Platinum Group Element Concentrations Research Articles

Fractionation of highly siderophile and chalcogen elements in the lower oceanic crust: Insights from the troctolites of the Alpine-Apennine Jurassic ophiolites

The present study aims at investigating the role of reactive porous flow in the fractionation of highly siderophile (HSE: Os, Ir, Ru, Rh, Pt, Pd, Au and Re) and chalcogen (S, Se, Te) elements during construction of the lower oceanic crust in (ultra-)slow spreading ridges. At this purpose, we analyzed the whole-rock HSE and chalcogen elements, and Re-Os isotopes in olivine-rich troctolites embedded within large-scale gabbroic sequences from the Alpine-Apennine Jurassic ophiolites. Leucotroctolites and chromitites associated with the olivine-rich troctolites were also investigated. The olivine-rich troctolites have initial γOs ranging from +0.2 to +5.9. Their primitive mantle-normalized patterns are characterized by a slight enrichment of Os over Ir, and an increase from Ir to Ru, Rh, Pt, Pd and Au, nearly flat Au-Te-Se-S, and weak Re depletion with respect to S. This HSE and chalcogen element, and Os isotopic signature was acquired in response to sulfide segregation, which was most likely triggered by reaction between an olivine-rich matrix and migrating MORB-type melts. The chromitite layers occurring within the olivine-rich troctolites exhibit high concentrations of platinum group elements (PGE: Os, Ir, Ru, Rh, Pt and Pd). Formation of the chromitites might produce melts depleted in PGE that reactively migrated within the olivine-rich matrix, and ultimately locally led to olivine-rich troctolites characterized by a slight increase of the PGE/chalcogen element fractionation. The leucotroctolites differ from associated olivine-rich troctolites in the lower concentrations of HSE and chalcogen elements, with subparallel primitive mantle-normalized patterns but slightly higher Se/Te values. The crystallization of the olivine-rich troctolites might release HSE and chalcogen elements-depleted melts that reacted with an olivine + plagioclase crystal mush to form the leucotroctolites. Alternatively, formation of the leucotroctolites involved a process of reacting melt flow characterized by a low melt/crystal matrix ratio, which led to a relatively low proportion of trapped melt and related sulfides. At (ultra-)slow spreading ridges, the crystallization of sulfides in high-Mg# lower crustal rocks may exert a significant control in shaping the HSE and chalcogen element signature of erupted basalts.

Insights from canonical correlation analysis into sulfide migration during formation of disseminated ores in magmatic Ni–Cu–PGE sulfide deposits

Magmatic Ni–Cu–platinum group element (PGE) sulfide deposits form as the result of segregation of immiscible sulfide liquid from mafic–ultramafic magma. Sulfide ores formed in this process commonly take their places in the lower part of mafic–ultramafic intrusion, and many researchers attribute this phenomenon to gravity settling of dense sulfide droplets within lighter silicate magma. Some laboratory experiments, however, suggest that not all the sulfide droplets can migrate downward through crystal mush, especially those forming disseminated ores. On the basis of geochemical analysis, we employ a multivariate statistical method to investigate whether downward motion of sulfide droplets can happen during formation of disseminated ores. Two typical magmatic Ni–Cu–PGE sulfide deposits, namely the Hongqiling and Kalatongke deposits, were selected, and the relationship between sulfide composition (bulk-rock Cu, Ni, S, and PGE contents) and silicate composition (bulk-rock SiO2, Al2O3, K2O, Na2O, CaO, and MgO contents) was investigated by canonical correlation analysis (CCA). The result shows that there is a strong relationship between the sulfide and silicate compositions in the disseminated ores, which indicates that the sulfide droplets may have formed from the local crystal mushes, and furthermore that they have not migrated away from the crystal mushes. Hence, we conclude that sulfide droplets that form disseminated ores may tend not to migrate downward for long distances after segregating from mafic–ultramafic magma.

Characterisation of road-dust sediment in urban systems: a review of a global challenge

PurposeThe proportion of people living in urbanised areas is predicted to rise to > 65% by 2050, and therefore, more humans than ever will be exposed to urban environmental pollution. Accumulation of organic and inorganic substances on street and road surfaces is a major global challenge requiring scientifically robust methods of establishing risk that inform management strategies. This aim of this contribution is to critically review the global literature on urban road–deposited sediment contamination with a specific focus on variability in sampling and analytical methods.Materials and methodsIn order to assess the concentration of contaminants in global road-deposited sediment (RDS), a comprehensive search of published RDS studies was completed. We review methodological approaches used in RDS studies to highlight the variability in datasets as a result of sampling technique, grain size fractionation, geochemical and mineralogical characterisation methods and establishing the influence of local geology on contaminant concentrations. We also consider emerging contaminants in RDS, and we provide a workflow diagram which promotes a standardised sampling and analysis regime that we believe can reduce data variability and promote collaboration when it comes to tackling the important issue of RDS contamination.Results and discussionAcross the literature, Asia (except China) and Africa are underrepresented in RDS studies despite these continents having the largest and fastest growing populations, respectively. The removal of tetraethyl lead from gasoline produced a noticeable decrease in lead concentrations in global RDS, and platinum group element (PGE) concentrations in RDS were consistent with catalytic converter usage. Research into the impact of electric vehicles on non-exhaust emissions suggests other contaminants such as zinc may become more prominent in the future. Most RDS studies consider grain size fractions larger than > 20 μm due to sampling constraints despite RDS < 20 μm being most relevant to human health. The use of chemical extraction methods to establish contaminant geochemistry is popular; however, most extraction procedures are not relevant or specific to minerals identified in RDS through microscopic and spectroscopic investigations.ConclusionsThis review highlights considerable variability in sampling and analytical approach which makes it difficult to identify broad global patterns in RDS contamination. To remove this variability from future RDS research, this review suggests a workflow plan which attempts to improve the comparability between RDS studies. Such comparability is crucial in identifying more discrete RDS trends and informing future emission policy.

Emergences of New Technology for Ultrafast Automated Mineral Phase Identification and Quantitative Analysis Using the CORIOSITY Laser-Induced Breakdown Spectroscopy (LIBS) System

Geochemical and mineralogical characterization studies play an important role in the definition of mineral deposits. Each mineral system has a unique set of minerals with different chemical makeup and physical properties. Platinum-group elements (PGEs), for example, are scarce resources with many applications. The optimization of extraction process efficiency is therefore crucial to prevent resource shortage and increased bulk prices. To improve the mineral liberation process, high throughput sensors must be added alongside the production line as part of fast process analysis implementation. Current analytical methods are either ineffective to assess PGE content, or unusable in the conditions of the processing facilities. This article shows how Laser-induced breakdown spectroscopy (LIBS) technology, developed by ELEMISSION Inc, can circumvent these drawbacks by enabling automated, ultra-fast, and precise quantitative mineral analyses in any working environment. The drill core samples that were used in this study were collected at the Stillwater platinum group element mine in the United States. The data used for the mineralogical database was validated using the TESCAN Integrated Mineral Analyzer (TIMA) instrument.

Mechanisms for Pd[sbnd]Au enrichment in porphyry-epithermal ores of the Elatsite deposit, Bulgaria

Porphyry Cu can contain significant concentrations of platinum-group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd). In this study, we provide a comprehensive in situ analysis of noble metals (PGE, Au, Ag) for (CuFe)-rich sulfides from the Elatsite, one of the world's PGE-richest porphyry Cu deposits. These data, acquired using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), indicate that Pd was concentrated in all the (CuFe)-rich sulfides at ppm-levels, with higher values in pyrite (~6 ppm) formed at the latest epithermal stage (i.e., quartz–galena–sphalerite assemblage) than in bornite and chalcopyrite (<5 ppm) from the hypogene quartz–magnetite–bornite–chalcopyrite ores. Likewise, Au is significantly more concentrated in pyrite (~5 ppm) than in the (CuFe)-rich sulfides (≤0.08 ppm). In contrast, Ag reaches hundreds of ppm in pyrite and bornite (~240 ppm) but is in much lesser amounts in chalcopyrite (<25 ppm). The inspection of the time-resolved spectra collected during LA-IPC-MS analyses indicates that noble metals are present in the sulfides in two forms: (1) structurally bound (i.e., solid solution) in the lattice of sulfides and, (2) as nano- to micron-sized inclusions (PdTe and Au). These observations are further confirmed by careful investigations of the PGE-rich (CuFe)-rich sulfides by combining high-spatial resolution of field emission scanning electron microscope (FESEM) and focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM). A typical Pd-bearing mineral includes the composition PdTe2 close to the ideal merenskyite but with a distinct crystallographic structure, whereas Au is mainly found as native element. Our detailed mineralogical study coupled with previous knowledge on noble-metal inclusions in the studied ores reveals that noble metal enrichment in the Elatsite porphyry ores was mainly precipitated from droplets of Au-Pd-Ag telluride melt (s) entrained in the high-temperature hydrothermal fluid. These telluride melts could separate at the time of fluid unmixing from the silicate magma or already be present in the latter either derived from deep-seated crustal or mantle sources. Significant enrichment in Pd and Au (the latter correlated with As) in low-temperature pyrite is interpreted as remobilization of these noble metals from pre-existing hypogene ores during the epithermal overprinting.

Using precious metal probes to quantify mid-ocean ridge magmatic processes

Basalts from the East Pacific Rise (EPR), Siqueiros transform zone and Mid-Atlantic Ridge (MAR) area have been analyzed for the platinum-group elements (PGE) and a wide range of incompatible elements. The low PGE content of the most primitive mid-ocean ridge basalts (MORB) suggests that they leave the mantle sulfide-saturated but become sulfide under-saturated, as a consequence of decompression, during their ascent from the mantle to the MOR magma chamber. Because the pressure drop is small, the ascending magma enters the magma chamber slightly sulfide under-saturated and requires only a small amount of fractional crystallization to return it to sulfide-saturation. Sulfide-saturation is marked by the Pd content of the melt falling by over an order of magnitude at ca. 9.5 wt.% MgO. However, once the magma has become sulfide-saturated, it shows no evidence of a further decline in Pd with decreasing MgO as the system evolves. This must result from regular replenishment of the underlying axial magma chamber by fresh batches of primitive magma. Most replenishments occur when the MgO content of the resident melt in the magma chamber is between ∼9 to 6.5 wt.% MgO. We combine the tight constraints imposed by highly compatible Pd abundances, with those imposed by strongly incompatible elements, to produce the first model that successfully accounts for the variations of both classes of elements in open system mid-ocean ridges magma chambers for normal-type MORB (N-MORB). We show that the lack of decline in the Pd content of sulfide-saturated mid-ocean ridge basalts, with decreasing MgO, requires frequent small replenishments (between 1% and 4%) of similar magnitude, rather than large initial inputs that systematically decline from near 100% to near zero during the life of an individual ridge system.Assuming the spreading rate of ∼110 mm/yr for the EPR at 9°N, and 14 yr between the 1991–1992 and 2005–2006 eruptions, the calculated volume of erupted and intruded magma is 2.3 × 103 m3/m of ridge length. If the expelled melt represents 0.5% of the accessible magma in the chamber, as suggested by the Pd modeling, the volume of the magma accessible during tapping is 4.6 × 105 m3/m of ridge length.

Petrogenesis and ore potential of Permian mafic intrusions in the Dacaotan area, eastern Tianshan: Constraints from whole‐rock platinum‐group element contents and Sr–Nd isotopes

The eastern Tianshan is an important Ni–Cu mineralization belt that contains several ore‐bearing mafic–ultramafic intrusions. The eastern part of this belt has been well studied, whereas the western part is poorly studied. Here, we present studies of two mafic intrusions (DC3 and DC4) from the Dacaotan area in the western part of the eastern Tianshan. The gabbrosof the DC3 and DC4 intrusions contain plagioclase and clinopyroxene, and are characterized by light rare earth element enrichment, negative Nb anomalies, depleted platinum group element contents, high and variable Cu/Pd ratios, positive εNd (6.0–7.5) values, and low initial 87Sr/86Sr ratios (0.7033–0.7036). The two intrusions have geochemical affinities with intrusions in the Huangshan area, despite mineralogical differences, with orthopyroxene and amphibole being present in the Huangshan intrusions. The two studied mafic intrusions formed from a high‐Mg basaltic magma derived from anhydrous and depleted mantle. Due to the low degree (&lt;8%) of partial melting, the magma was PGE‐depleted and sulphide remained in the mantle source. The PGE contents were further depleted by early magmatic sulphide segregation. Given the limited contamination (&lt;10%) by the upper crust and coeval A‐type granites, these two intrusions have poor potential for Ni–Cu sulphide mineralization.

Low-Sulfide Platinum Group Element Ores of the Norilsk-Talnakh Camp

Abstract Low-sulfide platinum group element (PGE) mineralization of the Norilsk-type intrusions is located within the Upper Gabbroic Series, which comprises rocks heterogeneous in texture and composition. The highest grade of 10 to 50 g/t PGEs is confined primarily to chromitiferous taxitic gabbrodolerite, which forms irregular lens- and vein-like bodies that interfinger with contact gabbrodolerite, intrusion breccia, leucogabbro, and gabbrodolerite variably enriched in olivine, from olivine free up to picritic compositions. The abundant amygdules and pegmatoidal textures in Upper Gabbroic Series taxitic rocks, as well as the high enrichment of halogen in minerals (e.g., ≤4.6 wt % Cl in apatite), indicate a higher volatile content of the local magma compared to the magma that precipitated the Main Series. The observed diversity in spinel compositions, which evolve from chromite to Cr magnetite as well as toward hercynite, titanomagnetite, and ulvöspinel, is also indicative of crystallization from a fluid-saturated mush that subsequently reacted, to varying degrees, with contaminated trapped melt and immiscible fluid. The high PGE/S ratio is a primary feature of this mineralization style, albeit the ratio partly increased during sulfide replacement and resorption. The PGE tenor of bulk sulfides calculated as ΣPGE (g/t) in 100% sulfides exceeds 160 and may reach up to 1,400 to 2,500 in low-S ores (0.2–3 wt % S), whereas the value does not exceed 42 in the Talnakh disseminated ore and ranges from 35 to 120 in the Norilsk disseminated ore (1–10 wt % S). Several PGE peaks in the vertical sections correlate well with Cu, Ni, S, and Cr peaks, as well as with observed elevated proportion of amygdules. Low-sulfide ores are composed of two primary sulfide assemblages of pyrrhotite + pentlandite + chalcopyrite and pentlandite + pyrrhotite. The primary sulfides are depleted in the heavier 34S isotope relative to sulfides of the corresponded main orebodies (e.g., mean δ34S = 8.9‰ versus δ34S = 12.3‰, respectively, in the Kharaelakh intrusion). A secondary pyrite + millerite + chalcopyrite assemblage has isotope composition enriched in 34S by 2 to 6‰ δ34S with respect to primary sulfides. The directly measured PGE content in sulfides (e.g., 11–2,274 g/t Pd in pentlandite and 0.10–33.3 g/t Rh in pyrrhotite) is within the range of the typical Norilsk-type magmatic sulfide compositions. The textural setting and diversity of platinum group minerals (PGMs) favor the hypothesis of fluid-controlled crystallization. However, the distinct PGM assemblages in Norilsk 1 and Talnakh-Kharaelakh low-sulfide ores are comparable with those of the corresponding presumably magmatic disseminated and massive orebodies. The most remarkable characteristic is the widespread Pt-Fe alloys in Norilsk 1 and their absence in Talnakh-Kharaelakh, which is interpreted to reflect better preservation of the high-temperature PGMs in Norilsk 1 in contrast to their substantial replacement in more oxidized fluid-enriched environments in Talnakh-Kharaelakh.

Platinum group elements in gabbroic intrusions from the Valerianov‐Beltau‐Kurama arc: Implications for genesis of the Kalmakyr porphyry Cu–Au deposit

Porphyry Cu–Au ores areamong the important types of porphyry deposits. Some of these are enriched in Pd and Pt, which in some cases have economic potential for PGE (platinum group element) recovery. The behaviour of PGE and S‐saturation in mafic intrusions associated with porphyry deposits are, however, poorly constrained. Here we investigate the PGE concentrations of gabbroic intrusions from Akcha, Beleuti, and Kalmakyr in the Almalyk porphyry Cu–Au ore field in Uzbekistan through Ni–S analyses employing fire assay‐isotope dilution method. The results reveal extremely high Pd/Ir ratio and a negative Ru anomaly for the Beleuti and Akcha gabbro which we attribute to fractional crystallization of olivine and Ru–Os–Ir alloys. The extremely high Cu/Pd ratio (2.56 × 105–2.98 × 106) and depleted PGE contents of the Kalmakyr gabbro possibly represent immiscible separation of sulphide. During the emplacement of the parental magma of Kalmakyr gabbro, crustal contamination might have resulted in S‐saturation and sulphide segregation. Sulphide‐bearing crust was remobilized during the increasing maturity of the island and long‐lived arc magmatism, which released the sulphide into the hydrothermal system of the porphyry deposit. We propose that this process favoured the enrichment of Pt–Pd and sulphide in the Kalmakyr porphyry Cu–Au deposit.

Geochemical characteristics of platinum-group elements in polymetallic nodules from the Northwest Pacific Ocean

Polymetallic nodules and cobalt (Co)-rich crusts are enriched in platinum-group elements (PGEs), especially platinum (Pt) and may be important sinks of PGEs. At present, little information is available on PGEs in polymetallic nodules, and their geochemical characteristics and the causes of PGEs enrichment are unclear. Here, PGEs of polymetallic nodules from abyssal basin in the Marcus-Wake Seamount area of the Northwest Pacific Ocean are reported and compared with the published PGEs data of polymetallic nodules and Co-rich crusts in the Pacific. The total PGEs (LPGE) content of polymetallic nodules in study area is 258×10−9 in average, markedly higher than that of Clarion-Clipperton Zone (CCZ) nodules (ΣPGE=127×10−9) and lower than that of Co-rich crusts in the Marcus-Wake Seamount (ΣPGE=653×10−9), similar to that of Co-rich crusts in the South China Sea (ΣPGE=252×10−9). The CI chondrite-normalized PGEs patterns in different regions of polymetallic nodules and cobalt-rich crusts are highly consistent, with all being characterized by positive Pt and negative Pd anomalies. These results, together with those of previous studies, indicate that PGEs in polymetallic nodules and Co-rich crusts are mainly derived directly from seawater. Pt contents of polymetallic nodules from the study area are negatively correlated with water depth, and Pt/ΣPGE ratios in nodules there are also lower than those of the Co-rich crusts in the adjacent area, indicating that sedimentary water depth and oxygen fugacity of ambient seawater are the possible important controlling factors for Pt accumulation in crusts and nodules.

Platinum-group element and Au geochemistry of Late Archean to Proterozoic calc-alkaline and alkaline magmas in the Yilgarn Craton, Western Australia

The Yilgarn Craton of Western Australia is one of the largest Archean cratons in the world and is well-known for its metal endowment. In order to provide new insights into its metallogenic fertility and the nature of the upper mantle that lies underneath the craton, this study investigates the poorly constrained platinum-group element (PGE) and gold signatures of a selected suite of calc-alkaline lamprophyres, ultramafic lamprophyres, carbonatites and orangeites, ranging in age from the Proterozoic to the Late Archean. Proterozoic ultramafic lamprophyres and carbonatites within the Eastern Goldfields Superterrane (EGS) of the Yilgarn Craton have anomalously low PGE contents (Ir = 0.1–1.3 ppb; Ru = <0.08 to 3.6 ppb; Rh = <0.04 to 0.4 ppb; Pt = <0.17 to 3.3 ppb; Pd = <0.12 to 4.4 ppb) and variable Au contents (<0.4 to 9.8 ppb). Based on their low PGE contents and unfractionated PGE patterns with (Pd/Ir)N ratios up to ~6, it is suggested that these magmas may derive from extremely low-degree partial melting of the convective mantle. Conversely, the Late Archean calc-alkaline lamprophyres in the EGS exhibit comparatively fractionated PGE patterns with (Pd/Ir)N ratios up to ~27 and variable Au concentrations, including localised anomalous enrichments (up to 13.8 ppb). The fractionated PGE patterns are explained by incongruent melting of mantle sulfides with potential contribution from PPGE- and Au-bearing alloys, which would preferentially contribute Pt, Pd and Au over Ir, Ru and Rh. Combination of elevated Au and volatile contents in these rocks is consistent with derivation from a mantle source that was metasomatised by slab-derived fluids along a laterally extensive Late Archean subduction setting. This process may have provided a first-order control on the exceptional gold endowment of the Eastern Goldfields Superterrane.

Petrogenesis, platinum-group element geochemistry and geodynamic evolution of the Cretaceous Chilas gabbros, Kohistan island arc, NE Pakistan

Kohistan, an intra-oceanic arc, formed due to the India-Asia collision-related tectonics. The arc is comprised of mafic-ultramafic and crustal lithologies. Chilas Complex, one of the major mafic-ultramafic body that lies at the base of the Kohistan arc, is dominantly composed of massive gabbronorites with local ultramafic-mafic intrusive bodies. The ultramafic rocks were considered as the products of fractional crystallization whereas gabbronorites were reported to have formed at the root zone of the magma chamber either from melts or due to fractional crystallization, based on major and trace element data. To understand the petrogenesis and origin of the Chilas gabbros, we conducted platinum group elements (PGEs) geochemistry combined with whole-rock major and trace element compositions. Geochemical data of the Chilas gabbros show tholeiite series, likely derived from a depleted lithospheric mantle source via peridotite melts. Presence of hornblende and relatively higher Al/Ti ratios of clinopyroxene in the Chilas gabbros suggest hydrous magma, ascribed to mantle wedge metasomatism by slab-derived fluids. Poor correlations between MgO vs. Ni, Cr, and V, Ni vs. Cr, Dy/Yb vs. SiO2, Sr/Y vs. Eu/Eu* and relatively low TiO2 indicate a minimal role of fractional crystallization. Low contents of LOI (0–3.24 wt%), Ce/Ce* (0.92–1.01), and positive relation of La, Ta, and Hf with Zr strongly support the insignificant impact of hydrothermal alteration. Enrichment of PGEs, such as Pt (0.63–13.75 ppb), Pd (0.43–13.87 ppb), and lower Pd/Ir ratios (0.76–40.04) suggest low degree partial melting of the parent magma. Higher Pd, Pd/Ir ratios compared to Pt and Pt/Pd, combined with enrichment of PPGE over IPGE, suggest the participation of slab-dehydrated fluids and mantle metasomatism however Cu/Ir vs. Ni/Pd, V-Pd/Ir and La-Pd/Ir ratios point towards olivine fractionation in the magma. Lower Cu/Pd ratios, relationships of Ru and Pt against Cr, and Os diminution corroborate S-undersaturation in parental magma. The PGEs contents and Pd/Pt ratios attest depleted mantle source for their production. In view of Cu/Zr and Cu/Pd ratios, it is substantiated that the sulphide segregation cannot be a promising reason for PGEs depletion. Therefore, we infer PGEs depletions in parental magma are due to PGEs-depleted mantle source, though sulfide retention in mantle source cannot be eliminated. The geochemical fingerprints in tectonic diagrams and negative anomalies of Nb and Zr in the studied samples provide credible facts that favour arc magmatism. Based on major and trace element data and PGEs values, we consider that the Chilas gabbros were formed from a lithospheric mantle that was metasomatized by fluids generated at the mantle wedge and derived from mafic melts in an arc setting. Geochemical data and their plotting on various tectonic discrimination diagrams indicate Chilas Complex as a remnant of the Neo-Tethyan oceanic arc system.

Formation of the Flatreef deposit, northern Bushveld, by hydrodynamic and hydromagmatic processes

New lithological and whole rock compositional data show that the main platinum-group element (PGE) horizons of the Flatreef succession show strong compositional similarities to the Merensky and Bastard reefs of the western Bushveld Complex (WBC), notably in terms of many immobile and incompatible minor and trace elements such as TiO2, Zr, Y, and REE. However, Al2O3, CaO, and Na2O contents are markedly lower in the Flatreef, whereas MgO contents are higher. In view of broadly similar silicate mineral compositions in the Flatreef and the WBC reefs, we suggest that the major element compositional differences between the rocks are largely due to higher modal proportions of orthopyroxene and olivine and lower proportions of plagioclase in the Flatreef. The thickness of the mineralised interval is much greater in the Flatreef than in the WBC (several 10 s of m vs ~ 1 m) and the abundance of sulfides in the Flatreef is typically somewhat higher (on average ~ 1.5% vs ~ 1%). These data, complemented by textural observations, are interpreted to reflect enhanced hydrodynamic crystal sorting accompanied by percolation of sulfide melt through incompletely solidified cumulates. Further genetic constraints are provided by metal data: The concentration of Ni (~ 3000 ppm) in the Flatreef is broadly similar to that in the Merensky Reef of the WBC, but Cu contents are markedly higher (average ~ 1500 ppm vs 700 ppm in the WBC). The concentrations of most PGE are slightly lower (Flatreef ~ 1.5–2 ppm Pt, ~ 100–150 ppb Rh; WBC MR 3.7 ppm Pt, 240 ppb Rh), but Pd has broadly similar contents (Flatreef ~ 1.2–2 ppm; WBC MR 1.54 ppm). The relatively high Cu content of the Flatreef is interpreted as a result of assimilation of Cu sulfides from the sedimentary floor rocks. The reason for the enrichment of Pd relative to Pt, especially in the basal rocks, remains unclear. It could reflect mobilisation of Pd via a fluid phase from the country rocks or the interior of the intrusion, relatively enhanced partitioning of Pd into the sulfides, or relative Pt depletion of the earliest magma pulses in response to Pt alloy fractionation triggered by contamination with reducing country rocks.

Magmatic PGE Sulphide Mineralization in Clinopyroxenite from the Platreef, Bushveld Complex, South Africa

The Platreef, at the base of the northern limb of the Bushveld Complex in South Africa, hosts platinum-group element (PGE) mineralization in association with base-metal sulphides (BMS) and platinum-group minerals (PGM). However, whilst a magmatic origin of the stratiform mineralization of the upper Platreef has been widely confirmed, the processes responsible for the PGE and BMS mineralization and metasomatism of the host rocks in the Platreef are still under discussion. In order to contribute to the present discussion, we present an integrated petrographical, mineral-chemical, whole-rock trace- and major-element, sulphur- and neodymium-isotope, study of Platreef footwall clinopyroxenite drill core samples from Overysel, which is located in the northern sector of the northern Bushveld limb. A metasomatic transformation of magmatic pyroxenite units to non-magmatic clinopyroxenite is in accordance with the petrography and whole-rock chemical analysis. The whole-rock data display lower SiO2, FeO, Na2O and Cr (&lt;1700 ppm), and higher CaO, concentrations in the here-studied footwall Platreef clinopyroxenite samples than primary magmatic Platreef pyroxenite and norite. The presence of capped globular sulphides in some samples, which display differentiation into pyrrhotite and pentlandite in the lower, and chalcopyrite in the upper part, is attributed to the fractional crystallization of a sulphide liquid, and a downward transport of the blebs. In situ sulphur (V-CDT) isotope BMS data show isotopic signatures (δ34S = 0.9 to 3.1 ‰; Δ33S = 0.09 to 0.32‰) close to or within the pristine magmatic range. Elevated (non-zero) Δ33S values are common for Bushveld magmas, indicating contamination by older, presumably crustal sulphur in an early stage chamber, whereas magmatic δ34S values suggest the absence of local crustal contamination during emplacement. This is in accordance with the εNd (2.06 Ga) (chondritic uniform reservoir (CHUR)) values, of −6.16 to −6.94, which are similar to those of the magmatic pyroxenite and norite of the Main Zone and the Platreef in the northern sector of the northern Bushveld limb. Base-metal sulphide textures and S–Se-ratios give evidence for a secondary S-loss during late- to post-magmatic hydrothermal alteration. The textural evidence, as well as the bulk S/Se ratios and sulphide S isotopes studies, suggest that the mineralization in both the less and the pervasively hydrothermally altered clinopyroxenite samples of Overysel are of magmatic origin. This is further supported by the PPGE (Rh, Pt, Pd) concentrations in the BMS and mass-balance calculations, in both of which large proportions of the whole-rock Pd and Rh are hosted by pentlandite, whereas Pt and the IPGE (Os, Ir, Ru) were interpreted to mainly occur in discrete PGM. However, the presence of pentlandite with variable PGE concentrations on the thin section scale may be related to variations in the S content, already at S-saturation during magmatic formation, and/or post-solidification mobilization and redistribution.

Critical elements in porphyry copper deposits of China

As the world’s major source of Cu, Mo, and Au, porphyry copper deposits are magmatic-hydrothermal systems in which base and precious metals are deposited from aqueous solutions at temperatures generally >300°C. During formation of the deposits, metal-transporting fluids typically affected large volumes (up to ~100 km3) of upper crustal rocks, which has led to enormous mass redistribution and local concentration of many elements. Several critical elements, including Re, Se, and Te that are typically not found as primary ores, are locally concentrated in some porphyry copper deposits. Presently, mining and milling of porphyry copper deposits supply ~80% of the world’s Re and nearly all of the Se and Te. China has about 70 economic porphyry copper deposits, including 11 giant and 16 large deposits, with total pre-mining resources of ~78 million tonnes (Mt) Cu averaging 0.2% to 1% Cu, ~4.7 Mt Mo averaging 0.01% to 0.08% Mo, and 1400 tonnes (t) Au averaging 0.5 g/t Au. Rhenium, Se, Te, and PGE (platinum group elements) have been reported to be enriched in some porphyry copper deposits in China, but their tonnage, grade, occurrence, and resource potential remain unclear. In this study, based on a simple synthesis of critical elements in the porphyry copper deposits worldwide and geological characteristics of Chinese porphyry copper deposits, we systematically summarize these attributes of critical elements, particularly Re, in the porphyry copper deposits of China. The porphyry copper deposits in China are mainly concentrated in the following belts or districts: The Gangdese belt in southern Tibet, the Yulong belt in eastern Tibet, the Duolong district in central Tibet, the Zhongdian belt in northwestern Yunnan Province, the Central Asian orogenic belt across northern China, the Zhongtiaoshan belt in Shanxi Province, the Middle-Lower Yangtze River Valley belt, and the Dexing district in Jiangxi Province. Chinese porphyry copper deposits were formed during Paleoproterozoic, Ordovician, Carboniferous, Late Triassic to Early Cretaceous, and Eocene to Miocene, with the majority forming during the latter two time periods. Approximately 45% of the giant and ~30% of the large porphyry copper deposits in China formed in arc settings, whereas at least 35% of the giant and ~45% of the large porphyry copper deposits in China occured in post-collisional settings. The porphyry copper deposits in China typically contain ~3−313 t of Re at average grades ranging from 0.03 to 0.5 g/t Re, with ten deposits containing >50 t Re. The Re-rich porphyry copper deposits in China were mainly formed during Jurassic and Eocene to Miocene. The three largest deposits (Yulong, Jiama, and Qulong), in terms of contained Re, were formed during Eocene to Miocene and in a postcollisional setting. Rhenium in these porphyry copper deposits mainly occurs in molybdenite, and is associated with potassic and/or phyllic alteration. Average Re content in molybdenite from these deposits ranges from 30 to 1000 ppm, but shows a negative correlation with the Mo grade of the corresponding deposit. In contrast, there are only limited data on the endowment of Se, Te, and PGE for Chinese porphyry copper deposits. Similar to porphyry copper deposits worldwide, Se, Te, and PGE in Chinese porphyry copper deposits are concentrated in the sulfide minerals. The contents of Se and Te in sulfide minerals from several deposits (e.g., Bolong, Shaxi) range from ~3 to 700 ppm and are typically highest (generally >300 ppm) in Cu-bearing sulfides (e.g., bornite, chalcopyrite). Concentrations of PGE in ores of Chinese porphyry copper deposits are highly variable, with Pd+Pt contents ranging from 0.2 to 450 ppb. In summary, Chinese porphyry copper deposits, particularly those in postcollisional settings, show similar grades of Re, Se, Te, and PGE to porphyry copper deposits worldwide, indicating a large potential of these critical elements in Chinese porphyry copper deposits to meet the nation’s economic needs. To better understand the occurrence, resource potential, and enrichment processes of critical elements in the porphyry copper deposits of China, detailed case studies and regional comparisons, as well as improvements in analytical techniques, are a pressing need.

PGE Prospecting Features by Results of SP and Geoelectrochemistry Methods

Platinum-group elements (PGE) prospecting can be carried out with use of geochemical or geophysical methods. Geochemical methods can study objects located at the surface only, and geophysical methods are not always effective because of too low concentrations of PGE in the host rocks do not change the ores physical properties. Geoelectrochemical methods are suitable for deep-lying ores prospecting. Problem of movable forms creation of passive PGE can be fixed takin into account natural electrical processes. It is shown by laboratory experiment and tested during field works. Laboratory data confirmed the influence of electric current on the transition of PGE dozens presents in the dissolved form. The complex geophysical and geoelectrochemical surveys was carried out on the territory of Aganozerskiy (South Karelia), Svetloborskiy and Kachkanar (Middle Urals) massifs containing PGE mineralization. Preconditions for the creation of self-potential (SP) anomalies of redox nature are allocated within these massifs and characteristics of self-potential anomalies are investigated. SP sources are prerequisite for the mobile PGE forms halos creation if they are close to platinum mineralization zones. Moving up in the jet halos by natural ionic flotation mechanism and capillary rise in a circle of meteoric water evaporation and seepage can form zones of elevated concentrations of PGE secondary fixed forms near the surface, which can be detected by different geoelectrochemical methods. It can be concluded that geoelectrochemical methods are not always effective, but in the presence of sources of SP in a geological environment. The interpretation of the geoelectrochemistry anomaly for noble metals should take into account the effect of activators of the mobile forms formation.

Spectroscopic Assessment of Platinum Group Elements of PM10 Particles Sampled in Three Different Areas in Jeddah, Saudi Arabia.

Platinum group elements (PGE) including Ru, Rh, Pt and Pd have been quantified in air particulate matter with an aerodynamic diameter equal or less than 10 microns (PM10) using inductively coupled plasma mass spectrometry (ICP-MS). PM10 aerosols have been collected from three sites representing various activities in Jeddah city, Saudi Arabia. These locations are residential site with heavy traffic, industrial site and heavy traffic and a light traffic site outside the city. To obtain reasonable data of the PGE concentrations, a group from 10 to 15 PM10 samples were collected every month. The annual and seasonal variation of the mass concentration of the PGE were demonstrated. In all locations, Pt and Pd were relatively higher than Ru and Rh possibly because their main use is in automobile catalytic converters. Concentrations of observed PGE in PM10 could be arranged in ascending order as: Rh < Ru < Pd < Pt. In case of Ru and Pt, there are clear similarities in terms of the overall mean concentrations at the sampling locations. Due to the high concentration of Ru, Rh and Pd at low traffic site, there are certainly other sources of these elements rather than vehicle catalytic converters. However, at the industrial/heavy traffic location, high concentrations of Ru were detected during February 2015. In addition, high Pt concentrations were also detected at the light traffic site during May 2015. Results indicate that Pt source in PM10 is mainly the automobile catalytic converters.

Early sulfide saturation in arc volcanic rocks of southeast China: Implications for the formation of co-magmatic porphyry–epithermal Cu–Au deposits

It is widely considered that arc magmas are highly oxidized, and can thus dissolve a large amount of sulfur, thereby preventing significant sulfide saturation prior to fluid saturation. Therefore, chalcophile metals (e.g., Cu and Au) are retained in the magma and finally extracted by exsolved hydrothermal fluids. To test this hypothesis, we analyzed the abundances of platinum-group elements (PGEs) in a suite of arc volcanic rocks, which are the extrusive counterparts of magmas associated with the world-class Zijinshan porphyry–epithermal Cu–Au ore district in SE China. All of these volcanic rocks are depleted in PGEs (e.g., Pd = 0.02–0.40 ppb) in comparison with fertile arc magmas, and the PGE contents decrease with decreasing MgO from basalt to dacite. The results show that the parental magmas for these rocks reached sulfide saturation before they evolved to 7 wt.% MgO, which is earlier than the onset of magnetite crystallization. Sulfide liquid and monosulfide solid solution (MSS) were removed from the magma before it evolved into a dacitic composition. This process extracted most of the Au and Cu from the magma. Modeling results indicate that Au concentrations would not exceed 7–10 times the Pd concentrations in the residual silicate magma, irrespective of the partition coefficients between the sulfide and silicate melt. Given the low Pd contents in dacitic arc magmas worldwide, depletion of Au and Cu might be a common feature of highly evolved arc magmas. Thus, the hydrothermal ore fluids separated from such evolved arc magmas would not contain enough metals to form the giant Zijinshan porphyry–epithermal Cu–Au ore district. We propose a model in which the magmas parental to the arc volcanic rocks achieved S saturation, and thus large amounts of sulfides accumulated in the underlying magma chamber before the magmas were extruded from depth to the surface. During solidification of the magma chamber, these deposits formed from exsolved magmatic hydrothermal fluids that dissolved abundant pre-existing magmatic Cu–Au-rich sulfide assemblages. Release of large amounts of Au, Cu and S to the ore-forming aqueous fluids by dissolution of sulfides can account for the metal and S budgets of giant porphyry–epithermal Cu–Au deposits.

Sulfide segregation mechanism of magmatic Ni mineralization in western Beishan region, Xinjiang, NW China: Case study of the Hongshishan mafic–ultramafic complex

A series of early Permian mafic–ultramafic complexes associated with Ni-Cu mineralization are distributed in western Beishan region, Xinjiang, NW China. The Ni mineralization in this area consists of two sub-belts, which have the same magma conduit at depth, similar rock types and similar emplacement ages, but different mineralization types. The Ni mineralization in the north (Hongshishan) sub-belt consists of low-tenor disseminated sulfide, whereas that in the south (Pobei) sub-belt consists of disseminated sulfide and vein-type sulfide with high tenor, suggesting different sulfide segregation mechanisms. The Hongshishan complex consists of dunite, wehrlite, olivine clinopyroxenite, troctolite, olivine gabbro, and gabbro (from earlier to later). The mafic rocks occur along margins of the complex, and the mineralized ultramafic rocks are confined to the center. The dunite and wehrlite host significant amounts of disseminated sulfide. The parental magma of the Hongshishan complex may have originated from 17.0% partial melting of the depleted mantle. It is characterized by high temperature (1368 ℃), high Mg (picritic affinity, 14.52 wt% MgO), oxidation and platinum group element (PGE) depletion, as constrained by the major and trace elements, olivine and chromite mineralogy, and PGE contents. Two stages of sulfide segregation have been recognized. Early sulfide segregation at depth, which is indicated by elevated Cu/Pd ratios and sulfide inclusions in chromite, produces the PGE-depleted parental magma. Later in situ segregation results in disseminated sulfide mineralization. Model of the olivine crystallization and PGE content shows that 0.01%−0.015% of the sulfide is segregated in situ, with R = 100–500. Significant crustal contamination is suggested by xenoliths of wall rock as well as negative Nb, Ta, and Ti anomalies and positive Pb and Sr anomalies in intrusive rocks. The addition of crustal Si and decrease in FeO by fractional crystallization are the main factors triggering S-oversaturation and later in situ segregation. The early segregation at depth is more likely caused by the addition of crustal S, although the δ34S values of sulfides (-0.75‰ to 1.15‰) indicate the isotopic signature of mantle sulfur. For comparison, the development of vein-type sulfide mineralization in the Poyi deposit is ascribed to assimilation of S-bearing Archean rocks. Finally, a model of “early segregation at depth + later in situ segregation + multistage pulsation” is proposed for the Ni mineralization in this area.

Determination of platinum group elements in catalysts recycling products by SEM with energy dispersive spectrometer

Analysis of platinum group elements (PGE) extracted from various catalysts used in the car, petroleum and chemical industries requires use of microanalytical methods. PGE content in the platinum powder concentrates K176 and K177 was studied by SEM-EDS. The content of main elements was determined using analytical lines Fe Kα1, Si Kα1, Sn Lα1, Pt Lα1, Re Lα1. The obtained data for the chemical composition are in good agreement with the result obtained by X-ray fluorescence analysis and ICP-MS method. Powdered platinum concentrates are considered to be ferrosilicide (FeSi), where PGE are localized at the phase boundaries and in separate patches of the K176 sample, or distributed over the volume of particles in the K177 sample.