Fractionation Of Platinum Group Elements Research Articles

Controls on Pt/Pd ratios in Bushveld magmas and cumulates: a review complemented by new W isotope data

The Bushveld Complex of South Africa is underlain by a fine-grained sill complex which most workers interpret to represent the quenched parent magmas to the intrusion. The sills have unusually high Pt contents (up to ~ 25 ppb) and Pt/Pd ratios (average 1.50) exceeding those in most other mantle magmas globally. Unusually high Pt/Pd is also found in many Bushveld cumulates. Understanding the origin of the high Pt/Pd is important for exploration, in view of the contrasting monetary value of the metals, but also for unravelling the petrogenesis of the intrusion. Here, we review existing platinum-group element (PGE) data and present the first radiogenic W isotope data on a Bushveld rock, to evaluate a range of potential models, including PGE fractionation prior to final magma emplacement and within the Bushveld magma chamber, magma derivation from the sub-continental lithospheric mantle (SCLM), contamination of Bushveld magma with Pt-rich continental crust, and a meteoritic component in the mantle source to the magmas or in the crust with which the magmas interacted. We identify three key processes causing fractionation of metals prior to final magma emplacement and within the Bushveld chamber, namely crystallisation of Pt alloys, partial melting of cumulus sulfides triggered by flux of volatiles followed by sulfide melt percolation, and mobilisation of PGE by percolation of volatiles through the cumulate pile. The currently available W and Ru isotope data are inconsistent with derivation of the Bushveld magmas from mantle or crustal sources containing an enhanced meteoritic component relative to normal post-Hadean mantle.

Highly siderophile element behavior in the subduction zone mantle: Constraints from data on the Yap Trench peridotites

The highly siderophile elements (HSEs) in peridotites from the Yap Trench are investigated to understand their behavior in the subduction zone mantle, which is characterized by high melt depletion and metasomatism. Results reveal that the abundance of HSEs in Yap Trench peridotites is extremely low compared with that in oceanic peridotites from the mid-ocean ridge and other subduction-zone environments, indicating the extensive extraction of the sulfide melt. Chondrite-normalized HSE patterns are heterogeneous and exhibit strong fractionation of platinum-group elements (PGEs) and slight enrichment of Re and Au. The Ru/Ir (1.64–16.12), Os/Ir (0.15–7.19), and Pt/Pd (0.53–13.17) ratios in most of the studied samples are higher than those in CI chondrite (Ru/Ir: 1.49; Os/Ir: 1.06; and Pt/Pd: 1.67). These suprachondritic PGE ratios result from the exhaustion of the base metal sulfide (BMS) and the formation of platinum-group minerals and alloys, such as Os–Ru-rich sulfides and PtFe alloys, that are selectively enriched with certain HSEs. Mantle metasomatism appears to have no systematic influence on PGEs, although it may increase the abundance of Re and Au in the Yap Trench peridotites. Moreover, compared to abyssal peridotites, subduction-related peridotites have fractionated PGE patterns, particularly for the iridium group, suggesting that subduction conditions may promote the fractionation of the PGEs. However, suprachondritic PGE ratios are generally observed in subduction-related peridotites with a low Al2O3 content (<1 wt%) instead of subduction-related fertile samples. This suggests that highly depleted and subduction-related conditions are required for the fractionation of PGEs. We recommend that the high oxygen fugacity, hydrous melting, and high degree melting of the subduction-zone mantle may result in the exhaustion of the BMS in highly depleted peridotites, promoting the formation of platinum-group minerals and HSE-rich alloys, in which the HSEs are significantly fractionated.

Refertilization of depleted mantle peridotite in the Nagaland–Manipur ophiolite, north‐east India: Constraints from PGE, mineral, and whole‐rock geochemistry

This paper discusses whole‐rock geochemistry, mineral chemistry, and platinum group element (PGE) systematics of depleted mantle rocks (harzburgite and dunite) from the northern part of Nagaland–Manipur Ophiolite (NMO), north‐east India, to comprehend their source features, fractionation behaviour of PGE during magmatic evolution, and its tectonic origin. The studied ultramafic rocks are characterized by a low concentration of CaO (0.57–0.71 wt%), Al2O3 (0.18–0.92 wt%) with ∑REE of 1.135–2.702 ppm and high concentrations of MgO (38.70–44.21 wt%), Cr (1,843–4,572 ppm), and Ni (894–4,138 ppm). They show U‐shaped REE patterns [LREE and HREE enrichment (La/Sm)N = 1.85–4.11, (Dy/Yb)N = 0.51–0.85]. Olivine ranges Fo 88.18 to Fo92.23, whereas Cpx and Opx range En44.84 to En47.89 and En86.37 to En93.37 respectively. The chrome spinel Cr# [Cr/(Cr + Al)] and Mg# [Mg/(Mg + Fe2+)] are 0.47–0.83 and 0.31–0.60, respectively, which indicates recrystallization from a boninitic magma in a Supra‐Subduction Zone setting. Conventional thermometry indicates the equilibration temperatures of the dunite sample yielded high temperatures of ~850°C, suggesting their formation due to later interaction with high‐temperature percolating melts. The PGE contents in harzburgite are low (125.6–142.8 ppb) as compared to the dunite (248–360 ppb). They have high PPGE/IPGE and negative Pt* (Pt/Pt* = 0.73) anomaly, which is characteristic of re‐entry of PPGE into the system via reaction with percolating basaltic melt in the mantle wedge. Significantly higher concentration of PPGEs than IPGEs in the samples, indicating recrystallization of PPGEs with early sulphide fractionation. The presence of significant Rh and Pd enhancements relative to Pt in all samples suggests that Pt was removed during PGE fractionation. This could be one of the reasons for both harzburgite and dunite's sulphide undersaturation. PGE distribution in NMO ultramafic rocks was therefore validated as being governed by sulphide saturation in parental magma and altered not only by partial melting but also by fractionation during their production in the Supra‐Subduction Zone environment.

Noble Metals in Arc Basaltic Magmas Worldwide: A Case Study of Modern and Pre-Historic Lavas of the Tolbachik Volcano, Kamchatka

Platinum-group elements (PGE) and gold are a promising tool to assess the processes of mantle melting beneath the subduction zones. However, fractionation processes in magmas inevitably overwrite the initial metal budgets of magmas, making constraints on the melting processes inconclusive. Moreover, little is still known about the geochemical behavior of a particular metal in a single arc magmatic system, from mantle melting towards magma solidification. Here we compare noble metals in lavas from several eruptions of the Tolbachik volcano (Kamchatka arc) to better understand the effects of magma differentiation, estimate primary melt compositions and make constraints on the mantle melting. We show that Ir, Ru, Rh and, to a lesser extent, Pt are compatible during magmatic differentiation. The pronounced incompatible behavior of Cu and Pd, observed in Tolbachik magmas, rules out the significant influence of sulfide melts on the early magmatic evolution in this particular case. Gold is also incompatible during magmatic differentiation; however, its systematics can be affected by the inferred gold recycling in the plumbing system of Tolbachik. Although the Tolbachik lavas show only slightly higher PGE fractionation than in MORB, a notable negative Ru anomaly (higher Pt/Ru and Ir/Ru) is observed. We attribute this to be a result of greater oxidation in the subarc mantle (by 1–4 log units), which promotes crystallization of Ru-bearing phases such as Fe3+-rich Cr-spinel and laurite. The estimated Pd contents for the parental melt of the Tolbachik lavas approaches 6.5 ppb. This is several times higher than reported MORB values (1.5 ± 0.5 ppb), suggesting the enrichment of Pd in the mantle wedge. Our results highlight the influence of the subduction-related processes and mantle wedge refertilization on the noble metal budgets of arc magmas.

Nano- and Micrometer-Sized PGM in Ni-Cu-Fe Sulfides from an Olivine Megacryst in the Udachnaya Pipe, Yakutia, Russia

ABSTRACT This paper focuses on a nanoscale study of nano- and micrometer-size Os-rich mineral particles hosted in a Ni-Fe-Cu sulfide globule found in an olivine megacryst from the Udachnaya pipe (Yakutia, Russia). These platinum-group element mineral particles and their host sulfide matrices were investigated using a combination of techniques, including field emission gun electron probe microanalyzer, field emission scanning electron microscopy, and focused ion beam and high-resolution transmission electron microscopy. The sulfide globule is of mantle origin, as it is hosted in primitive olivine (Fo90–93), very likely derived from the crystallization of Ni-Fe-Cu sulfide melt droplets segregated by liquid immiscibility from a basaltic melt in a volume of depleted subcontinental lithospheric mantle. Microscopic observations by means of field emission scanning electron microscopy and single-spot analysis and mapping by field emission gun electron probe microanalyzer reveal that the sulfide globule comprises a core of pyrrhotite with flame-like exsolutions (usually &amp;lt;10 μm thickness) of pentlandite, which is irregularly surrounded by a rim of granular pentlandite and chalcopyrite. Elemental mapping by energy dispersive spectroscopy (acquired using the high-resolution transmission electron microscopy) of the pyrrhotite (+ pentlandite) core reveals that pentlandite exsolution in pyrrhotite is still observable at the nanoscale as fringes of 100 to 500 nm thicknesses. The sulfide matrices of pyrrhotite, pentlandite, and chalcopyrite contain abundant nano- and micrometer-size platinum group element mineral particles. A careful inspection of eight of these platinum group element particles under focused ion beam and high-resolution transmission electron microscopy showed that they are crystalline erlichmanite (OsS2) with well-developed crystal faces that are distinctively oriented relative to their sulfide host matrices. We propose that the core of the Ni-Fe-Cu sulfide globule studied here was derived from a precursor monosulfide solid solution originally crystallized from a sulfide melt at &amp;gt;1100 °C, which later decomposed into pyrrhotite and the pentlandite flame-like exsolutions upon cooling at &amp;lt;600 °C. Once solidified, the solid monosulfide solid solution reacted with non-equilibrium Cu-and Ni-rich sulfide melt(s), giving rise to the granular pentlandite in equilibrium with chalcopyrite now forming the rim of the sulfide globule. Meanwhile, nano- to micron-sized crystals of erlichmanite crystallized directly from or slightly before monosulfide solid solution from the sulfide melt. Thus, Os, and to a lesser extent Ir and Ru, were physically partitioned by preferential uptake via early formation of nanoparticles at high temperature instead of low-temperature exsolution from solid Ni-Fe-Cu sulfides. The new data provided in this paper highlight the necessity of studying platinum group element mineral particles in Ni-Fe-Cu sulfides using analytical techniques that can image nanoscale textural features in order to better understand the mechanisms of platinum group element fractionation in magmatic systems. These processes may play a crucial role in controlling the background geochemical budgets for siderophile and chalcophile elements in a wide range of mantle-derived magmas.

Origin of the Fanjingshan Mafic-Ultramafic Rocks, Western Jiangnan Orogen, South China: Implications for PGE Fractionation and Mineralization

The Fanjingshan mafic-ultramafic rocks in the west Jiangnan Orogen of South China are considered to be a potential target for mineral exploration. However, the petrogenesis and magma evolution of these rocks are not yet clearly constrained, let along their economic significance. The compositions of platinum group elements (PGE) in the Fanjingshan mafic-ultramafic rocks can provide particular insight into the generation and evolution of the mantle-derived magma and thus the potential of Cu-Ni-PGE sulphide mineralization. The Fanjingshan mafic-ultramafic rocks have relatively high Pd-subgroup PGE (PPGE) relative to Ir-subgroup PGE (IPGE) in the primitive mantle-normalized diagrams. Meanwhile, the Fanjingshan mafic-ultramafic rocks have low Pd/Ir (11–28) ratios, implying relatively low degree of partial melting in the mantle. Low Cu/Pd ratios (545–5 216) and high Cu/Zr ratios (0.4–5.8 with the majority greater than 1) of Fanjingshan ultramafic rocks indicate that the S-undersaturated parental magma with relatively high PGE was formed. Although the Fanjingshan mafic rocks have remarkably higher Cu/Pd ratios (8 913–107 016) likely resulting from sulphide segregation, the degree of sulphide removal is insignificant. Fractionation of olivine rather than chromite and platinum group minerals or alloys governed the fractionation of PGE and produced depletion of IPGE (Os, Ir and Ru) relative to PPGE (Rh, Pt and Pd), as supported by the positive correlation between Pd/Ir and V, Y and REE. Collectively, original S-undersaturated magma and insignificant crustal contamination during magma ascent and emplacement result in the separation of immiscible sulphide impossible and thus impede the formation of economic Cu-Ni-PGE sulphide mineralization within the Fanjingshan mafic-ultramafic rocks.

The behavior of Pt, Pd, Cu and Ni in the Se-sulfide system between 1050 and 700 °C and the role of Se in platinum-group elements fractionation in sulfide melts

The behavior of Pt, Pd, Ni and Cu in Se-sulfide system and the role of Se in platinum-group elements (PGE) fractionation have been experimentally investigated at temperatures between 1050 and 700°C in evacuated silica tubes. At 1050°C, Se partially partitions into a vapor phase. At 980°C, monosulfide solid solution (mss) and sulfide melt are the only stable phases. No Pt or Pd-bearing discrete selenide phases form down to 700°C. Instead cooperite (PtS) forms at 900°C. Both mss and sulfide melt can accommodate wt.% levels of Se over the whole temperature range covered by the experiments. The addition of Se in the sulfide system leads to an increase in the activity coefficients of Ni and Pd in sulfide melt. This is reflected by an increase in the partition coefficients of Ni and Pd between mss and sulfide melt. The Pt-Se activity coefficient in sulfide melt is lower than that of Pt-S. Owing to selenium’s high solubility in sulfides, there never become oversaturated in Se to the extent that discrete selenides form. As such, base metal sulfides are expected to control the geochemical behavior of Se in natural systems. Interestingly, partition coefficients for the platinum-group elements (Os, Ir, Ru, Pt, Rh, Pd) between mss and sulfide melt are undistinguishable regardless of whether Se is present or not. These results imply that Se plays little role in the fractionation of PGE as sulfide melt cools down and crystallize. Furthermore, our experimental results provide evidence that Se is volatile at magmatic temperature and is likely to be degassed like sulfur.

Chalcophile elements in Martian meteorites indicate low sulfur content in the Martian interior and a volatile element-depleted late veneer

It is generally believed that the Martian mantle and core are rich in sulfur and that shergottites originated from sulfide-saturated magma. However, recent work suggests that the high FeO contents would require very high S concentrations in shergottite parent magmas at sulfide saturation. Here we combine new and published data on chalcophile elements in shergottites, nakhlites and ALH84001 to constrain the sulfide saturation state of the parent magmas and the chalcophile element concentrations in their mantle sources.Regardless of the MgO content and the long-term depletion history of incompatible lithophile elements as indicated by initial ε143Nd, different groups of shergottites display limited variations in ratios of Pt, Pd, Re, Cu, S, Se and Te. The emplacement of most shergottites within the crust and limited variations of ratios of chalcophile elements with substantial differences in volatility during eruption (e.g., Cu/S, Cu/Se and Pt/Re) indicate little degassing losses of S, Se, Te and Re from shergottites. Limited variations in ratios of elements with very different sulfide–silicate melt partition coefficients and negative correlations of chalcophile elements with MgO require a sulfide-undersaturated evolution of the parent magmas from mantle source to emplacement in the crust, consistent with the FeO-based argument. Sulfide petrography and the komatiite-like fractionation of platinum group elements (PGE) in shergottites also support this conclusion. The absence of accumulated sulfides in the ancient Martian cumulate ALH84001 results in very low contents of PGE, Re, Cu, Se and Te in this meteorite, hinting that sulfide-undersaturated magmas may have occurred throughout the Martian geological history. The negative correlation of Cu and MgO contents in shergottites suggests approximately 2±0.4(1s) μg/g Cu in the Martian mantle. The ratios of Cu, S, Se and Te indicate 360±120 μg/g (1s) S, 100±27 ng/g (1s) Se and 0.50±0.25 ng/g (1s) Te in the Martian mantle. At such low S concentrations, all S in Martian mantle sources may dissolve in basaltic melts that form at >5 % partial melting.Assuming equilibrium metal–silicate partitioning, and provided that the compositional model of the Martian mantle based on SNC meteorites is correct, Martian mantle inventories of Cu, S and Se were mostly established by core formation and the Martian core should contain <5–10 wt.% S only (depending on the choice of metal–silicate partition coefficients). The low S content in the Martian interior is consistent with the low Zn content in the Martian mantle, which indicates about 5 wt.% S in the core. In contrast, the highly siderophile PGE, Re and Te were added to the mantle by late accreted material after the Martian core formed. The near chondritic PGE ratios and the very low ratio of volatile Te to refractory PGE reflect a strongly volatile element-depleted late veneer and imply that the delivery of Martian water, presumably from carbonaceous chondrite like materials, must have occurred before accretion of the late veneer, likely within 2–3 million years after formation of the solar system.

Platinum-group elements fractionation by selective complexing, the Os, Ir, Ru, Rh-arsenide-sulfide systems above 1020 °C

The platinum-group element (PGE) contents in magmatic ores and rocks are normally in the low μg/g (even in the ng/g) level, yet they form discrete platinum-group mineral (PGM) phases. IPGE (Os, Ir, Ru)+Rh form alloys, sulfides, and sulfarsenides while Pt and Pd form arsenides, tellurides, bismuthoids and antimonides. We experimentally investigate the behavior of Os, Ru, Ir and Rh in As-bearing sulfide system between 1300 and 1020°C and show that the prominent mineralogical difference between IPGE (+Rh) and Pt and Pd reflects different chemical preference in the sulfide melt. At temperatures above 1200°C, Os shows a tendency to form alloys. Ruthenium forms a sulfide (laurite RuS2) while Ir and Rh form sulfarsenides (irarsite IrAsS and hollingworthite RhAsS, respectively). The chemical preference of PGE is selective: IPGE+Rh form metal–metal, metal-S and metal-AsS complexes while Pt and Pd form semimetal complexes. Selective complexing followed by mechanical separation of IPGE (and Rh)-ligand from Pt- and Pd-ligand associations lead to PGE fractionation.

Platinum-group mineralization at the margin of the Skaergaard intrusion, East Greenland

Two occurrences of platinum-group elements (PGEs) along the northern margin of the Skaergaard intrusion include a sulfide-bearing gabbro with slightly less than 1 ppm PGE + Au and a clinopyroxene-actinolite-plagioclase-biotite-ilmenite schist with 16 vol% sulfide and 1.8 ppm PGE + Au. Both have assemblages of pyrrhotite, pentlandite, and chalcopyrite typical for orthomagmatic sulfides. Matching platinum-group mineral assemblages with sperrylite (PtAs2), kotulskite (Pd(Bi,Te)1–2), froodite (PdBi2), michenerite (PdBiTe), and electrum (Au,Ag) suggest a common origin. Petrological and geochemical similarities suggest that the occurrences are related to the Skaergaard intrusion. The Marginal Border Series locally displays Ni depletion consistent with sulfide fractionation, and the PGE fractionation trends of the occurrences are systematically enriched by 10–50 times over the chilled margin. The PGE can be explained by sulfide-silicate immiscibility in the Skaergaard magma with R factors of 110–220. Nickel depletion in olivine suggests that the process occurred within the host cumulate, and the low R factors require little sulfide mobility. The sulfide assemblages are different to the chalcopyrite-bornite-digenite assemblage found in the Skaergaard Layered Series and Platinova Reef. These differences can be explained by the early formation of sulfide melt, while magmatic differentiation or sulfur loss caused the unusual sulfide assemblage within the Layered Series. The PGEs indicate that the sulfides formed from the Skaergaard magma. The sulfides and PGEs could not have formed from the nearby Watkins Fjord wehrlite intrusion, which is nearly barren in sulfide. We suggest that silicate-sulfide immiscibility led to PGE concentration where the Skaergaard magma became contaminated with material from the Archean basement.

Geochemistry of platinum-group elements and mineral composition in chromitites and associated rocks from the Abdasht ultramafic complex, Kerman, Southeastern Iran

The Abdasht complex is a major ultramafic complex in south-east Iran (Esfandagheh area). It is composed mainly of dunite, harzburgite, podiform chromitites, and subordinate lherzolite and wehrlite. The podiform chromitites display massive, disseminated, banded and nodular textures. Chromian spinels in massive chromitites exhibit a uniform and restricted composition and are characterized by Cr# [=Cr/(Cr+Al)] ranging from 0.76 to 0.77, Mg# [=Mg/(Mg+Fe2+)] from 0.63 to 0.65 and TiO2<0.2wt.%. These values may reflect crystallization of the chromian spinels from boninitic magmas. Chromian spinels in peridotites exhibit a wide range of Cr# from 0.48 to 0.86, Mg# from 0.26 to 0.56 and very low TiO2 contents (averaging 0.07wt.%). The Fe3+# is very low, (<0.08wt.%) in the chromian spinel of chromitites and peridotites of the Abdasht complex which reflects crystallization under low oxygen fugacities.The distribution of platinum group elements (PGE) in Abdasht chromitites displays a high (Os+Ir+Ru)/(Rh+Pt+Pd) ratio with strongly fractionated chondrite-normalized PGE patterns typical of ophiolitic chromitites. Moreover, the Pd/Ir value, which is an indicator of PGE fractionation, is very low (<0.1) in the chromitites.The harzburgite, dunite and lherzolite samples are highly depleted in PGE contents relative to chondrites. The PdN/IrN ratios in dunites are unfractionated, averaging 0.72, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru anomaly, and their PdN/IrN ratio averages 2.4 and 2.3 respectively. Moreover, the PGE chondrite and primitive mantle normalized patterns of harzburgite, dunite and lherzolite are relatively flat which are comparable to the highly depleted mantle peridotites.The mineral chemistry data and PGE geochemistry indicate that the Abdasht chromitites and peridotites were generated from a melt with boninitic affinity under low oxygen fugacity in a supra-subduction zone setting. The composition of calculated parental melts of the Abdasht chromitites is consistent with the differentiation of arc-related magmas.

Partitioning of Si and platinum group elements between liquid and solid Fe–Si alloys

Crystallization of the Earth’s inner core fractionates major and minor elements between the solid and liquid metal, leaving physical and geochemical imprints on the Earth’s core. For example, the density jump observed at the Inner Core Boundary (ICB) is related to the preferential partitioning of lighter elements in the liquid outer core. The fractionation of Os, Re and Pt between liquid and solid during inner core crystallization has been invoked as a process that explains the observed Os isotopic signature of mantle plume-derived lavas (Brandon et al., 1998; Brandon and Walker, 2005) in terms of core–mantle interaction. In this article we measured partitioning of Si, Os, Re and Pt between liquid and solid metal. Isobaric (2 GPa) experiments were conducted in a piston-cylinder press at temperatures between 1250°C and 1600°C in which an imposed thermal gradient through the sample provided solid–liquid coexistence in the Fe–Si system. We determined the narrow melting loop in the Fe–Si system using Si partitioning values and showed that order–disorder transition in the Fe–Si solid phases can have a large effect on Si partitioning. We also found constant partition coefficients (DOs, DPt, DRe) between liquid and solid metal, for Si concentrations ranging from 2 to 12 wt%. The compact structure of Fe–Si liquid alloys is compatible with incorporation of Si and platinum group elements (PGEs) elements precluding solid–liquid fractionation. Such phase diagram properties are relevant for other light elements such as S and C at high pressure and is not consistent with inter-elemental fractionation of PGEs during metal crystallization at Earth’s inner core conditions. We therefore propose that the peculiar Os isotopic signature observed in plume-derived lavas is more likely explained by mantle source heterogeneity (Meibom et al., 2002; Baker and Krogh Jensen, 2004; Luguet et al., 2008).

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

AbstractPotential 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.

Different Origins of the Fractionation of Platinum-Group Elements in Raobazhai and Bixiling Mafic-Ultramafic Rocks from the Dabie Orogen, Central China

Concentrations of the platinum group elements (PGEs), including Ir, Ru, Rh, Pt, and Pd, have been determined for both Raobazhai and Bixiling mafic-ultramafic rocks from the Dabie Orogen by fire assay method. Geochemical compositions suggest that the Raobazhai mafic-ultramafic rocks represent mantle residues after variable degrees of partial melting. They show consistent PGE patterns, in which the IPGEs (i.e., Ir and Ru) are strongly enriched over the PPGEs (i.e., Pt and Pd). Both REE and PGE data of the Raobazhai mafic-ultramafic rocks suggest that they have interacted with slab-derived melts during subduction and/or exhumation. The Bixiling ultramafic rocks were produced through fractional crystallization and cumulation from magmas, which led to the fractionated PGE patterns. During fractional crystallization, Pd is in nonsulfide phases, whereas both Ir and Ru must be compatible in some mantle phases. We suggest that the PGE budgets of the ultramafic rocks could be fractionated by interaction with slab-derived melts and fractional crystallization processes.

Rhenium–osmium isotope and platinum-group elements in the Xinjie layered intrusion, SW China: Implications for source mantle composition, mantle evolution, PGE fractionation and mineralization

The Xinjie mafic–ultramafic layered intrusion in the Emeishan large igneous province (ELIP) hosts Cu–Ni–platinum group element (PGE) sulfide ore layers within the lower part and Fe–Ti–V oxide-bearing horizons within the middle part. The major magmatic Cu–Ni–PGE sulfide ores and spatially associated cumulate rocks are examined for their PGE contents and Re–Os isotopic systematics. The samples yielded a Re–Os isochron with an age of 262 ± 27 Ma and an initial 187Os/ 188Os of 0.12460 ± 0.00011 ( γ Os( t) = −0.5 ± 0.1). The age is in good agreement with the previously reported U–Pb zircon age, indicating that the Re–Os system remained closed for most samples since the intrusion emplacement. They have near-chondritic γ Os( t) values ranging from −0.7 to −0.2, similar to those of the Lijiang picrites and Song Da komatiites. Exceptionally, two samples from the roof zone and one from upper sequence exhibit radiogenic γ Os( t) values (+0.6 to +8.6), showing minor contamination by the overlying Emeishan basalts. The PGE-rich ores contain relatively high PGE and small amounts of sulfides (generally less than 2%) and the abundance of Cu and PGE correlate well with S, implying that the distribution of these elements is controlled by the segregation and accumulation of a sulfide liquid. Some ore samples are poor in S (mostly <800 ppm), which may due to late-stage S loss caused by the dissolution of FeS from pre-existing sulfides through their interaction with sulfide-unsaturated flowing magma. The combined study shows that the Xinjie intrusion may be derived from ferropicritic magmas. The sharp reversals in Mg#, Cr/FeO T and Cr/TiO 2 ratios immediately below Units 2–4, together with high Cu/Zr ratios decreasing from each PGE ore layer within these cyclic units, are consistent with multiple magma replenishment episodes. The sulfides in the cumulate rocks show little evidence of PGE depletion with height and thus appear to have segregated from successive inputs of fertile magma. This suggests that the Xinjie intrusion crystallized from in an open magma system, e.g., a magma conduit. The compositions of the disseminated sulfides in most samples can be modeled by applying an R factor (silicate–sulfide mass ratio) of between 1000 and 8000, indicating the segregation of only small amounts of sulfide liquid in the parental ferropicritic magmas. Thus, continuous mixing between primitive ferropicritic magma and differentiated resident magma could lead to crystallization of chromite, Cr-bearing magnetite and subsequently abundant Fe–Ti oxides, thereby the segregation of PGE-rich Cu-sulfide. When considered in the light of previous studies on plume-derived komatiites and picrites worldwide, the close-to-chondritic Os isotopic composition for most Xinjie samples, Lijiang picrites and Song Da komatiites suggest that the ferropicritic magma in the ELIP were generated from a plume. This comprised recycled Neoproterozic oceanic lithosphere, including depleted peridotite mantle embedded with geochemically enriched domains. The ascending magmas thereafter interacted with minor (possibly <10%) subducted/altered oceanic crust. This comparison suggests that the komatiitic melts in the ELIP originated from a greater-than normal degree of melting of incompatible trace element depleted, refractory mantle components in the plume source.

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

The distribution of platinum-group elements (PGEs), together with spinel composition, of podiform chromitites and serpentinized peridotites were examined to elucidate the nature of the upper mantle of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco. The mantle section is dominated by harzburgite with less abundant dunite. Chromitite pods are also found as small lenses not exceeding a few meters in size. Almost all primary silicates have been altered, and chromian spinel is the only primary mineral that survived alteration. Chromian spinel of chromitites is less affected by hydrothermal alteration than that of mantle peridotites. All chromitite samples of the Bou Azzer ophiolite display a steep negative slope of PGE spidergrams, being enriched in Os, Ir and Ru, and extremely depleted in Pt and Pd. Harzburgites and dunites usually have intermediate to low PGE contents showing more or less unfractionated PGE patterns with conspicuous positive anomalies of Ru and Rh. Two types of magnetite veins in serpentinized peridotite, type I (fibrous) and type II (octahedral), have relatively low PGE contents, displaying a generally positive slope from Os to Pd in the former type, and positive slope from Os to Rh then negative from Rh to Pd in the latter type. These magnetite patterns demonstrate their early and late hydrothermal origin, respectively. Chromian spinel composition of chromitites, dunites and harzburgites reflects their highly depleted nature with little variations; the Cr# is, on average, 0.71, 0.68 and 0.71, respectively. The TiO 2 content is extremely low in chromian spinels, <0.10, of all rock types. The strong PGE fractionation of podiform chromitites and the high-Cr, low-Ti character of spinel of all rock types imply that the chromitites of the Bou Azzer ophiolite were formed either from a high-degree partial melting of primitive mantle, or from melting of already depleted mantle peridotites. This kind of melting is most easily accomplished in the supra-subduction zone environment, indicating a genetic link with supra-subduction zone magma, such as high-Mg andesite or arc tholeiite. This is a general feature in the Neoproterozoic upper mantle.

Fractionation and Reactivity of Platinum Group Elements During Estuarine Mixing

The fractionation of platinum group elements (PGE) rhodium(III), palladium(II), and platinum(IV), has been studied after their addition in aqueous form to unfiltered river water samples (Tugela river, South Africa) and to mixtures of river water and seawater. The particulate fraction of PGE averaged about 70 (Rh), 50 (Pd), and 25% (Pt) of total metal and was dependent on both particle concentration and salinity. The aqueous (<0.45 microm) pool of PGE was dominated by entities of less than 0.1 microm in diameter, and for Pd and Rh hydrophobic complexes of metal, operationally defined by their retention on a C-18 column, were significant. Distribution coefficients, based on the w/w concentration of metal on particles relative to the corresponding concentration in the aqueous pool, either increased (Rh and Pd) or declined (Pt) with increasing salinity. These observations are interpreted in terms of a number of general and metal-specific mechanisms. Thus, the behavior of Pd appears to be controlled by its association with relatively small (<0.1 microm) dissolved organic ligands, a significant fraction of which is hydrophobic and is subject to salting out upon estuarine mixing. Rhodium may also be partly subject to this mechanism of removal, but kinetic considerations and results of X-ray analysis of filter-retentates suggest that adsorption of cationic hydroxychlorides and the destabilization and precipitation of hydroxy-complexes induced by the rise in pH across the estuarine gradient are more important. Unlike Pd, the binding of Pt by organic ligands is kinetically hindered. Thus, in contrast to Pd, particle-water reactivity of Pt is controlled by electrostatic interactions between the particle surface and inorganic aqueous species. The results of this study improve our understanding of and ability to predict the transport and fate of PGE in estuaries where these metals are mobilized or discharged.

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.

Evidence from meimechites and other low-degree mantle melts for redox controls on mantle-crust fractionation of platinum-group elements

Understanding of the geochemistry of the chalcophile elements [i.e., Os, Ir, Ru, Pt, Pd (platinum-group elements), and Au, Cu, Ni] has been informed for at least 20 years by the common assumption that when crust-forming partial melts are extracted from the upper mantle, sulfide liquid in the restite sequesters chalcophile elements until the extent of partial melting exceeds approximately 25% and all of the sulfide has been dissolved in silicate melt [Hamlyn, P. R. & Keays, R. R. (1985) Geochim. Cosmochim. Acta 49, 1797-1811]. Here we document very high, unfractionated, chalcophile element concentrations in small-degree partial melts from the mantle that cannot be reconciled with the canonical residual sulfide assumption. We show that the observed high, unfractionated platinum-group element concentrations in small-degree partial melts can be attained if the melting takes place at moderately high oxygen fugacity, which will reduce the amount of sulfide due to the formation of sulfate and will also destabilize residual monosulfide solid solution by driving sulfide melts into the spinel-liquid divariant field. Magmas formed at high oxygen fugacity by small degrees of mantle melting can be important agents for the transfer of chalcophile elements from the upper mantle to the crust and may be progenitors of significant ore deposits of Pt, Pd, and Au.

The provenance of fertile off-craton lithospheric mantle: Sr–Nd isotope and chemical composition of garnet and spinel peridotite xenoliths from Vitim, Siberia

Nd and Sr isotope compositions were obtained for pure garnet and pyroxene separates from coarse peridotite xenoliths from the Vitim volcanic province east of Lake Baikal. Internal Sm–Nd isochrons give ages of 24–42 Ma. These dates are older than the eruption age for the host picrite tuff (∼16 Ma) indicating that garnet and clinopyroxene may not have been in isotopic equilibrium in the mantle (at 19–23 kbar, 990–1070 °C). In spite of their fertile major element chemistry, many peridotites have extremely depleted Nd and Sr isotope compositions (calculated from mineral analyses: ɛ Nd T =+14 to +27; 87Sr/ 86Sr=0.7017–0.7028) and therefore plot outside the MORB field in the Sr–Nd isotope diagram. Sm–Nd and Rb–Sr model ages for unmetasomatised peridotites are concordant for each sample within ±0.4 Ga and suggest a depletion event of a primitive mantle ∼2 Gy ago, also consistent with Re–Os data on the same xenolith suite [Pearson, D.G., Irvine, G.J., Ionov, D.A., Boyd, F.R., Dreibus, G.E., 2004. Re–Os isotope systematics and Platinum Group Element fractionation during mantle melt extraction: a study of peridotite xenoliths from N. Lesotho and S. Namibian kimberlites, the Vitim volcanic field and massif peridotites from Beni Bousera. Chem. Geol. 208, 29–59]. This suggests that the mantle depletion event was roughly matched with formation of the mature continental crust in the region (∼2.0 Ga according to U–Pb and Sm–Nd dating) and implies that the mantle peridotites have been attached to the continental lithosphere since that time and survived several major tectono-thermal events. The Paleoproterozoic formation age for the fairly fertile Vitim mantle domain indicates that average lithospheric mantle compositions cannot be used to assess lithospheric formation ages in continental off-craton mantle.