Platinum group element geochemistry of komatiites from the Alexo and Pyke Hill areas, Ontario, Canada

Thirty-three whole-rock drill core samples and thirteen olivine, chromite, and sulfide separates from three differentiated komatiite lava flows at Alexo and Pyke Hill, Canada, were analyzed for PGEs using the Carius tube digestion ID-ICP-MS technique. The emplaced lavas are Al-undepleted komatiites with ∼27% MgO derived by ∼50% partial melting of LILE-depleted Archean mantle. Major and minor element variations during and after emplacement were controlled by 30 to 50% fractionation of olivine Fo_93-94. The emplaced lavas are characterized by (Pd/Ir)_N = 4.0 to 4.6, (Os/Ir)_N = 1.07, and Os abundances of ∼2.3 ppb. Variations in PGE abundances within individual flows indicate that Os and Ir were compatible (bulk D_Os,Ir = 2.4-7.1) and that Pt and Pd were incompatible (bulk D_Pt,Pd < 0.2) during lava differentiation, whereas bulk D_Ru was close to unity. Analyses of cumulus olivine separates indicate that PGEs were incompatible in olivine (D_PGEs^Ol-Liq = 0.04-0.7). The bulk fractionation trends cannot be accounted for by fractionation of olivine alone, and require an unidentified Os-Ir-rich phase. The composition of the mantle source (Os = 3.9 ppb, Ir = 3.6 ppb, Ru = 5.4 ppb, Pt and Pd = 5.7 ppb) was constrained empirically for Ru, Pt, and Pd; the Os/Ir ratio was taken to be identical to that in the emplaced melt, and the Ru/Ir ratio was taken to be chondritic, so that the absolute IPGE abundances of the source were determined by Ru. This is the first estimate of the PGE composition of a mantle source derived from analyses of erupted lavas. The suprachondritic Pd/Ir and Os/Ir of the inferred Abitibi komatiite mantle source are similar to those in off-craton spinel lherzolites, orogenic massif lherzolites, and enstatite chondrites, and are considered to be an intrinsic mantle feature. Bulk partition coefficients for use in komatiite melting models derived from the source and emplaced melt compositions are: D_Os,Ir = 2.3, D_Ru = 1.0, D_Pt,Pd = 0.07. Ruthenium abundances are good indicators of absolute IPGE abundances in the mantle sources of komatiite melts with 26 to 29% MgO, as Ru fractionates very little during both high degrees of partial melting and lava differentiation.     

Geochemical study of peridotites from the Manipur Ophiolite Complex,Northeast India with special reference to their PGE concentration

The peridotites of the Manipur Ophiolite Complex (MOC) have been examined based on mineral chemistry, major elements and PGE contents. They represent high-magnesian cumulates with Mg# > 0.90 (Mg/Mg+Fe) in olivine and Cr# > 0.12 (Cr/Cr+Al) in spinel. High Mg* contents of the olivine show that these rocks are most likely derived from partial melting of the residual upper mantle. The peridotites contain higher concentration of Palladium Group PGE (PPGE) (Rh=4.4−6.6ppb; Pd=336−458ppb and Pt=14.6−36.4ppb) than the Iridium Group PGE (IPGE) (Os=2.4−5.8ppb; Ir=3.2−4.16ppb and Ru=5.2−7ppb). These are characterized by overall enrichment of PGE concentration (σPGE=365.8 − 516.6 ppb) and high ratio of (Pt+Pd)/(Os+Ir+Ru). This suggests that the rocks are formed by partial melting and crystal fractionation of olivine-rich (picritic) magma.     

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。     

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.     

塔里木大火成岩省瓦吉里塔格霞石岩铂族元素地球化学特征

作为塔里木大火成岩省形成最晚的火成岩,新疆巴楚瓦吉里塔格霞石岩的岩浆源区性质的确定对于揭示塔里木大火成岩省的深部地质过程具有重要的约束作用。对瓦吉里塔格霞石岩的铂族元素地球化学特征进行了研究,铂族元素(PGE)分析结果显示,原始地幔标准化的PGE呈正斜率型分布,且Pd/Ir值高于原始地幔比值,说明霞石岩的铂族元素发生了分异。霞石岩全岩的PGE与Mg O呈正相关,Pd/Ir、Cu/Pd与Mg O则呈负相关,说明PGE的分异主要受到橄榄石的结晶分异作用控制,也是其Cu/Pd值极高及岩浆S饱和的因素之一,同时Cu/Pd值说明霞石岩岩浆为硫饱和岩浆,但是没有因素导致岩浆S过饱和进而发生硫化物的熔离。与其他大火成岩省岩石相比,瓦吉里塔格霞石岩极度亏损PGE,SCSS(硫承载量)计算结果表明母岩浆在形成之初就发生S过饱和,主要是地幔低程度部分熔融造成的,据此认为地幔源区的部分熔融程度在塔里木大火成岩省Cu-Ni硫化物铂族元素矿床形成过程中起着至关重要的作用。     

Noble Metal Enrichment Processes in the Merensky Reef, Bushveld Complex

We have analysed sulphides, silicates, and chromites of theMerensky Reef for platinum-group elements (PGEs), Re and Auusing laser ablation-inductively coupled plasma mass spectrometryand synthetic pyrrhotite standards annealed with known quantitiesof noble metals. Os, Ir and Ru reside in solid solution in pyrrhotiteand pentlandite, Rh and part of the Reef’s Pd in pentlandite,whereas Pt, Au, Re and some Pd form discrete phases. Olivineand chromite, often suspected to carry Os, Ir and Ru, are PGEfree. All phases analysed contain noble metals as discrete micro-inclusionswith diameters typically <100 nm. Inclusions in sulphidescommonly have the element combinations Os–Ir–Ptand Pt–Pd–Au. Inclusions in olivine and chromiteare dominated by Pt ± Au–Pd. Few inclusion spectracan be related to discrete noble metal phases, and few inclusionshave formed by sub-solidus exsolution. Rather, some PGE inclusions,notably those in olivine and chromite, are early-magmatic nuggetstrapped when their host phases crystallized. We suggest thatthe silicate melt layer that preceded the Merensky Reef wasPGE oversaturated at early cumulus times. Experiments combinedwith available sulphide–silicate partition coefficientssuggest that a silicate melt in equilibrium with a sulphidemelt containing the PGE spectrum of the Merensky ore would indeedbe oversaturated with respect to the least soluble noble metals.Sulphide melt apparently played little role in enriching thenoble metals in the Merensky Reef; rather, its role was to immobilizea pre-existing in situ stratiform PGE anomaly in the liquid-stratifiedmagma chamber. KEY WORDS: Bushveld Complex; Merensky Reef; laser-ablation ICP-MS; platinum-group mineralization     

Sulphide Segregation in Ferropicrites from the Pechenga Complex, Kola Peninsula, Russia

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 (     

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 Elements and Microstructures of Normal Merensky Reef from Impala Platinum Mines, Bushveld Complex

The Merensky Reef of the Bushveld Complex contains one of theworld’s largest concentrations of platinum-group elements(PGE). We have investigated ‘normal’ reef, its footwalland its hanging wall at Impala Platinum Mines. The Reef is 46cm thick and consists from bottom to top of leuconorite, anorthosite,chromitite and a very coarse-grained melanorite. The footwallis leuconorite and the hanging wall is melanorite. The onlyhydrous mineral present is biotite, which amounts to 1%, orless, of the rock. All of the rocks contain 0·1–5%interstitial sulphides (pyrrhotite, pentlandite and chalcopyrite),with the Reef rocks containing the most sulphides (1–5%).Lithophile inter-element ratios suggest that the magma fromwhich the rocks formed was a mixture of the two parental magmasof the Bushveld Complex (a high-Mg basaltic andesite and a tholeiiticbasalt). The Reef rocks have low incompatible element contentsindicating that they contain 10% or less melt fraction. Nickel,Cu, Se, Ag, Au and the PGE show good correlations with S inthe silicate rocks, suggesting control of the abundance of thesemetals by sulphides. The concentration of the chalcophile elementsand PGE in the silicate rocks may be modelled by assuming thatthe rocks contain sulphide liquid formed in equilibrium withthe evolving silicate magma. It is, however, difficult to modelthe Os, Ir, Ru, Rh and Pt concentrations in the chromititesby sulphide liquid collection alone, as the rocks contain 3–4times more Os, Ir, Ru, Rh and Pt than the sulphide-collectionmodel would predict. Two possible solutions to this are: (1)platinum-group minerals (PGM) crystallize from the sulphideliquid in the chromitites; (2) PGM crystallize directly fromthe silicate magma. To model the concentrations of Os, Ir, Ru,Rh and Pt in the chromitites it is necessary to postulate thatin addition to the 1% sulphides in the chromitites there isa small quantity (0·005%) of cumulus PGM (laurite, cooperiteand malanite) present. Sulphide liquids do crystallize PGM atlow f_S2. Possibly the sulphide liquid that was trapped betweenthe chromite grains lost some Fe and S by reaction with thechromite and this provoked the crystallization of PGM from thesulphide liquid. Alternatively, the PGM could have crystallizeddirectly from the silicate magma when it became saturated inchromite. A weakness of this model is that at present the exactmechanism of how and why the magma becomes saturated in PGMand chromite synchronously is not understood. A third modelfor the concentration of PGE in the Reef is that the PGE arecollected from the underlying cumulus pile by Cl-rich hydrousfluids and concentrated in the Reef at a reaction front. Althoughthere is ample evidence of compaction and intercumulus meltmigration in the Impala rocks, we do not think that the PGEwere introduced into the Reef from below, because the rocksunderlying the Reef are not depleted in PGE, whereas those overlyingthe Reef are depleted. This distribution pattern is inconsistentwith a model that requires introduction of PGE by intercumulusfluid percolation from below. KEY WORDS: Merensky Reef; platinum-group elements; chalcophile elements; microstructures     

The concentrations of the noble metals in Southern African flood-type basalts and MORB: implications for petrogenesis and magmatic sulphide exploration

Concentrations of the platinum-group elements have been determined in several suites of southern African flood-type basalts and mid-ocean ridge basalt (MORB), covering some 3 Ga of geologic evolution and including the Etendeka, Karoo, Soutpansberg, Machadodorp, Hekpoort, Ventersdorp and Dominion magmas. The magmas cover a compositional range from 3.7 to 18.7% MgO, 26–720 ppm Ni, 16–250 ppm Cu, and <1–255 ppb total platinum-group elements (PGE). The younger basalts (Etendeka, Karoo) tend to be depleted in PGE relative to Cu, while most of the older basalts (Hekpoort, Machadodorp, Ventersdorp, Dominion) show no PGE depletion relative to Cu. Further, the younger basalts tend to have lower average Pt/Pd ratios than the older basalts, and the MORBs have lower average Pt/Pd than the continental basalts within the broad groupings of "old" and "young" basalts. This may reflect (1) a decreasing degree of mantle melting through geologic time, and (2) source heterogeneity, in that the MORBs are derived from predominantly asthenospheric mantle, whereas the continental basalts also contain a lithospheric mantle component enriched in Pt. In addition to these factors, some PGE fractionation also occurred during differentiation of the magmas, with Pd showing incompatible behaviour and the other PGE variably compatible behaviour. The examined southern African flood-type basalts and MORB appear to offer limited prospects for magmatic sulfide ores, largely because they show little evidence for significant chalcophile metal depletion that could be the result of sulphide extraction during ascent and crystallization.Editorial responsibility: I. Parsons     

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 Geochemical Characteristics of the Picrites and High-Ti Basalts in the Binchuan Area,Yunnan Province

The Binchuan area of Yunnan is located in the western part of the Emeishan large igneous province in the western margin of the Yangtze Block.In the present study,the Wuguiqing profile in thickness of about 1440 m is mainly composed of high-Ti basalts,with minor picrites in the lower part and andesites,trachytes,and rhyolites in the upper part.The picrites have relatively higher platinum-group element（PGE） contents（ΣPGE=16.3-28.2 ppb）,with high Cu/Zr and Pd/Zr ratios,and low S contents（5.03-16.9 ppm）,indicating the parental magma is S-unsaturated and generated by high degree of partial melting of the Emeishan large igneous province（ELIP） mantle source.The slightly high Cu/Pd ratios（11 000-24 000） relative to that of the primitive mantle suggest that 0.007%sulfides have been retained in the mantle source.The PGE contents of the high-Ti basalts exhibit a wider range（ΣPGE=0.517-30.8 ppb）.The samples in the middle and upper parts are depleted in PGE and haveε_Nd（260 Ma） ratios ranging from -2.8 to -2.2,suggesting that crustal contamination of the parental magma during ascent triggered sulfur saturation and segregation of about 0.446%-0.554% sulfides,and the sulfide segregation process may also provide the ore-forming material for the magmatic Cu-Ni-PGE sulfide deposits close to the studied basalts.The samples in this area show Pt-Pd type primitive mantle-normalized PGE patterns,and the Pd/Ir ratios are higher than that of the primitive mantle（Pd/Ir=1）,indicating that the obvious differentiation between Ir-group platinum-group elements（IPGE） and Pd-group platinum-group elements（PPGE） are mainly controlled by olivine or chromites fractionation during magma evolution.The Pd/Pt ratios of most samples are higher than the average ratio of mantle（Pd/Pt=0.55）,showing that the differentiation happened between Pt and Pd.The differentiation in picrites may be relevant to Pt hosted in discrete refractory Pt-alloy phase in the mantle;whereas the differentiation in the high-Ti basalts is probably associated with the fractionation of Fe-Pt alloys,coprecipitating with Ir-Ru-Os alloys.Some high-Ti basalt samples exhibit negative Ru anomalies,possibly due to removal of laurite collected by the early crystallized chromites.     

滇西金宝山富铂钯岩体岩浆源区研究：铂族元素和Sr-Nd同位素约束

金宝山杂岩体位于扬子板块西缘,毗邻哀牢山造山带北段,岩体中蕴含丰富的铂钯资源,是峨眉山大火成岩省(ELIP)中大型岩浆型铂族元素矿床。岩体的主要组成为辉石橄榄岩,矿体以似层状、透镜状产出于辉石橄榄岩中。地幔是镍矿床和铂族元素矿床最重要的源区,因而对Ni、Cu及PGE等元素行为的研究,是剖析岩浆型Ni-Cu-PGE矿床源区特征的一个重要研究方向。该研究获得金宝山岩体中辉橄岩铂族元素及Sr-Nd同位素数据,结合前人对ELIP中不同类型岩石系列PGE成分研究及Ni、Cu、PGE等元素在岩浆和硫化物中的分配系数,半定量模拟得到金宝山原始岩浆的形成源于地幔中高度部分熔融(25%~40%)形成的富PGE岩浆(含12.8×10-9 Pd,9.8×10-9 Pt,0.6×10-9 Rh和0.7×10-9 Ir),其铂族元素成分与ELIP苦橄岩成分相当,并且岩浆在演化的过程中遭受了10%~20%地壳混染作用。利用批式部分熔融公式及各铂族元素在硅酸盐矿物和熔体之间的分配系数反演计算得到产生金宝山熔体的地幔约含有5.3×10-9 Pd,7.5×10-9 Pt,0.75×10-9 Rh和1.5×10-9 Ir,相比原始地幔而言并没有表现出明显富集PGE的特征。这表明地幔中高度部分熔融+大量岩浆与硫化物的充分反应是形成大型岩浆型铂族元素矿床的一种可具备的条件。     

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     

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 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.     

A geochemical and Nd isotopic study of Barberton komatiites (South Africa): implication for the Archean mantle

The Komati Formation of the Barberton greenstone belt (BGB), South Africa, is composed of both Al-undepleted and -depleted komatiites. The Al-undepleted komatiites are characterised by Al₂O₃/TiO₂ and CaO/Al₂O₃ ratios of 15–18 and 1.1–1.5, respectively, and exhibit chondritic trace element contents and (Gd/Yb)_N ratios. In contrast, the Al-depleted komatiites show significantly lower Al₂O₃/TiO₂ ratios of 8–12, highly variable CaO/Al₂O₃ (0.19–2.81) ratios combined with (Gd/Yb)_N ratios varying from 1.08 to 1.56. A Sm–Nd whole rock isochron for komatiites of the Komati Formation gives an age of 3657±170 Ma. ¹⁴⁷Sm/¹⁴⁴Nd ratios (0.1704 and 0.1964) are all lower than the chondritic value of 0.1967. The komatiite _i,Nd(3.45) values cluster at +1.9±0.7.

Trace element distribution indicates that most of the primary geochemical and isotopic features of the komatiites were preserved in line with the conservation of the primary chemical composition of clinopyroxene. High field strength element and rare earth element abundances indicate that crustal contamination and post-crystallisation processes did not disturb the primary features of komatiites.

The Sm/Nd and Nb/U ratios of komatiites indicate that the Barberton greenstone belt mantle source has undergone melt extraction prior to komatiite formation. Variations of Al₂O₃/TiO₂, (Gd/Yb)_N, Zr/Sm and Sm/Nd ratios of komatiites indicate that a batch melting of slightly depleted mantle source during with garnet and/or clinopyroxene remained in the residue can produce the geochemical isotopic feature of the Barberton greenstone belt komatiites. Typical geochemical fingerprints of subduction-related processes (LILE enrichment, HFSE depletion compared to REE), as known from modern subduction zones, are not observed. Komatiites exhibit Ti/Zr, La/Nb, Nb/U, Sr/Nd and Ba/La ratios comparable to those of oceanic island basalt and mid-ocean ridge basalt. (La/Nb)_PMN, (Sm/Yb)_PMN, positive δNb values and flat or slightly enriched REE patterns suggest that BGB komatiites are part of an oceanic plateau rather than an oceanic island such as Iceland. Therefore, an oceanic plateau or mid-ocean ridge, in connection with an oceanic plateau, such as Ontong Java plateau or Caribbean–Colombian oceanic plateau, is a suitable tectonic setting for the formation of the BGB komatiites.     

Origin of Paleoproterozoic Komatiites at Jeesiorova, Kittila Greenstone Complex, Finnish Lapland

Komatiites from the 2 Ga Jeesiörova area in Finnish Laplandhave subchondritic Al₂O₃/TiO₂ ratios like those in Al-depletedkomatiites from Barberton, South Africa. They are distinct inthat their Al abundances are higher than those of the Al-depletedrocks and similar to levels in Al-undepleted komatiites. Moderatelyincompatible elements such as Ti, Zr, Eu, and Gd are enriched.Neither majorite fractionation nor hydrous melting in a supra-subductionzone setting could have produced these komatiites. Their highconcentrations of moderately incompatible elements may haveresulted from contamination of their parental melt through interactionwith metasomatic assemblages in the lithospheric mantle or enrichmentof their mantle source in basaltic melt components. Re–Osisotope data for chromite from the Jeesiörova rocks yieldan average initial ¹⁸⁷Os/¹⁸⁸Os of 0·1131 ± 0·0006(2), _Os(I) = 0·1 ± 0·5. These data, coupledwith an initial _Nd of +4, indicate that melt parental to thekomatiites interacted minimally with ancient lithospheric mantle.If their mantle source was enriched in a basaltic component,the combined Os–Nd isotopic data limit the enrichmentprocess to within 200 Myr prior to the formation of the komatiites.Their Os–Nd isotopic composition is consistent with derivationfrom the contemporaneous convecting upper mantle. KEY WORDS: Finnish Lapland; Jeesiörova; komatiites; mantle geochemistry; petrogenesis; redox state; Re/Os isotopes; Ti enrichment     

Platinum-group element constraints on source composition and magma evolution of the Kerguelen Plateau using basalts from ODP Leg 183

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ∼0.1 (Ir, Ru) to ∼5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (∼30%) and fractional crystallization (∼45%).First order approximations of the fractionation required to produce the KP basalts from an ∼30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available K_d values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.     

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.