os）, Pd/Ir, Cu/（Ni＋Cu）, and so on.） for platinum-group elements for Jinchuan sulfide copper-nickel deposit show the same features as those for sulfide copper-nickel deposit related to basic magma, which also illustrates its original magma property representative of Mg-high tholeiite. Therefore, it is the marie （not ultramafic） magma that resulted in the formation of the superlarge sulfide copper-nickel deposit enriched in Cu and PGE. To sum up, the geochemical characteristics of platinum-group elements in rocks and ores from Jinchuan copper-nickel sulfide deposit are constrained by the continental rift tectonic environment, the parent magma features, the enriched mantel magma source, the complex metallogenesis and PGE geochemical signatures, and this would be rather significant for the study about the genetic mechanism of copper-nickel sulfide deposits.     

Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.     

Platinum-group element systematics in Mid-Oceanic Ridge basaltic glasses from the Pacific, Atlantic, and Indian Oceans

The concentrations of Ir, Ru, Pt and Pd have been determined in 29 Mid-Oceanic Ridge basaltic (MORB) glasses from the Pacific (N = 7), the Atlantic (N = 10) and the Indian (N = 11) oceanic ridges and the Red Sea (N = 1) spreading centers. The effect of sulfide segregation during magmatic differentiation has been discussed with sample suites deriving from parental melts produced by high (16%) and low (6%) degrees of partial melting, respectively. Both sample suites define positive and distinct covariation trends in platinum-group elements (PGE) vs. Ni binary plots. The high-degree melting suite displays, for a given Ni content, systematically higher PGE contents relative to the low-degree melting suite. The mass fraction of sulfide segregated during crystallization (X_sulf), the achievement of equilibrium between sulfide melt and silicate melts (R_eff), and the respective proportions between fractional and batch crystallization processes (S_b) are key parameters for modeling the PGE partitioning behavior during S-saturated MORB differentiation. Regardless of the model chosen, similar sulfide melt/silicate melt partition coefficients for Ir, Ru, Pt and Pd are needed to model the sulfide segregation process, in agreement with experimental data. When corrected for the effect of magmatic differentiation, the PGE data display coherent variations with partial melting degrees. Iridium, Ru and Pt are found to be compatible in nonsulfide minerals whereas the Pd behaves as a purely chalcophile element. The calculated partition coefficients between mantle sulfides and silicate melts (assuming a PGE concentration in the oceanic mantle at ∼0.007 × CI-chondritic abundances) increase from Pd (∼10³) to Ir (∼10⁵). This contrasting behavior of PGE during S-saturated magmatic differentiation and mantle melting processes can be accounted for by assuming that Monosufide Solid Solution (Mss) controls the PGE budget in MORB melting residues whereas MORB differentiation processes involve Cu-Ni-rich sulfide melt segregation.     

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     

The Concentration of the Platinum-Group Elements in South African Komatiites: Implications for Mantle Sources, Melting Regime and PGE Fractionation during Crystallization

We have analysed 18 samples of komatiite from five consecutivelava flows of the Komati Formation at Spinifex Creek, BarbertonMountain Land. Our samples include massive komatiite, varioustypes of spinifex-textured komatiite, and flow-top breccias.The rocks have low platinum-group element (PGE) contents andPd/Ir ratios relative to komatiites from elsewhere, at 0·45–2ppb Os, 1–1·4 ppb Ir, <1–5 ppb Ru, 0·33–0·79ppb Rh, 1·7–6 ppb Pt, 1·6–6·1ppb Pd, and Pd/Ir 3·3. Pt/Pd ratios are c. 1·1.Platinum-group elements are depleted relative to Cu (Cu/Pd =15 300). They display a tendency to increase in the less magnesiansamples, suggesting that the magmas were S-undersaturated uponeruption and that all PGE were incompatible with respect tocrystallizing olivine. Komatiites from the Westonaria Formationof the Ventersdorp Supergroup and the Roodekrans Complex nearJohannesburg have broadly similar PGE patterns and concentrationsto the Komati rocks, suggesting that the PGE contents of SouthAfrican ultrabasic magmas are controlled by similar processesduring partial mantle melting and low-P magmatic crystallization.Most workers believe that the Barberton komatiites formed byrelatively moderate-degree batch melting of the mantle at highpressure. Based on the concentration of Zr in the Komati samples,we estimate that the degree of partial melting was between 26and 33%. We suggest that the low PGE contents and Pd/Ir ratiosof all analysed South African komatiites are the result of sulphideshaving been retained in the mantle source during partial melting.The difference in Pd/Ir between our samples and Al-undepletedkomatiites from elsewhere further suggests that the PGE arefractionated during progressive partial melting of the mantle.Thus, our data are in agreement with other recent studies showingthat the PGE are hosted by different phases in the mantle, withPd being concentrated by interstitial Cu-rich sulphide, andthe IPGE (Os, Ir, Ru) and Rh resting in monosulphide solid solutionincluded within silicates. Pt is possibly controlled by a discreterefractory phase, as Pt/Pd ratios of most komatiites worldwideare sub-chondritic. KEY WORDS: platinum-group elements; komatiites; Barberton; mantle melting; South Africa     

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.     

Platinum-group elements distribution and spinel composition in podiform chromitites and associated rocks from the upper mantle section of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco

The distribution of platinum-group elements (PGEs), together with spinel composition, of podiform chromitites and serpentinized peridotites were examined to elucidate the nature of the upper mantle of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco. The mantle section is dominated by harzburgite with less abundant dunite. Chromitite pods are also found as small lenses not exceeding a few meters in size. Almost all primary silicates have been altered, and chromian spinel is the only primary mineral that survived alteration. Chromian spinel of chromitites is less affected by hydrothermal alteration than that of mantle peridotites. All chromitite samples of the Bou Azzer ophiolite display a steep negative slope of PGE spidergrams, being enriched in Os, Ir and Ru, and extremely depleted in Pt and Pd. Harzburgites and dunites usually have intermediate to low PGE contents showing more or less unfractionated PGE patterns with conspicuous positive anomalies of Ru and Rh. Two types of magnetite veins in serpentinized peridotite, type I (fibrous) and type II (octahedral), have relatively low PGE contents, displaying a generally positive slope from Os to Pd in the former type, and positive slope from Os to Rh then negative from Rh to Pd in the latter type. These magnetite patterns demonstrate their early and late hydrothermal origin, respectively. Chromian spinel composition of chromitites, dunites and harzburgites reflects their highly depleted nature with little variations; the Cr# is, on average, 0.71, 0.68 and 0.71, respectively. The TiO₂ content is extremely low in chromian spinels, <0.10, of all rock types. The strong PGE fractionation of podiform chromitites and the high-Cr, low-Ti character of spinel of all rock types imply that the chromitites of the Bou Azzer ophiolite were formed either from a high-degree partial melting of primitive mantle, or from melting of already depleted mantle peridotites. This kind of melting is most easily accomplished in the supra-subduction zone environment, indicating a genetic link with supra-subduction zone magma, such as high-Mg andesite or arc tholeiite. This is a general feature in the Neoproterozoic upper mantle.     

陕西太白金矿含金角砾岩中铂族元素特征

采用硫镍火法试金(NiS-FA)结合电感耦合等离子质谱(ICP-MS)分析了太白金矿硫化物和含金角砾岩中铂族元素的含量,结果显示,与秦岭地区八卦庙相比铂族元素含量较高,而低于原始地幔,其中铂(Pt)、钯(Pd)、钌(Ru)富集,并结合前人研究资料对铂族元素的来源和迁移机制进行探讨。铂族元素可能受深源的影响,IPGE(Ir、Os、Ru)可能主要以硫化物形式存在而PPGE(Rh、Pt、Pd)可能主要以单质存在。     

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.     

阜新中生代火山岩的铂族元素特征——以碱锅和乌拉哈达为例

采用镍锍火试金法结合ICP—MS分析了碱锅玄武岩和乌拉哈达高镁安山岩样品中的Ir．Ru、Rh、Pt和Pd的含量。原始地幔标准化后的PGE分布模式呈正斜率型，Pd／Ir值高于相应的地幔比值，表明铂族元素发生了分异，这是由于在部分熔融过程中，Ir存在于地幔矿物相尖晶石和合金中，而Pd赋存于硫化物中造成的，乌拉哈达高镁安山岩中的铂族元素还可能在结晶分异过程中受到先期结晶的矿物相和合金的影响。阜新火山岩Pt的负异常可能是包含Pt的金属合金残留在地幔中造成。     

Abundance and distribution of PGE and Au in the island-arc mantle: implications for sub-arc metasomatism

Ultramafic xenoliths from a veined mantle wedge beneath the Kamchatka arc have non-chondritic, fractionated chondrite-normalized platinum-group element (PGE) patterns. Depleted (e.g., low bulk-rock Al₂O₃ and CaO contents) mantle harzburgites show clear enrichment in the Pd group relative to the Ir group PGEs and, in most samples, Pt relative to Rh and Pd. These PGE signatures most likely reflect multi-stage melting which selectively concentrates Pt in Pt–Fe alloys while strongly depleting the sub-arc mantle wedge in incompatible elements. Elevated gold concentrations and enrichment of strongly incompatible enrichment (e.g., Ba and Th) in some harzburgites suggest a late-stage metasomatism by slab-derived, saline hydrous fluids. Positive Pt, Pd, and Au anomalies coupled with Ir depletions in heavily metasomatized pyroxenite xenoliths probably reflect the relative mobility of the Pd and Ir groups (especially Os) during sub-arc metasomatism which is consistent with Os systematics in arc mantle nodules. Positive correlations between Pt, Pd, and Au and various incompatible elements (Hf, U, Ta, and Sr) also suggest that both slab-derived hydrous fluids and siliceous melts were involved in the sub-arc mantle metasomatism beneath the Kamchatka arc.     

Heterogeneously depleted Precambrian lithosphere deduced from mantle peridotites and associated chromitite deposits of Al'Ays ophiolite,Northwestern Arabian Shield,Saudi Arabia

The mantle section of Al'Ays ophiolite consists of heterogeneously depleted harzburgites, dunites and large-sized chromitite pods. Two chromitite-bearing sites (Site1 and Site2), about 10 km apart horizontally from one another, were examined for their upper mantle rocks. Cr-spinels from the two sites have different chemistry; Cr-rich in Site1 and Al-rich in Site2. The average Cr-ratio = (Cr/(Cr + Al) atomic ratio) of Cr-spinels in harzburgites, dunites and chromitites is remarkably high 0.78, 0.77 and 0.87, respectively, in Site1, compared with those of Site2 which have intermediate ratio averages 0.5, 0.56 and 0.6, respectively. The platinum-group elements (PGE) in chromitites also show contrasting patterns from Site1 to Site2; having elevated IPGE (Os, Ir, Ru) and strongly depleted in PPGE (Rh, Pt, Pd) with steep negative slopes in the former, and gentle negative slopes in the latter. The oxygen fugacity (Δlog fO₂) values deduced from harzburgites and dunites of Site1 show a wide variation under reducing conditions, mostly below the FMQ buffer. The Site2 harzburgites and dunites, on the other hand are mostly above the FMQ buffer. Two magmatic stages are suggested for the lithospheric evolution of Al'Ays ophiolite in response to a switch of tectonic setting. The first stage produced a peridotites–chromitites suite with Al-rich Cr-spinels, possibly beneath a mid-ocean ridge setting, or most likely in back-arc rift of a supra-subduction zone setting. The second stage involved higher degrees of partial melting, produced a peridotites–chromitites suite with Cr-rich Cr-spinels, possibly in a fore-arc setting. The coexistence of compositionally different mantle suites with different melting histories in a restricted area of an ophiolite complex may be attributable to a mechanically juxtaposed by mantle convection during recycling. The mantle harzburgites and dunites are apt to be compositionally modified during recycling process; being highly depleted (Site1 case) than their original composition (Site2 case).