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1.
This paper presents the first study of accessing the Pt, Pd and Rh levels in road dusts collected from Hyderabad city, India, as these metals, emitted from automobile catalytic converters, are accumulating in the environment causing concern about human health and ecological risks. Samples were analyzed by ICP-MS following preconcentration by NiS-fire assay and Te coprecipitation. Pt (1.5–43 ng/g), Pd (1.2–58 ng/g) and Rh (0.2–14.2 ng/g) concentrations obtained were above upper crust values, but were lower when compared with several other cities around the world. Dust samples from road junctions and traffic signals with heavy and erratic traffic flow showed higher PGE levels than those from roads with low and free flow traffic suggesting that traffic flow conditions greatly influenced emission of PGE from the catalyst. Significant correlation of Pt, Pd and Rh indicate a common source for these metals. PGE were also positively correlated with Ce, Zr, Hf and Y. These positive inter-element correlations identified traffic as the main source of PGE emission to the roadway environment. The results obtained indicate to an appreciable increase in auto catalyst-derived PGE. In consideration of the adverse effects of PGE, monitoring their level and transformation paths is of prime importance.  相似文献   

2.
A method was developed for the determination of platinum‐group elements (PGE) in geological samples by isotope dilution‐inductively coupled plasma‐mass spectrometry combined with sulfide fire assay preconcentration. Samples were fused and PGE analytes were concentrated in sulfide buttons. The buttons were dissolved using HCl leaving PGE analytes in insoluble residues, which were digested in HNO3 and simultaneously processed for the distillation of Os. The remaining solutions were further prepared for the purification of Ru, Rh, Pd, Ir and Pt using a tandem assembly of cation and Ln resin columns. The eluents were directly analysed by membrane desolvation‐ICP‐MS. Ruthenium, Pd, Os, Ir and Pt were determined by isotope dilution, whereas Rh was determined by conventional reference material calibration combined with 193Ir as the internal standard element. The method was validated using a series of PGE reference materials, and the measurement data were consistent with the recommended and the literature values. The measurement precision was better than 10% RSD. The procedural blanks were 0.121 ng for Ru, 0.204 for Rh, 0.960 ng for Pd, 0.111 ng for Os, 0.045 ng for Ir and 0.661 ng for Pt, and the limits of detection (3s) were 0.011 ng g?1 for Ru, 0.008 ng g?1 for Rh, 0.045 ng g?1 for Pd, 0.009 ng g?1 for Os, 0.006 ng g?1 for Ir and 0.016 ng g?1 for Pt when a test portion mass of 10 g was used. This indicates that the proposed method can be used for the determination of trace amounts of PGE in geological samples.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
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/YbN < 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.  相似文献   

6.
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements V, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in Fremdlinge with a spatial resolution of 15 to 25 μm. A sulfide vein in a refractory inclusion in Allende (CV3-oxidized) is enriched in Rh, Ru, and Os with no detectable Pd, Re, Ir, or Pt, indicating that Rh, Ru, and Os were redistributed by sulfidation of the inclusion, causing fractionation of Re/Os and other siderophile element ratios in Allende CAIs. Fremdlinge in compact Type-A inclusions from Efremovka (CV3-reduced) exhibit subsolidus exsolution into kamacite and taenite and minimal secondary formation of V-magnetite and schreibersite. Siderophile element partitioning between taenite and kamacite is similar to that observed previously in iron meteorites, while preferential incorporation of the light PGEs (Ru, Rh, Pd) relative to Re, Os, Ir, and Pt by schreibersite was observed. Fremdling EM2 (CAI Ef2) has an outer rim of P-free metal that preserves the PGE signature of schreibersite, indicating that EM2 originally had a phosphide rim and lost P to the surrounding inclusion during secondary processing. Most Fremdlinge have chondrite-normalized refractory PGE patterns that are unfractionated, with PGE abundances derived from a small range of condensation temperatures, ∼1480 to 1468 K at Ptot = 10−3 bar. Some Fremdlinge from the same CAI exhibit sloping PGE abundance patterns and Re/Os ratios up to 2 × CI that likely represent mixing of grains that condensed at various temperatures.  相似文献   

7.
方解石作为木落稀土矿床常见的脉石矿物,其中的铂族元素(简称PGE)地球化学特征有可能记录了地质流体的性质。采用ICP-MS分析木落方解石中PGE的含量,并对铂族元素的分布、相关性、成因进行了探讨。木落方解石可以分为两类:I型方解石和Ⅱ型方解石。I型方解石中∑PGE(不含Os)0.62～1.33ng/g,具相对低的Pd/Pt、Pd/Rh、Pd/Ru、Pd/Ir比值,不太显著的Pt-Pd分配模式,为岩浆成因方解石,与成矿作用密切相关;Ⅱ型方解石中∑PGE(不含Os)1.85～2.97ng/g,具相对高的Pd/Pt、Pd/Rh、Pd/Ru、Pd/Ir比值和显著的Pt-Pd分配模式,为热液成因方解石,代表了成矿作用后的一期地质流体作用,与成矿关系不大,仅局部地区存在改造前次流体作用形成的稀土矿体。富CO2热液具有携带PGE的能力,并能够导致PGE的分异,与富CO2岩浆相比,富CO2热液对铂族元素具有一定程度的富集作用。  相似文献   

8.
This study represents the first detailed investigation of platinum-group elements (PGEs) in road-deposited sediment (RDS) in Hawaii, USA. Thirty-three sample locations, in two urban watersheds in Honolulu, Oahu, Hawaii were sampled. The <63 μm fraction of RDS was digested with aqua regia, followed by matrix separation with Dowex AG50-X8 cation exchange resin. PGEs were analyzed with inductively coupled plasma-mass spectrometry (ICP-MS) equipped with a desolvating nebulizer. Concentrations of Rh, Pd and Pt in residential streets reached 64, 105 and 506 ng/g, respectively. Maximum enrichment ratios, computed as RDS concentrations relative to baseline values, exceeded 400, indicating a significant anthropogenic signal with the sequence Rh > Pt > Pd. Iridium concentrations were uniformly low <1 ng/g, and enrichment ratios support a geogenic source. Significant interelement PGE correlations (Pd–Pt–Rh), combined with the magnitude of PGE pair-wise ratios (Pt/Pd, Pt/Rh and Pd/Rh), and relative percentages comparable to European RDS and roadside soil in Indiana, USA all suggest an automobile source. Attrition of PGE-loaded automobile catalytic converters and subsequent loss to the environment by exhaust emissions explains the significant environmental signal of PGEs in road environments of Hawaii. Further PGE work is required to quantify urban transport paths as PGEs are known to bioaccumulate, cause cellular damage and may have detrimental human health effects.  相似文献   

9.
The abundances of the highly siderophile elements (HSE) Re, Os, Ir, Ru, Pt, Rh, Pd and Au, and 187Os/188Os isotope ratios have been determined for a set of carbonaceous, ordinary, enstatite and Rumuruti chondrites, using an analytical technique that permits the precise and accurate measurement of all HSE from the same digestion aliquot. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS analysis. The monoisotopic elements Rh and Au were quantified relative to the abundance of Ir.Differences in HSE abundances and ratios such as Re/Os, 187Os/188Os, Pd/Ir and Au/Ir between different chondrite classes are further substantiated with new data, and additional Rh and Au data, including new data for CI chondrites. Systematically different relative abundances of Rh between different chondrite classes are reminiscent of the behaviour of Re. Carbonaceous chondrites are characterized by low average Rh/Ir of 0.27 ± 0.03 (1s) which is about 20% lower than the ratio for ordinary (0.34 ± 0.02) and enstatite chondrites (EH: 0.33 ± 0.01; EL: 0.32 ± 0.01). R chondrites show higher and somewhat variable Rh/Ir of 0.37 ± 0.07.Well-defined linear correlations of HSE, in particular for bulk samples of ordinary and EL chondrites, are explained by binary mixing and/or dilution by silicates. The HSE carriers responsible for these correlations have a uniform chemical composition, indicating efficient homogenization of local nebular heterogeneities during or prior to the formation of the host minerals in chondrite components. Excepting Rumuruti chondrites and Au in carbonaceous chondrites, these correlations also suggest that metamorphism, alteration and igneous processes had negligible influence on the HSE distribution on the bulk sample scale.Depletion patterns for Rh, Pd and Au in carbonaceous chondrites other than CI are smoothly related to condensation temperatures and therefore consistent with the general depletion of moderately volatile elements in carbonaceous chondrites. Fractionated HSE abundance patterns of ordinary, enstatite and Rumuruti chondrites, however, are more difficult to explain. Fractional condensation combined with the removal of metal phases at various times, and later mixing of early and late formed metal phases may provide a viable explanation. Planetary fractionation processes that may have affected precursor material of chondrite components cannot explain the HSE abundance patterns of chondrite groups. HSE abundances of some, but not all Rumuruti chondrites may be consistent with solid sulphide-liquid sulphide fractionation processes during impact induced melting.  相似文献   

10.
Summary The Jinchuan deposit is a platinum group element (PGE)-rich sulfide deposit in China. Drilling and surface sampling show that three categories of platinum group element (PGE) mineralization occur; type I formed at magmatic temperatures, type II occurs in hydrothermally altered zones of the intrusion, and type III in sheared dunite and lherzolite. All ore types were analyzed for Os, Ir, Ru, Rh, Pd, Pt and Au, as well as for Cu, Ni, Co and S. Type I ore has (Pt + Pd)/(Os + Ir + Ru + Rh) ratios of <7 and relatively flat chondrite-normalized noble metal patterns; the platinum group minerals (PGM) are dominated by sperrylite and moncheite associated with chalcopyrite, pyrrhotite and pentlandite. Type II has (Pt + Pd)/(Os + Ir + Ru + Rh) ratios from 40 to 330 and noble metal distribution patterns with a positive slope; the most common PGM are sperrylite and Pd bismuthotelluride phases concentrated mostly at the margins of base metal sulfides. Type III ores have the highest (Pt + Pd)/(Os + Ir + Ru + Rh) ratios from 240 to 710; the most abundant PGM are sperrylite and phases of the Pt–Pd–Te–Bi–As–Cl system. It is concluded that the Jinchuan deposit formed as a result of primary magmatic crystallization followed by hydrothermal remobilization, transport, and deposition of the PGE.  相似文献   

11.
为探讨贵州下寒武统黑色岩系中铂族元素物质来源及钼-镍、钒多金属形成的沉积环境与成矿作用,在钼-镍、钒多金属层及其顶底页岩、底部硅质岩中采集样品测试分析。通过对样品中金、铂族元素含量(质量分数)及其地球化学特征值研究,结果表明：黑色岩系中金及铂族元素含量显示协同变化特征;Pd富集,Ru、Ir亏损明显,Pt、Rh、Os基本持平或略有变化;样品的原始地幔标准值标准化模式配分曲线从Os、Ru、Rh、Ir、Pt到Pd大致呈“W”型,配分曲线略呈左倾,总体上呈现w(Pd)>w(Pt)>w(Os)>w(Rh)>w(Ru)>w(Ir)的变化关系;黑色岩系铂族元素来源与正常海水及海底热水喷流作用关系密切,地外来源可能性极小;黑色岩系钼-镍、钒多金属层中铂族元素的富集存在单独成矿作用或成矿作用的叠加,而且在钒多金属层内局部存在分层或条带分异。  相似文献   

12.
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.  相似文献   

13.
Platinum group elements (PGE) enrichment occurs in Zn–Cu and Ni-rich ophiolities in a number of geological settings. Platinum group elements (PGE) mineralization in Pyroxenite from the Faryab ophiolities of Zagros belt in south Iran was studied. The ophiolite rocks represent blocks of Tethyan oceanic crust that were emplaced on the continental margin during the late Cretaceous period. Much of lower ophiolitic section is composed of homogeneous harzburgite, while upper sections harzburgite interlayer with dunite and pyroxenite are included. This study focused on pyroxenite that includes most of sulfide mineralization in Faryab. More than 500 samples were investigated from polished thin sections; that cover all area of Faryab. The sulfide phases include pyrrhotite, pentlandite, millerite, violarite, smythite, and heazlewoodite. The results show that in almost all the samples Os is below the 2 ppb detection limit, Platinum values vary from <5 to 91 ppb and the light PGE (Ru, Rh, and Pd) relative to the heavy PGE (Os, Ir, and Pt) are more concentrated. Calculation showed that in pyroxenites Pd–Pt is occurring with orthopyroxenite and Rh–Os is occurring in clinopyroxenite. Ni/Pd ratios in Faryab vary between 7 and 356 and Pd/Ir ratio is 0.1–27. This indicates that in Faryab area partial melt of mantle occurred. Pd/Rh ratio in Faryab is 0.1–11, and Pd/Pt varies between 0.2 and 1.5. Pd/Ir ratio in Faryab decreases and shows that PGE in Faryab occurred.  相似文献   

14.
The distribution of platinum group elements (PGEs) in massive sulfides and hematite–magnetite±pyrite assemblages from the recently discovered basalt-hosted Turtle Pits hydrothermal field and in massive sulfides from the ultramafic-hosted Logatchev vent field both on the Mid-Atlantic Ridge was studied and compared to that from selected ancient volcanic-hosted massive sulfide (VHMS) deposits. Cu-rich samples from black smoker chimneys of both vent fields are enriched in Pd and Rh (Pd up to 227 ppb and Rh up to 149 ppb) when compared to hematite–magnetite-rich samples from Turtle Pits (Pd up to 10 ppb, Rh up to 1.9 ppb). A significant positive correlation was established between Cu and Rh in sulfide samples from Turtle Pits. PGE chondrite-normalized patterns (with a positive Rh anomaly and Pd and Au enrichment), Pd/Pt and Pd/Au ratios close to global MORB, and high values of Pd/Ir and Pt/Ir ratios indicate mafic source rock and seawater involvement in the hydrothermal system at Turtle Pits. Similarly shaped PGE chondrite-normalized patterns and high values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides at Logatchev likely reflect a similar mechanism of PGE enrichment but with involvement of ultramafic source rocks.  相似文献   

15.
ＩＮＴＲＯＤＵＣＴＩＯＮＬｏｗｅｒＣａｍｂｒｉａｎｂｌａｃｋｒｏｃｋｓｅｒｉｅｓｅｘｉｓｔｓｂｒｏａｄｌｙｉｎｍｏｒｅｔｈａｎ１０ｐｒｏｖｉｎｃｅｓｉｎＳｏｕｔｈＣｈｉｎａ（Ｃｈｅｎｅｔａｌ．,１９９０）．Ｔｈｅｂｏｔｏｍｏｆｔｈｅｓｅｒｉｅｓｓｐｏ...  相似文献   

16.
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.  相似文献   

17.
The Palaeoproterozoic Ni–Cu sulphide deposits of the PechengaComplex, Kola Peninsula, occur in the lower parts of ferropicriticintrusions emplaced into the phyllitic and tuffaceous sedimentaryunit of the Pilgujärvi Zone. The intrusive rocks are comagmaticwith extrusive ferropicrites of the overlying volcanic formation.Massive lavas and chilled margins from layered flows and intrusionscontain <3–7 ng/g Pd and Pt and <0·02–2·0ng/g Ir, Os and Ru with low Pd/Ir ratios of 5–11. Theabundances of platinum group elements (PGE) correlate with eachother and with chalcophile elements such as Cu and Ni, and indicatea compatible behaviour during crystallization of the parentalmagma. Compared with the PGE-depleted central zones of differentiatedflows (spinifex and clinopyroxene cumulate zones) the olivinecumulate zones at the base contain elevated PGE abundances upto 10 ng/g Pd and Pt. A similar pattern is displayed in intrusivebodies, such as the Kammikivi sill and the Pilgujärvi intrusion.The olivine cumulates at the base of these bodies contain massiveand disseminated Ni–Cu-sulphides with up to 2 µg/gPd and Pt, but the PGE concentrations in the overlying clinopyroxenitesand gabbroic rocks are in many cases below the detection limits.The metal distribution observed in samples closely representingliquid compositions suggests that the parental magma becamesulphide saturated during the emplacement and depleted in chalcophileand siderophile metals as a result of fractional segregationof sulphide liquids. Relative sulphide liquid–silicatemelt partition coefficients decrease in the order of Ir >Rh > Os > Ru > Pt = Pd > Cu. R-factors (silicate-sulphidemass ratio) are high and of the order of 104–105, andthey indicate the segregation of only small amounts of sulphideliquid in the parental ferropicritic magma. In differentiatedflows and intrusions the sulphide liquids segregated and accumulatedat the base of these bodies, but because of a low silicate–sulphidemass ratio the sulphide liquids had a low PGE tenor and Pt/Irand Cu/Ir ratios similar to the parental silicate melts. Duringcooling the sulphide liquid crystallized 40–50% of monosulphidesolid solution (mss) and the residual sulphide liquid becameenriched in Cu, Pt and Pd and depleted in Ir, Os and Ru. TheCu-rich sulphide liquid locally assimilated components of thesurrounding S-rich sediments as suggested by the radiogenicOs isotopic composition of some sulphide ores (  相似文献   

18.
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.  相似文献   

19.
The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations (r = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5–2) and Pt/Ru ratios (7–28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values (<2) similar to CI-chondrite (∼1). The chondrite-normalized PGE patterns are similar to those of igneous rocks, except that Pd is relatively depleted. The water depth of Fe-Mn crust formation appears to have a first-order control on both major element and PGE enrichments. These relationships are defined statistically by significant (r > 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations (r > 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE (r < 0.5). The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its positive correlations with Ce and Co demonstrate a common link for the high concentrations of all three elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.  相似文献   

20.
The contents of the platinum-group elements (PGEs: Os, Ir, Ru, Rh, Pt, Pd) in the Abulangdang ultramafic intrusion have been determined using ICP-MS after nickel sulfide fire assay preconcentration. Different samples show significant differences in absolute PGE abundance. They display a pronounced negative incline in mantle-normalized patterns which are characterized by strong enrichment in IPGEs (Os, Ir, Ru) and depleting to slight enrichment in PPGEs (Rh, Pt, Pd). The characteristics of PGE distribution in the Abulangdang rocks are due to the combined action of sulfide and non-sulfide (spinel/chromite or alloy or micro-granular aggregation of metals). In comparison with the mafic-ultramafic rocks which host Ni-Cu-PGE deposits in the Emeishan Large Igneous Province (ELIP), it is assumed that the Abulangdang ultramafic intrusion may be the product of early-stage magma activity in the ELIP.  相似文献   

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