PGE distribution in massive sulfides from the P<Emphasis Type="SmallCaps">ACMANUS</Emphasis> hydrothermal field,eastern Manus basin,Papua New Guinea: implications for PGE enrichment in some ancient volcanogenic massive sulfide deposits

The distribution of platinum group elements (PGE) in Cu- and Zn-rich samples from the Roman Ruins and Satanic Mills vent sites in the PACMANUS hydrothermal field (Papua New Guinea) was studied and compared to that from selected ancient volcanogenic massive sulfide (VMS) deposits. Samples from the Satanic Mills site are enriched in Pd and Rh when compared to samples from Roman Ruins and reach highest values in active and inactive Cu-rich black smoker chimneys and chalcopyrite-cemented dacite breccias (up to 356 ppb Pd and up to 145 ppb Rh). A significant positive correlation was established between Cu and Pd and Rh in samples from both vent sites. Comparisons of chondrite normalized patterns and values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides and probable source rocks (felsic volcanic rocks/MORB) along with the evidence for a magmatic component in the PACMANUS hydrothermal system indicate that leaching of back-arc volcanic rocks together with addition of magmatic volatiles to the convecting hydrothermal system was the most important factor for PGE enrichment at PACMANUS and likely at some PGE-enriched ancient VMS deposits.An erratum to this article can be found at Editorial handling: B. Lehmann     

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.     

Siderophile and chalcophile elemental constraints on the origin of the Jinchuan Ni-Cu-(PGE) sulfide deposit, NW China

The Jinchuan deposit, NW China, is one of the world’s most important Ni-Cu-(PGE) sulfide deposits related to a magma conduit system and is hosted in an ultramafic intrusion. The intrusion is composed of lherzolite and dunite with the two largest sulfide ore bodies (named as ore body 1 and 2) in its middle portion. The sulfide ores may be disseminated, net-textured, or massive. The disseminated and net-textured sulfide ores are characterized by variable but generally low PGE concentrations: 10-3200 ppb Pt, 240-9800 ppb Pd, 17-800 ppb Ir, 25-1500 ppb Ru, and 15-400 ppb Rh in 100% sulfides. The massive sulfide ores are extremely low in Pt (<30 ppb) on a 100% sulfides and have very high Cu/Pd ratios, ranging from 10⁴ to 4.5 × 10⁵. The low PGE contents suggest that the sulfide ores formed from the silicate magmas that had already experienced prior-sulfide separation.Our calculations indicate that if the first stage basaltic magmas had contained 6.3 ppb Pt, 6.2 ppb Pd, and 0.1 ppb Ir, 0.008% sulfide removal would result in PGE-depletion in the residual magma with 0.57 ppb Pt, 0.25 ppb Pd, and 0.009 ppb Ir. The Jinchuan sulfides were formed by a second stage of sulfide segregation from a PGE-depleted magma under silicate/sulfide liquid ratios (R-factor) ranging from 10³ to 10⁴ in a deep-seated staging chamber. The massive sulfide ores and some of the net-textured sulfide ores exhibit strong negative Pt-anomalies that cannot be explained by sulfide segregation under variable R-factors. Instead, the sulfide melts that formed the massive ores were segregated from magmas experienced prior fractionation of Pt-Fe alloy. Alternatively, the Pt may have been selectively leached by hydrothermal fluids during remobilization of the sulfide melts that produced the massive sulfides, which occur in cross-cutting veins. We propose that the Jinchuan intrusion and ore bodies were formed by injections of sulfide-free and sulfide-bearing olivine mushes from a deep-seated staging chamber.     

Genesis of the Jinchuan PGE deposit, China: evidence from fluid inclusions, mineralogy and geochemistry of precious elements

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.     

PGE distribution in massive sulfide deposits of the Iberian Pyrite Belt

We present the first platinum group elements (PGE) data on seven massive sulfide deposits in the Iberian Pyrite Belt (IPB), one of the world largest massive sulfide provinces. Some of these deposits can contain significant PGE values. The highest PGE values were identified in the Cu-rich stockwork ores of the Aguas Teñidas Este (Σ PGE 350 ppb) and the Neves Corvo (Σ PGE 203 ppb) deposits. Chondrite normalized PGE patterns and Pd/Pt and Pd/Ir ratios in the IPB massive, and stockwork ores are consistent with the leaching of the PGE from the underlying rock sequence.     

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.     

Partitioning of platinum-group elements and Au in the Fe−Ni−Cu−S system: experiments on the fractional crystallization of sulfide melt

Partitioning of platinum-group elements (PGE) between sulfide liquid and monosulfide solid solution (mss) has been investigated by crystallizingmss from Fe–Ni–Cu sulfide liquid at 1,000–1,040° C, using bulk compositions and PGE contents typical of magmatic sulfides associated with mafic and ultramafic systems. Products were analyzedin situ for PGE and Au using SIMS. Sulfide liquid compositions were more Ni- and Cu-rich than coexistingmss. Liquid/mss partition coefficients are: Os-0.23±0.04, Ir-0.28±0.11, Ru-0.24±0.05, Rh-0.33±0.06, Pt-4.8±0.7, Pd-4.8±1.9, Au-11.4. Partitioning of PGE is independent of PGE concentration and Ni content in the composition range investigated. Additionally, Henry's law appears to be obeyed up to minor-element contents in the sulfide liquid andmss. Osmium, Ir, Ru, and Rh are compatible elements in the anhydrous Fe–Ni–Cu–S system, whereas Pt, Pd and Au are incompatible elements. These affinities correspond to the partitions of PGE between massive and Cu-rich magmatic sulfides. However, the detailed precious-metal compositions of the Cu-rich sulfides of mafic rock systems, disseminated ores of komatiites and Cu-rich assemblage of droplet ore from the Noril'sk-Talnakh deposits are not consistent with those expected for pristine fractionated sulfide liquids.     

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     

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.     

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

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

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

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

喀拉通克铜镍矿床铂族元素地球化学特征及其成矿作用意义

喀拉通克铜镍矿床位于准噶尔板块北缘,矿区主要矿体赋存于Y1-Y3号岩体中。矿石构造类型为致密块状和浸染状两大类,其中前者与后者呈贯入接触,不同浸染状类型之间为过渡关系。岩石和矿石的PGE总量偏低,且以PPGE为主,IPGE含量较低。整体上岩石中的PGE含量显示随基性程度降低而变小。矿石中的PGE含量随硫化物含量增加增大,显示PGE主要分布于硫化物熔离形成的物相中。100%硫化物计算后,矿石PGE含量平均仅为573×10^-9。各岩体中浸染状矿石PGE组成并无明显差异;岩石和矿石具有相似的PGE分配模式,均属于Pt-Pd配分型。岩石Ni/Cu-Pd/Ir关系以及岩石地球化学资料显示,形成喀拉通克岩体的初始岩浆为MgO含量较高的玄武质岩浆,属于PGE不亏损的岩浆。基于PGE不亏损的大陆拉斑玄武岩初始岩浆推算,喀拉通克矿床母岩浆明显亏损PGE,而深部硫化物熔离可能是导致母岩浆PGE亏损的主要原因。岩石和矿石Pd/Pt比值总体特征,岩石Cr与Ni、Ir、Ru和Rh相关性,以及硫同位素和岩石学资料分析表明,初始岩浆在地壳深部发生的橄榄石、铬铁矿等矿物的分离结晶作用,可能是促使硫过饱和与深部熔离的主要因素。IPGE与PPGE分异特征及其相关分析,结合矿床宏观地质特征,推断该矿床浸染状矿的成矿作用经历了初始岩浆（PGE不亏损）→橄榄石等矿物分离结晶→硫化物深部熔离→成矿母岩浆（PGE亏损）→上侵并结晶分异的成矿过程。块状矿则可能是这一过程中PGE亏损的成矿母岩浆相对滞后熔离形成的硫化物熔体贯入的结果。     

First report of platinum-group minerals from a hornblende gabbro dyke in the vicinity of the Southeast Extension Zone of the Voisey’s Bay Ni-Cu-Co deposit, Labrador

Summary This study reports the first documented occurrence of platinum group-minerals (PGM) in the vicinity of the Voisey’s Bay magmatic sulfide ore deposit. The PGM are present in a sulfide poor, hornblende gabbro dyke in the Southeast Extension Zone of the massive sulfide Ovoid deposit. The dyke has somewhat elevated concentrations of platinum-group elements (PGE) and gold (up to 1.95 g/t Pt, 1.41 g/t Pd, and 6.59 g/t Au), as well as Cu, Pb, Ag, Sn, Te, Bi and Sb. The PGM formed by magmatic processes and were little disturbed by subsequent infiltration of an externally-supplied hydrothermal fluid. To date, no similar PGM occurrences have been discovered in the Ovoid deposit itself. Whole rock REE patterns indicate that the dyke is geochemically related to the main conduit troctolites, which carry the bulk of the massive sulfide mineralization at Voisey’s Bay. The PGE mineralization is Pt- and Pd-rich, where the Pt and Pd occur predominantly as discrete PGM with minor Pd in solid solution in galena (average=1.8 ppm) and pentlandite (average=2 ppm). The discrete PGM are predominantly hosted by disseminated base-metal sulfides (bornite, chalcopyrite, and galena) (56 vol%) and are associated with other precious metal minerals (13 vol%) with only ∼3 vol% of the PGM hosted by silicate minerals. In whole rock samples, the PPGE (Pt, Pd, and Rh) correlate with abundances of chalcopyrite, bornite, galena, and other precious metal minerals (PMM), whereas the IPGE (Ir, Ru, and Rh) correlate with pyrrhotite and pentlandite. There are no correlations of the PGE with chlorine. Lead isotope compositions of galena associated with the PGE mineralization in the Southeast Extension Zone are broadly similar to those for galena in the Ovoid. The lead isotope compositions are much different from those in the Voisey’s Bay Syenite, which is a potential external hydrothermal fluid source. The observed Cu-rich, Pb-rich sulfide compositions and associated Pt-Pd-Au-Ag-Sn-Te-Bi-Sb assemblage in the dyke can be produced magmatically as late ISS differentiates (e.g., Prichard et al., 2004). Melting temperatures of the PGM are also consistent with a magmatic origin. Following crystallization of PGM from magmatic sulfide, an external REE-enriched hydrothermal fluid was introduced to the system, producing secondary amphibole and locally remobilizing the Pb and Sn from the sulfides hosting the PGM. Author’s address: M. A. E. Huminicki, Department of Earth Sciences, Memorial University of Newfoundland, St. John’s, NL, Canada A1B 3X5     

Geochemistry of the Kalatongke Ni–Cu–(PGE) sulfide deposit,NW China: implications for the formation of magmatic sulfide mineralization in a postcollisional environment

The Kalatongke (also spelt as Karatungk) Ni–Cu–(platinum-group element, PGE) sulfide deposit, containing 33 Mt sulfide ore with a grade of 0.8 wt.% Ni and 1.3 wt.% Cu, is located in the Eastern Junggar terrane, Northern Xinjiang, NW China. The largest sulfide ore body, which occupies more than 50 vol.% of the intrusion Y1, is dominantly comprised of disseminated sulfide with a massive sulfide inner zone. Economic disseminated sulfides also occur at the base of the intrusions Y2 and Y3. The main host rock types are norite in the lower part and diorite in the upper part of each intrusion. Enrichment in large ion lithophile elements and depletion in heavy rare earth elements relative to mid-ocean ridge basalt indicate that the mafic intrusions were produced from magmas derived from a metasomatized garnet lherzolite mantle. The average grades of the disseminated ores are 0.6 wt.% Ni and 1.1 wt.% Cu, whereas those of the massive ores are 2 wt.% Ni and 8 wt.% Cu. The PGE contents of the disseminated ores (14–69 ppb Pt and 78–162 ppb Pd) are lower than those of the massive ores (120–505 ppb Pt and 30–827 ppb Pd). However, on the basis of 100% sulfide, PGE contents of the massive sulfides are lower than those of the disseminated sulfides. Very high Cu/Pd ratios (>4.5 × 10⁴) indicate that the Kalatongke sulfides segregated from PGE-depleted magma produced by prior sulfide saturation and separation. A negative correlation between the Cu/Pd ratio and the Pd content in 100% sulfide indicates that the PGE content of the sulfide is controlled by both the PGE concentrations in the parental silicate magma and the ratio of the amount of silicate to sulfide magma. The negative correlations between Ir and Pd indicate that the massive sulfides experienced fractionation.     

The distribution of platinum group elements (PGE) and other chalcophile elements among sulfides from the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada, and the origin of palladium in pentlandite

Concentrations of platinum group elements (PGE), Ag, As, Au, Bi, Cd, Co, Mo, Pb, Re, Sb, Se, Sn, Te, and Zn, have been determined in base metal sulfide (BMS) minerals from the western branch (402 Trough orebodies) of the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada. The sulfide assemblage is dominated by pyrrhotite, with minor pentlandite, chalcopyrite, and pyrite, and they represent monosulfide solid solution (MSS) cumulates. The aim of this study was to establish the distribution of the PGE among the BMS and platinum group minerals (PGM) in order to understand better the petrogenesis of the deposit. Mass balance calculations show that the BMS host all of the Co and Se, a significant proportion (40–90%) of Os, Pd, Ru, Cd, Sn, and Zn, but very little (<35%) of the Ag, Au, Bi, Ir, Mo, Pb, Pt, Rh, Re, Sb, and Te. Osmium and Ru are concentrated in equal proportions in pyrrhotite, pentlandite, and pyrite. Cobalt and Pd (∼1 ppm) are concentrated in pentlandite. Silver, Cd, Sn, Zn, and in rare cases Au and Te, are concentrated in chalcopyrite. Selenium is present in equal proportions in all three BMS. Iridium, Rh, and Pt are present in euhedrally zoned PGE sulfarsenides, which comprise irarsite (IrAsS), hollingworthite (RhAsS), PGE-Ni-rich cobaltite (CoAsS), and subordinate sperrylite (PtAs₂), all of which are hosted predominantly in pyrrhotite and pentlandite. Silver, Au, Bi, Mo, Pb, Re, Sb, and Te are found predominantly in discrete accessory minerals such as electrum (Au–Ag alloy), hessite (Ag₂Te), michenerite (PdBiTe), and rhenium sulfides. The enrichment of Os, Ru, Ni, and Co in pyrrhotite, pentlandite, and pyrite and Ag, Au, Cd, Sn, Te, and Zn in chalcopyrite can be explained by fractional crystallization of MSS from a sulfide liquid followed by exsolution of the sulfides. The early crystallization of the PGE sulfarsenides from the sulfide melt depleted the MSS in Ir and Rh. The bulk of Pd in pentlandite cannot be explained by sulfide fractionation alone because Pd should have partitioned into the residual Cu-rich liquid and be in chalcopyrite or in PGM around chalcopyrite. The variation of Pd among different pentlandite textures provides evidence that Pd diffuses into pentlandite during its exsolution from MSS. The source of Pd was from the small quantity of Pd that partitioned originally into the MSS and a larger quantity of Pd in the nearby Cu-rich portion (intermediate solid solution and/or Pd-bearing PGM). The source of Pd became depleted during the diffusion process, thus later-forming pentlandite (rims of coarse-granular, veinlets, and exsolution flames) contains less Pd than early-forming pentlandite (cores of coarse-granular).     

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.     

Platinum-group elemental geochemistry of mafic and ultramafic rocks from the Xigaze ophiolite, southern Tibet

The Xigaze ophiolite in the central part of the Yarlung–Zangbo suture zone, southern Tibet, has a well-preserved sequence of sheeted dykes, basalts, cumulates and mantle peridotites at Jiding and Luqu. Both the basalts and diabases at Jiding have similar compositions with SiO₂ ranging from 45.9 to 53.5 wt%, MgO from 3.1 to 6.8 wt% and TiO₂ from 0.87 to 1.21 wt%. Their Mg^#s [100Mg/(Mg + Fe)] range from 40 to 60, indicating crystallization from relatively evolved magmas. They have LREE-depleted, chondrite-normalized REE diagrams, suggesting a depleted mantle source. These basaltic rocks have slightly negative Nb- and Ti-anomalies, suggesting that the Xigaze ophiolite represents a fragment of mature MORB lithosphere modified in a suprasubduction zone environment. The mantle peridotites at Luqu are high depleted with low CaO (0.3–1.2 wt%) and Al₂O₃ (0.04–0.42 wt%). They display V-shaped, chondrite-normalized REE patterns with (La/Gd)_N ratios ranging from 3.17 to 64.6 and (Gd/Yb)_N from 0.02 to 0.20, features reflecting secondary metasomatism by melts derived from the underlying subducted slab. Thus, the geochemistry of both the basaltic rocks and mantle peridotites suggests that the Xigaze ophiolite formed in a suprasubduction zone.Both the diabases and basalts have Pd/Ir ratios ranging from 7 to 77, similar to MORB. However, they have very low PGE abundances, closely approximating the predicted concentration in a silicate melt that has fully equilibrated with a fractionated immiscible sulfide melt, indicating that the rocks originated from magmas that were S-saturated before eruption. Moderate degrees of partial melting and early precipitation of PGE alloys explain their high Pd/Ir ratios and negative Pt-anomalies. The mantle peridotites contain variable amounts of Pd (5.99–13.5 ppb) and Pt (7.92–20.5 ppb), and have a relatively narrow range of Ir (3.47–5.01 ppb). In the mantle-normalized Ni, PGE, Au and Cu diagram, they are relatively rich in Pd and depleted in Cu. There is a positive correlation between CaO and Pd. The Pd enrichment is possibly due to secondary enrichment by metasomatism. Al₂O₃ and Hf do not correlate with Ir, but show positive variations with Pt, Pd and Au, indicating that some noble metals can be enriched by metasomatic fluids or melts carrying a little Al and Hf. We propose a model in which the low PGE contents and high Pd/Ir ratios of the basaltic rocks reflect precipitation of sulfides and moderate degrees of partial melting. The high Pd mantle peridotites of Xigaze ophiolites were formed by secondary metasomatism by a boninitic melt above a subduction zone.     

Mineralogy, geochemistry, and Nd isotope composition of the Rainbow hydrothermal field, Mid-Atlantic Ridge

Petrological, geochemical, and Nd isotopic analyses have been carried out on rock samples from the Rainbow vent field to assess the evolution of the hydrothermal system. The Rainbow vent field is an ultramafic-hosted hydrothermal system located on the Mid-Atlantic Ridge characterized by vigorous high-temperature venting (∼365°C) and unique chemical composition of fluids: high chlorinity, low pH and very high Fe, and rare earth element (REE) contents (Douville et al., Chemical Geology 184:37–48, 2002). Serpentinization has occurred under a low-temperature (<270°C) retrograde regime, later overprinted by a higher temperature sulfide mineralization event. Retrograde serpentinization reactions alone cannot reproduce the reported heat and specific chemical features of Rainbow hydrothermal fluids. The following units were identified within the deposit: (1) nonmineralized serpentinite, (2) mineralized serpentinite—stockwork, (3) steatite, (4) semimassive sulfides, and (5) massive sulfides, which include Cu-rich massive sulfides (up to 28wt% Cu) and Zn-rich massive sulfide chimneys (up to 5wt% Zn). Sulfide mineralization has produced significant changes in the sulfide-bearing rocks including enrichment in transition metals (Cu, Zn, Fe, and Co) and light REE, increase in the Co/Ni ratios comparable to those of mafic Cu-rich volcanic-hosted massive sulfide deposits and different ¹⁴³Nd/¹⁴⁴Nd isotope ratios. Vent fluid chemistry data are indicative of acidic, reducing, and high temperature conditions at the subseafloor reaction zone where fluids undergo phase separation most likely under subcritical conditions (boiling). An explanation for the high chlorinity is not straightforward unless mixing with high salinity brine or direct contribution from a magmatic Cl-rich aqueous fluid is considered. This study adds new data, which, combined with the current knowledge of the Rainbow vent field, brings compelling evidence for the presence, at depth, of a magmatic body, most likely gabbroic, which provides heat and metals to the system. Co/Ni ratios proved to be good tools used to discriminate between rock units, degree of sulfide mineralization, and positioning within the hydrothermal system. Deeper units have Co/Ni <1 and subsurface and surface units have Co/Ni >1.     

Controls on variations of platinum-group element concentrations in the sulfide ores of the Jinchuan Ni-Cu deposit, western China

Ongoing underground exploration in the giant Jinchuan Ni-Cu sulfide deposit in western China is beginning to emphasize the potential for Cu-, Pt-, and Pd-rich sulfide ores that may have formed by sulfide liquid fractionation. The success of such an effort relies on whether or not fractional crystallization of sulfide occurred in the Jinchuan system. In this paper, we used available PGE data to evaluate such a process. We found that about two thirds of the 126 samples analyzed to date exhibit significant decoupling not only between Pt and Pd but also between Ru, Rh, and Ir. The best explanation for the decoupling is postmagmatic hydrothermal alteration, which affected not only silicates but also sulfides. The effects of postmagmatic alteration must be considered when using metal and isotopic ratios to evaluate primary mineralization. PGE variations in the remaining one third of the samples with Ir/(Ir + Ru) = 0.3–0.7, Ir/(Ir + Rh) = 0.4–0.8, and Pt/(Pt + Pd) = 0.3–0.7 indicate variable R-factors within individual ore bodies as well as the entire deposit, consistent with the interpretation that multiple sulfide-bearing magmas from depth were involved in the formation of the Jinchuan deposit. The mantle-normalized PGE patterns of the least-altered samples from the Jinchuan deposit are similar to the picrite-related Pechenga Ni-Cu sulfide deposit in Russia. PGE variations that can be related to sulfide liquid fractionation are observed in orebody-1 and orebody-24 but not in orebody-2 at Jinchuan. Exploration for Cu-, Pt-, and Pd-rich sulfide ores that may have been expelled into fractures in the footwalls of orebody-1 and orebody-24 appears to be justified.     

Chemical evolution of metal in refractory inclusions in CV3 chondrites

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 P_tot = 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.