Major,trace and platinum group element (PGE) geochemistry of Archean Iron Ore Group and Proterozoic Malangtoli metavolcanic rocks of Singhbhum Craton,Eastern India: Inferences on mantle melting and sulphur saturation history

The geological and metallogenic history of the Singhbhum Craton of eastern India is marked by several episodes of volcanism, plutonism, sedimentation and mineralization spanning from Paleoarchean to Mesoproterozoic in a dynamic tectonic milieu. Distinct signatures of this Archean-Proterozoic geodynamic process are preserved in discrete crustal provinces that constitute the Singhbhum Craton. Here we report new major, trace and PGE geochemical data from the ~ 3.4 Ga Iron Ore Group (IOG) volcanic rocks of the Jamda-Koira basin, a part of the BIF-bearing volcano-sedimentary sequences of the Noamundi-Jamda-Koira iron ore basin in the western part of Singhbhum Granite (SBG), and ~ 2.25 Ga metavolcanic rocks of Malangtoli. The IOG and Malangtoli volcanic rocks are porphyritic basalts and despite belonging to different ages, they exhibit similar mineralogical composition marked by clinopyroxene, plagioclase (present as both phenocryst and groundmass), opaques and volcanic glass (restricted to groundmass). The igneous mineralogy of these rocks has been overprinted by greenschist to lower amphibolite grade of metamorphism. The Malangtoli samples show low and high MgO compositional varieties. Immobile trace element compositions classify the IOG samples as andesite having a calc-alkaline composition, whereas the Malangtoli rocks correspond to basalt and andesite displaying a tholeiitic to calc-alkaline trend. The IOG basalts show low to moderate PGE contents marked by 26.23–68.35 ppb of ΣPGE, whereas the Malangtoli basalts display a moderate to high concentration of PGE (ΣPGE = 43.01–190.43 ppb). The studied samples have relatively enriched ΣPPGE ranging from 24.1–63.3 ppb (IOG) and 34–227.3 ppb (Malangtoli) against 2.2–4.1 ppb and 1.9–8.9 ppb ΣIPGE contents respectively. PPGE/IPGE ratios for IOG and Malangtoli samples range from 7.7–17.6 and 4.8–59.9. HFSE, REE and PGE compositions suggest a low degree (< 1 to 1%) of partial melting in the garnet lherzolite domain for the generation of IOG volcanic rocks. The parental magma of the Malangtoli basalts were generated by lower to higher degrees (3–< 10%) of mantle melting at depths corresponding to spinel to garnet lherzolite regime. Trace element (Zr/Nb, Th/Ta, Th/Nb, Ni/Cu) and PGE (Pd/Ir, Pd/Pt, Cu/Pd, Ni/Pd, Cu/Ir) ratios corroborate a sulphide saturated and PGE depleted character of IOG volcanic rocks that underwent crustal assimilation. In contrast, the high MgO Malangtoli basalts exhibit sulphide undersaturated, PGE undepleted nature devoid of crustal contamination whereas the low MgO Malangtoli basalts are sulphide saturated, PGE depleted and crustally contaminated. The IOG volcanic rocks correspond to intraoceanic arc with polygenetic crustal signatures, and show affinity towards arc-generated calc-alkaline basalts. The low- and high MgO basalts of Malangtoli are affiliated to transitional arc to rift-controlled back arc tectonic setting in a basinal environment that developed proximal to an active convergent margin.     

First finding of merenskyite (Pd,Pt)Te2 in porphyry Cu-Mo ores in Russia

Contents of Pt and Pd were determined in weakly mineralized rocks, ores, and flotation concentrates of the Aksug porphyry Cu-Mo deposit, northeastern Tuva. In all studied samples they are above the detection limits: Pt = 17–96 ppb and Pd = 9–924 ppb. These elements are unevenly distributed throughout the rocks and ores, with Pd/Pt varying from 0.5 to 37. Study of Pd-rich ores (up to 924 ppb, Pd/Pt = 37) on a JEOL JSM 5600 scanning electron microscope revealed finest (2–5 μm) merenskyite inclusions (25.20% Pd, 1.21% Pt, 72.31% Te) in chalcopyrite. The calculated crystallochemical formula of merenskyite from ores of the Aksug deposit is (Pd_0.862Pt_0.023Cu_0.026Fe_0.025)Te_2.064. The merenskyite is associated with electrum (79.92% Au, 18.96% Ag), monazite, cobaltite, tennantite, and Sr-containing barite (4.6–18.0% Sr). Palladium mineralization occurs in massive chalcopyrite veinlets in zones of intensely propylitized rocks. The Devonian Aksug ore-bearing porphyry complex developed in the field of Early-Middle Cambrian intrusions of gabbro-diorite-plagiogranites associated with basalt-andesite effusions of island-arc complex. This might have led to high PGE contents in the Aksug rocks. The deposit formation proceeded with the participation of ore-bearing Cl-enriched fluids favoring the concentration and transport of PGE in porphyry copper systems.     

Geochemistry of peridotite and granite xenoliths during the early stage of weathering in the Nyos volcanic region (NW Cameroon): Implications for PGE exploration

Peridotite and granite xenoliths, in the early stage of weathering, occur in the Nyos volcanic region (NW Cameroon). Geochemical data shows that peridotites are marked by high concentrations of MgO (42.30 wt.%, with SiO₂/MgO ∼ 1), chromium (2100 ppm), nickel (2100 ppm) and cobalt (104 ppm), as well as by low lanthanide contents (ΣREE: 7.41 ppm). Granites display SiO₂ contents (70–73 wt.%), and are mostly peraluminous (1.40 > A/CNK < 1.6). They are also characterized by low contents in chromium (<24 ppm), nickel (ranging from 6 to 15 ppm) and cobalt (ranging from 3 to 6 ppm). Granites possess high lanthanide contents (ΣREE varying between 248.00 and 463.00 ppm), particularly in light lanthanides (LREE/HREE ratios ranging from 21 to 32). The chondrite-normalized patterns of the studied xenoliths are characterized by: (i) LREE enrichments in both rock types; (ii) negative Eu anomalies ([Eu/Eu*] ranging from 0.45 to 0.64) and weak positive Ce anomalies ([Ce/Ce*] ranging from 1.06 to 1.46) in granites. The weathering process provokes a remobilization of several trace elements notably light lanthanides.The geochemical survey of Platinum-Group Elements (PGE) done in these rocks in the early stage of weathering shows that PGE contents are less than 7 ppb in the peridotites. The highly concentrated elements are ruthenium (6.26 ppb) and platinum (5.53 ppb). The total PGE content is 14.57 ppb. These concentrations normalized with respect to chondrites display a flat spectrum from iridium to platinum. PGE contents in the granites are below detection limit except for two samples (LNY01 and LNY02) whose platinum content is close to 0.23 ppb.     

Dispersion Pattern of PGE and Ag in Chromiferous Ultramafic Suite of Rocks in Sukinda Valley,India

Potential chromite ore deposits of India are situated in Sukinda, Odisha, which may also be considered as a potential resource for platinum group elements (PGEs). This paper reports on PGE geochemistry in twenty six samples covering chromite ores, chromitites and associated ultramafic rocks of the Sukinda ultramafic complex. Platinum group element contents range from 213 to 487 ppb in the chromite ore body, from 63 to 538 ppb in rocks that have chromite dendrites or dissemination and from 38 to 389 ppb in associated olivine–peridotite, serpentinite, pyroxenite and brecciated rocks. The PGEs are divided into two sub‐groups: IPGE (Ir, Os, and Ru) and PPGE (Pd, Pt, and Rh) based on their chemical behaviour. The IPGE and PPGE in these three litho‐members show a contrasting relationship e.g. average IPGE content decreases from chromite to chromitite and associated rocks while PPGE increases in the same order. Appreciable Ag in chromitite (270–842 ppb) is recorded. Positive correlation between IPGE with Cr₂O₃ and with Al₂O₃ is observed while these are negatively correlated with MgO. Covariant relationships between Au and Mg in rocks devoid of chromite and between Ag and Fe in chromitite sample are observed. Chromite in all seams and some chromitite samples exhibit an IPGE‐enriched chondrite normalized pattern while PPGE are highly fractionated and show a steep negative slope, thereby indicating that PGE in the parental melt fractionates and IPGE‐compatible elements prefer to settle with chromite. The rocks devoid of chromite and rocks containing accessory chromite exhibit a nearly flat pattern in chondrite‐normalized PGE plots and this suggests a limited fractionation of PGE in these rocks. Variation in the distribution pattern of PGE and Ag in three typical litho‐members of the Sukinda Valley may be related to multiple intrusion of ultramafic magma, containing variable volume percentage of chromite.     

中亚造山带中斑岩铜钼矿的Re，Pt，Pd和Au含量

Precious metal(Pt,Pd and Au)and Re contents in rocks,ores and flotation concentrates of Siberian(Russia)andMongolian porphyry Cu-Mo and Mo-Cu deposits were studied.The following deposits are discussed:Early Devonian porphyry Mo-CuSora deposit(Kuznetsk Alatau Mountains,Russia)and porphyry Cu-Mo Aksug deposit,(northeastern Tuva,Russia);Triassicporphyry Cu-Mo Erdenetiin Ovoo deposit(northern Mongolia).The samples analyzed include unaltered host rocks of plutons,porphyryrocks of ore-bearing series,different types of altered rocks,mineral separate analyses of molybdenite,chalcopyrite and magnetite,aswell as flotation concentrates.Pt,Pd,Au and Re contents were determined using ICP/MS,AAS and inversion voltammetric analysis.PGE abundances in rocks and poorly mineralized samples span a large range from below detection limit to 65 ppb Pt and 74 ppbPd.Re concentrations in whole rock samples range from below detection limit to 89 ppb.Molybdenite has been shown to be the majorhost phase for Re.The results presented show that Aksug deposit reveals elevated PGE and Au contents in ore minerals and flotationconcentrates.High Pd contents in ores of the Aksug deposit are in accordance with the presence of palladium mineralization in the formof palladium telluride merenskyite(Pd,Pt)Te_2.The variety of precious metals and Re contents in the studied deposits could be caused by a complex interplay of several factors,including importance of primary metal concentrations derived from the source,transport of metals to the deposition area,physicochemical properties of the fluid(fo_2,pH,fs,T,P),and depositional conditions.Higher Re contents in molybdenite andchalcopyrite separates are typical for copper-rich Aksug and Erdenetiin Ovoo deposits.Rhenium concentration in sulfides frommolybdenum-rich Sora deposit is significantly lower.Highly oxidized,Cl-rich fluid style at Aksug and Erdenetiin Ovoo was favorable forhigh rhenium solubility and transport to depositional area.The occurrence of significant precious metals contents at Aksug were likelydue to:1)PGE and Au enriched source,2)favorable fluid style(high fo_2,high Cl-activity),promoting high solubility andtransportation of precious metals in ore-forming fluid as chloride complexes;3)moderately reducing depositional conditions from PGE-bearing solutions containing As and Te,facilitating PGM deposition.As for the porphyry systems at the Sora and Erdenetiin Ovoodeposits,they were probably devoid of precursors favorable for the enrichment in PGE and Au or the role of such precursors wasinsignificant.     

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.     

Chalcophile element constraints on magma differentiation of Quaternary volcanoes in Tengchong,SW China

The Tengchong volcanic field comprises numerous Quaternary volcanoes in SW China. The volcanic rocks are grouped into Units 1–4 from the oldest to youngest. Units 1, 3 and 4 are composed of trachybasalt, basaltic trachyandesite and trachyandesite, respectively, and Unit 2 consists of hornblende-bearing dacite. This rock assemblage resembles those of arc volcanic sequences related to oceanic slab subduction. Rocks of Units 1 and 3 contain olivine phenocrysts with Fo contents ranging from 65 to 85 mole%, indicating early fractionation of olivine and chromite prior to the eruption of magma. All the rocks from Units 1, 3 and 4 have very low PGE concentrations, with <0.05 ppb Ru and Rh, <0.2 ppb Pt and Pd, and Ir that is commonly close to, or slightly higher than detection limits (0.001 ppb). The small variations of Pt/Pd ratios (0.4–2.2) are explained by fractionation of silicate and oxide minerals. The 5-fold variations in Cu/Pd ratios (200,000–1,000,000) for the lavas at Tengchong, which do not vary systematically with fractionation, likely reflect retention of variable amounts of residual sulfide in the mantle source. In addition, all the rocks from Units 1, 3 and 4 have primitive mantle-normalized chalcophile element patterns depleted in PGE relative to Cu. Together with very low Cu/Zr ratios (0.06–0.24), these rocks are considered to have undergone variable degrees of sulfide-saturated differentiation in shallow crustal staging magma chambers. Large amounts of olivine and chromite crystallization probably triggered sulfide saturation of magma at depth for Units 1 and 3, whereas crustal contamination was responsible for sulfide saturation during ascent of magma for Unit 4.     

Platinum-group element geochemistry of mafic rocks from the Dongchuan area,southwestern China

Mafic intrusions and dykes are well preserved in the Yinmin and Lanniping districts, located within the western margin of the Yangtze Block, SW China. Although these mafic rocks from the two areas formed during different periods, they share similar ranges of PGE concentration. Most of the Yinmin gabbroic dykes contain relatively high PGE concentrations (PGEs = 13.9–87.0 ppb) and low S contents (0.003 %–0.020 %), higher than the maximum PGE concentrations of mafic magmas melting from the mantle. Two exceptional Yinmin samples are characterized by relatively low PGE (PGEs = 0.31–0.37 ppb) and high S (0.114 %–0.257 %) contents. In contrast, most samples from the Lanniping gabbroic intrusion have low PGE concentrations (PGEs = 0.12–1.02 ppb) and high S contents (0.130 %–0.360 %), except that the three samples exhibit relatively high PGE (PGEs = 16.3–34.8 ppb) and low S concentrations (0.014 %–0.070 %). All the Yinmin and Lanniping samples are characterized by the enrichment of PPGE relative to IPGE in the primitive-mantle normalized diagrams, and the high-PGE samples exhibit obvious Ru anomalies. This study suggests that during the ascent of the parental magma, removal of Os–Ir–Ru alloys and/or chromite/spinel leads to high Pd/Ir ratios and Ru anomalies for the Yinmin high-PGE samples and relatively lower Pd/Ir ratios and Ru anomalies for the Lanniping low-PGE samples. We propose that the magmas parental to the Yinmin gabbroic dykes are initially S-unsaturated, and subsequently, minor evolved magma reached sulfur saturation and led to sulfide segregation. Although the Lanniping parental magmas are originally not saturated in S, the high Cu/Pd ratios (3.8 × 10⁴ to 3.2 × 10⁶) for most of the Lanniping samples indicate the S-saturated state and sulfide segregation. A calculation shows that the PGE-poor magmas might have experienced 0.01 %–0.1 % sulfide segregation in the magma chamber. Therefore, our study provides a possible opportunity to discover PGE-enriched sulfide mineralization somewhere near or within the Lanniping mafic intrusion.     

Platinum‐Group Elements Geochemistry and Chromian Spinel Composition in Podiform Chromitites and Associated Peridotites from the Cheshmeh‐Bid Deposit,Neyriz, Southern Iran: Implications for Geotectonic Setting

Dunite and serpentinized harzburgite in the Cheshmeh-Bid area, northwest of the Neyriz ophiolite in Iran, host podiform chromitite that occur as schlieren-type, tabular and aligned massive lenses of various sizes. The most important chromitite ore textures in the Cheshmeh-Bid deposit are massive, nodular and disseminated. Massive chromitite, dunite, and harzburgite host rocks were analyzed for trace and platinum-group elements geochemistry. Chromian spinel in chromitite is characterized by high Cr~#(0.72-0.78), high Mg~#(0.62–0.68) and low TiO_2(0.12 wt%-0.2 wt%) content. These data are similar to those of chromitites deposited from high degrees of mantle partial melting. The Cr~# of chromian spinel ranges from 0.73 to 0.8 in dunite, similar to the high-Cr chromitite, whereas it ranges from 0.56 to 0.65 in harzburgite. The calculated melt composition of the high-Cr chromitites of the Cheshmeh-Bid is 11.53 wt%–12.94 wt% Al_2O_3, 0.21 wt%–0.33 wt% TiO_2 with FeO/MgO ratios of 0.69-0.97, which are interpreted as more refractory melts akin to boninitic compositions. The total PGE content of the Cheshmeh-Bid chromitite, dunite and harzburgite are very low(average of 220.4, 34.5 and 47.3 ppb, respectively). The Pd/Ir ratio, which is an indicator of PGE fractionation, is very low(0.05–0.18) in the Cheshmeh-Bid chromitites and show that these rocks derived from a depleted mantle. The chromitites are characterized by high-Cr~#, low Pd + Pt(4–14 ppb) and high IPGE/PPGE ratios(8.2–22.25), resulting in a general negatively patterns, suggesting a high-degree of partial melting is responsible for the formation of the Cheshmeh-Bid chromitites. Therefore parent magma probably experiences a very low fractionation and was derived by an increasing partial melting. These geochemical characteristics show that the Cheshmeh-Bid chromitites have been probably derived from a boninitic melts in a supra-subduction setting that reacted with depleted peridotites. The high-Cr chromitite has relatively uniform mantle-normalized PGE patterns, with a steep slope, positive Ru and negative Pt, Pd anomalies, and enrichment of PGE relative to the chondrite. The dunite(total PGE = 47.25 ppb) and harzburgite(total PGE =3 4.5 ppb) are highly depleted in PGE and show slightly positive slopes PGE spidergrams, accompanied by a small positive Ru, Pt and Pd anomalies and their Pdn/Irn ratio ranges between 1.55–1.7 and 1.36-1.94, respectively. Trace element contents of the Cheshmeh-Bid chromitites, such as Ga, V, Zn, Co, Ni, and Mn, are low and vary between 13–26, 466–842, 22-84, 115–179, 826–-1210, and 697–1136 ppm, respectively. These contents are compatible with other boninitic chromitites worldwide. The chromian spinel and bulk PGE geochemistry for the Cheshmeh-Bid chromitites suggest that high-Cr chromitites were generated from Cr-rich and, Ti-and Al-poor boninitic melts, most probably in a fore-arc tectonic setting related with a supra-subduction zone, similarly to other ophiolites in the outer Zagros ophiolitic belt.     

Geochemical Constraints on the Origin of the Ni–Cu Sulfide Ores in the Tejadillas Prospect (Cortegana Igneous Complex,SW Spain)

After the discovery of the Aguablanca ore deposit (the unique Ni–Cu mine operating in SW Europe), a number of mafic‐ultramafic intrusions bearing Ni–Cu magmatic sulfides have been found in the Ossa–Morena Zone of the Iberian Massif (SW Iberian Peninsula). The Tejadillas prospect is one of these intrusions, situated close to the border between the Ossa–Morena Zone and the South Portuguese Zone of the Iberian Massif. This prospect contains an average grade of 0.16 wt % Ni and 0.08 wt % Cu with peaks of 1.2 wt % Ni and 0.2 wt % Cu. It forms part of the Cortegana Igneous Complex, a group of small mafic‐ultramafic igneous bodies located 65 km west of the Aguablanca deposit. In spite of good initial results, exploration work has revealed that sulfide mineralization is much less abundant than in Aguablanca. A comparative study using whole‐rock geochemical data between Aguablanca and Tejadillas shows that the Tejadillas igneous rocks present a lower degree of crustal contamination than those of Aguablanca. The low crustal contamination of the Tejadillas magmas inhibited the assimilation of significant amounts of crustal sulfur to the silicate magmas, resulting in the sparse formation of sulfides. In addition, Tejadillas sulfides are strongly depleted in PGE, with total PGE contents ranging from 14 to 81 ppb, the sum of Pd and Pt, since Os, Ir, Ru and Rh are usually below or close to the detection limit (2 ppb). High Cu/Pd ratios (9700–146,000) and depleted mantle‐normalized PGE patterns suggest that the Tejadillas sulfides formed from PGE‐depleted silicate magmas. Modeling has led us to establish that these sulfides segregated under R‐factors between 1000 and 10,000 from a silicate melt that previously experienced 0.015% of sulfide extraction. All these results highlight the importance of contamination processes with S‐rich crustal rocks and multiple episodes of sulfide segregations in the genesis of high‐tenor Ni–Cu–PGE ore deposits in mafic‐ultramafic intrusions of the region.     

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。     

PGE mineralization and melt composition of chromitites in Proterozoic ophiolite complexes of Eastern Sayan,Southern Siberia

The Ospino-Kitoi and Kharanur ultrabasic massifs represent the northern and southern ophiolite branches respectively of the Upper Onot ophiolitic nappe and they are located in the southeastern part of the Eastern Sayan(SEPES ophiolites).Podiform chromitites with PGE mineralization occur as lensoid pods within dunites and rarely in harzburgites or serpentinized peridotites.The chromitites are classified into type I and type Ⅱ based on their Cr~#.Type I(Cr~# = 59-85) occurs in both northern and southern branches,whereas type Ⅱ(Cr~# = 76-90) occurs only in the northern branch.PGE contents range from ∑PGE 88-1189 ppb,Pt/Ir0.04-0.42 to ∑PGE 250-1700 ppb,Pt/Ir 0.03-0.25 for type I chromitites of the northern and southern branches respectively.The type Ⅱ chromitites of the northern branch have ∑PGE contents higher than that of type Ⅰ(468-8617 ppb,Pt/Ir 0.1-0.33).Parental melt compositions,in equilibrium with podiform chromitites,are in the range of boninitic melts and vary in Al_2O_3,TiO_2 and FeO/MgO contents from those of type I and type Ⅱ chromitites.Calculated melt compositions for type Ⅰ chromitites are(Al_2O_3)_(melt) = 10.6—13.5 wt.%,(TiO_2)_(melt) = 0.01-0.44 wt.%,(Fe/Mg)_(melt) = 0.42-1.81;those for type Ⅱ chromitites are:(Al_2O_3)_(melt) = 7.8-10.5 wt.%,(TiO_2)_(melt) = 0.01-0.25 wt.%,(Fe/Mg)_(melt) = 0.5-2.4.Chromitites are further divided into Os-Ir-Ru(Ⅰ) and Pt-Pd(Ⅱ) based on their PGE patterns.The type Ⅰ chromitites show only the Os-Ir-Ru pattern whereas type Ⅱ shows both Os-Ir-Ru and Pt-Pd patterns.PGE mineralization in type Ⅰ chromitites is represented by the Os-Ir-Ru system,whereas in type Ⅱ it is represented by the Os-Ir-Ru-Rh-Pt system.These results indicate that chromitites and PGE mineralization in the northern branch formed in a suprasubduction setting from a fluid-rich boninitic melt during active subduction.However,the chromitites and PGE mineralization of the southern branch could have formed in a spreading zone environment.Mantle peridotites have been exposed in the area with remnants of mantle-derived reduced fluids,as indicated by the occurrence of widespread highly carbonaceous graphitized ultrabasic rocks and serpentinites with up to 9.75 wt.%.Fluid inclusions in highly carbonaceous graphitized ultrabasic rocks contain CO,CO_2,CH4,N_2 and the δ~(13)C isotopic composition(-7.4 to-14.5‰) broadly corresponds to mantle carbon.     

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.     

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 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.     

A reconnaissance study of platinum group elements (PGE) contents from sulfide mineralization in pyroxenites in Faryab ophiolite of Iran

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.     

Unconventional PGE occurrences and PGE mineralization in the Great Dyke: metallogenic and economic aspects

Platinum group elements (PGE) are strategic materials because 96–99% of the world production is derived from just five mining districts and because they cannot be replaced as catalysts in many chemical processes. In order to lessen the strategic character of PGE, both conventional deposits and unconventional PGE mineralizations were investigated in an attempt to locate viable deposits which would diversify the supplier base. In the Great Dyke, conventional PGE mineralization occurs in the form of pristine sulfide ores mined underground and oxidic surface ores. New observations such as bimodal distributions of the PGE in the Main Sulfide Zone (MSZ), elevated Pt/Pd ratios in the oxidized MSZ compared to the sulfidic part and distinct differences between the platinum group mineral (PGM) assemblages of the MSZ and stream sediments of adjacent rivers emphasize the fact that even though the Great Dyke seems to be the second or third largest PGE occurrence in the world, the complicated PGE distributions and supergene redistributions should be kept in mind during planning and mine operation. Investigations of unconventional PGE occurrences in ophiolites, Alaskan-type intrusions, porphyry copper deposits and in the Kupferschiefer show that economically exploitable PGE concentrations can be expected in a broader variety of host rocks than considered favourable in the past. In the Albanian Mirdita ophiolite average contents of 860 ppb Pt and 60 ppb Pd were detected. Flotation concentrates of porphyry copper deposits, for example from Mamut, Malaysia, Santo Tomas, Philippines, Elacite, Bulgaria, and Ok Tedi, Papua New Guinea, contain between 827 and 1860 ppb Pd + Pt. In selected profiles of the Polish Kupferschiefer average contents of 255 ppb Pt, 94 ppb Pd, 2.4 ppm Au and 13.0 ppm Ag were analysed. The distribution of the PGE resources in the world and the annual production rates, however, underline the fact that the chances for a significant change in the supplier base are relatively low. The Bushveld Complex will remain the largest producer, followed by Noril'sk-Talnakh, Sudbury and Stillwater. If the operations in the Great Dyke reach their planned capacities, the Great Dyke will rank in third place among the PGE-producing deposits in the world. Received: 12 September 1998 / Accepted: 7 December 1999     

PGE fractionation in seafloor hydrothermal systems: examples from mafic- and ultramafic-hosted hydrothermal fields at the slow-spreading Mid-Atlantic Ridge

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.     

PGE mineralization in Archean volcanic systems: geochemical evidence from thick, differentiated mafic-ultramafic flows, Abitibi greenstone belt, Ontario, and implications for exploration

PGE-rich disseminated zones with discrete platinum-group minerals (Pd, Pt and Rh mineral phases) have been discovered in three thick (80–130 m), differentiated (peridotite-gabbro) mafic-ultramafic flows of the Archean Abitibi greenstone belt, Ontario. Three mineralization zones (whole-rock ∑PGE + Au = up to 1000 ppb) occur along four stratigraphic cross sections through a 2 km strike-length of the Boston Creek Flow ferropicritic basalt. Their occurrence most strikingly correlates with lenticular-podiform concentrations of disseminated chalcopyrite (1 %) and clinopyroxene + interstitial magnetite-ilmenite intergrowths (15–20% oxide), high concentrations of related metals (3000 ppm Cu, 3000 ppm S, 1200 ppb Ag, and 1000 ppm V), strong PGE depletion in adjacent rocks and along strike, and lithological and textural complexity in the margins of the central gabbro-diorite layer. The mineralization zone (whole-rock Ir + Pt + Pd + Au = 110 ppb) within Theo's Flow tholeiitic basalt is somewhat similar in occurrence, style, and composition to those within the Boston Creek Flow. In contrast, the mineralization zone (whole-rock Ir + Pt + Pd + Au = 340 ppb) in Fred's Flow komatiitic basalt most strikingly correlates with vesicle-filling intergrowths of pyrrhotite + pentlandite ± chalcopyrite (2 modal %) and high whole-rock concentrations of Ni (2500 ppm), Cu (700 ppm), and S (1.1%) in the upper chilled margin of the flow.Although apparently uneconomic, these flow-hosted PGE mineralization zones are of interest in exploration, because they are more similar in stratigraphie setting, style, and composition to PGE-rich disseminated Fe-Cu sulfide mineralization zones within thick differentiated intrusions than to mineralization zones in other Archean volcanic rocks. The characteristics of the mineralization zones and their host rocks, especially high degrees of PGE enrichment, vertical and horizontal patterns of PGE depletion, and accumulation of clinopyroxene + magnetite-ilmenite intergrowths, indicate a critical genetic role for variations in the regime of melt flowage. The mineralization zones in the Boston Creek and Theo's Flows are interpreted to have formed by simultaneous in situ formation of PGE-rich Fe-Cu sulfide and Fe-Ti oxide from flowing silicate liquid in the margins of internal lava channels. The mineralization zone in Fred's Flow is interpreted to have formed by ponding and coalescence of PGE-enriched sulfurous vapor bubbles in the upper chilled margin during olivine accumulation on the base of a dynamic lava channel. The relative abundance of PGE mineralization zones and high degree of PGE enrichment in the Boston Creek Flow suggest that the most favorable exploration targets are rocks crystallized from late-stage, highly fractionated derivative liquids in large differentiated terropicritic units.     

The source of platinum group elements in basalts of the ophiolite complex of the Kamchatsky Mys Peninsula (Eastern Kamchatka)

Contents of platinum group elements (PGE—Os, Ir, Ru, Rh, Pt, and Pd) and rhenium in basalts of different geochemical types from the ophiolite complex of the Kamchatsky Mys Peninsula have been determined by the isotope dilution-mass spectrometry method. The total contents of PGE in different basalts are commensurate (1.4-3.6 ppb), but the element ratios vary considerably. A specific feature of the rocks is the low degree of PGE fractionation (Pd/Ir = 0.9-6.6, Pt/Pd = 1.0-7.3), which makes them similar to the Hawaiian tholeiitic basalts and picrites. The most fractionated PGE pattern is observed for alkali basalt (Pd/Ir = 6.6), and the least fractionated one, for E-MORB (Pd/Ir = 1.7). The similarity of the PGE patterns of basalts of different geochemical types suggests their similar mantle sources. We propose a model explaining the geochemical features of the basalts of the Kamchatsky Mys ophiolite complex by an impurity of the Earth’s core material in the plume source. The Ir/Pd-Ru/Pd and Pd/10-Ir-Ru discrimination diagrams can be used to identify enriched (plume) basalts based on their PGE content.