Behaviour Of Platinum-group Elements Research Articles

Redox control of the partitioning of platinum and palladium into magmatic sulfide liquids

The partitioning behavior of platinum group elements in magmas is critical for their use as tracers of planetary accretion and in understanding magmatic sulfide deposits. Here we use laboratory experiments to determine sulfide liquid–silicate melt partition coefficients for platinum and palladium at 1.5 GPa, 1400 °C, and oxygen fugacity 1.5–2 log units above the fayalite–magnetite–quartz buffer. We find that the partitioning coefficients of these elements are 2.3 × 105 to 1.1 × 106 and are independent of the platinum and palladium concentration in the system. Combined with previous data obtained at oxygen fugacity below the fayalite–magnetite–quartz buffer, this indicates redox-controlled partitioning behavior whereby at oxidizing conditions platinum- and palladium-enrichments are achieved through their dissolution in sulfide liquids, while at reducing conditions the entrapment of platinum- and palladium-rich clusters in sulfide liquids is more critical. This redox-controlled partitioning behavior should be considered when studying crust–mantle differentiation and the formation of magmatic sulfide deposits.

Behavior of Platinum-Group Elements during Hydrous Metamorphism: Constraints from Awaruite (Ni3Fe) Mineralization

Abstract Natural Fe-Ni alloys are common in meteorites and, presumably, the Earth’s core, where they host significant platinum-group elements (PGE). However, little is known on PGE concentrations in hydrothermal or metamorphic Fe-Ni alloys (i.e., awaruite Ni3Fe) from terrestrial rocks. In this work, we examine the geochemistry of awaruite and related minerals from several placer deposits sourced from the suprasubduction ophiolitic (Kamchatsky Mys, Karaginsky Island, and Mamet) and Ural-Alaskan (Galmoenan) complexes of Kamchatka and the Koryak Highlands (Far East Russia) in order to assess the abundance of PGE in awaruite and constrain their mobility under metamorphic and hydrothermal conditions. Studied awaruite from ophiolitic and Ural-Alaskan type complexes formed via desulfurization of pentlandite during serpentinization. Three groups of platinum-group minerals (PGMs) are associated with awaruite from Kamchatsky Mys: (1) Pt-Fe alloys such as ferronickelplatinum (Pt2FeNi) or unnamed Ni2FePt alloys; (2) Os-Ir-Ru alloys of various composition; (3) Pd-Sb minerals which form together with serpentine during hydrothermal alteration. Despite the abundance of PGM inclusions, no significant PGE concentrations were measured in awaruite from the Kamchatsky Mys, Karaginsky Island, or Mamet ophiolites. In contrast, pentlandite relicts in awaruite from placers related to the Galmoenan Ural-Alaskan type complex contain exceptionally high, previously unreported, Os (up to 540 ppm). Awaruite that forms on behalf of this pentlandite does not show any significant Os enrichment. Rare Galmoenan awaruite analyses yield up to 3 ppm Pd. The new data are not in complete accordance with previous studies that reported relatively high (up to first 10 ppm) PGE content in awaruite. We attribute this to low PGE concentration in precursor sulfides and preferential partitioning of PGE into discrete secondary PGM within awaruite. Nevertheless, abundant inclusions of secondary PGM in awaruite provide evidence of PGE mobility during metamorphic and hydrothermal alteration of ultramafic rocks.

Volcano–Plutonic Complex of the Tumrok Range (Eastern Kamchatka): An Example of the Ural-Alaskan Type Intrusion and Related Volcanic Series

Zoned plutons, composed of dunites, pyroxenites, and gabbroic rocks, have been referred to as the Ural-Alaskan type complexes (UA-complexes) and occur in numerous paleo-arc settings worldwide. Many of these complexes are source rocks for economic placers of platinum-group metals. Thus, it is important to understand how UA-complexes form and the origin and behavior of platinum-group elements (PGEs). It is widely assumed that the UA-complexes result from differentiation of supra-subduction high-Ca high-Mg sub-alkaline magmas. However, there is a lack of direct evidence for the existence and differentiation of such magmas, mainly because cases of UA-complexes being spatially and temporally linked to co-genetic volcanics are unknown. We studied an UA-complex from the Tumrok range (Eastern Kamchatka) where a dunite-clinopyroxenite-gabbro assemblage is spatially and temporary related to high-Ca volcanics (i.e., picrites and basalts). Based on the mineral and chemical composition of the rocks, mineral chemistry, and composition of melt inclusions hosted within rock-forming minerals, we conclude that the intrusive assemblage and the volcanics are co-genetic and share the same parental magma of ankaramitic composition. Furthermore, the compositions of the plutonic rocks are typical of UA-complexes worldwide. Finally, the rocks studied exhibit a full differentiation sequence from olivine-only liquidus in picrites and dunites to eutectic crystallization of diopside or hornblende, plagioclase, and K-Na feldspar in plagio-wehrlites and gabbroic rocks. All these results make the considered volcano–plutonic complex a promising case for petrological studies and modelling of UA-complex formation.

Stability and structure of platinum sulfide complexes in hydrothermal fluids

Knowledge of the chemical speciation of platinum and the solubility of Pt-bearing minerals in hydrothermal fluids is required to assess Pt transport, remobilization and concentration in the Earth’s crust. In this study, we combined PtS(s) solubility measurements in a hydrothermal reactor allowing fluid sampling, in situ X-ray absorption spectroscopy, and first-principles molecular dynamics simulations to systematically investigate the structure, composition and stability of Pt sulfide complexes in model aqueous H2S-bearing solutions up to 300 °C and 600 bar. The results demonstrate that tetrahydrosulfide, PtII(HS)42–, is the major Pt-bearing complex in aqueous solutions saturated with PtS(s) over a wide range of dissolved hydrogen sulfide concentrations, from < 0.2 to ∼ 2 molal. The equilibrium constants of the dissolution reaction of PtS(s) generated in this study, PtS(s) + 3 H2S(aq) = Pt(HS)42– + 2 H+ (β4), are described by the equation log10β4 = 0.9 × 1000/T(K) – 19.7 (± 0.5) over the temperature range 25–300 °C and pressure range Psat–600 bar. Furthermore, the stepwise formation constants of four PtII-HS complexes, Pt(HS)+, Pt(HS)20, Pt(HS)3–, and Pt(HS)42–, were estimated, for the first time, from molecular dynamics simulations. The generated constants indicate that the maximum solubility of platinum in the form of Pt(HS)42– in reduced H2S-dominated hydrothermal fluids at moderate temperatures (≤ 350 °C) is close to 1 ppb Pt at near-neutral pH of 6–8 and hydrogen sulfide concentrations of 0.1 molal. Although this solubility is much greater than that of Pt-Cl, Pt-OH and Pt-SO4 complexes at such conditions, it is yet too low to account for significant Pt transport in most shallow-crust hydrothermal settings, characterized by the presence of both sulfide and sulfate. Complexes with S-bearing ligands, very likely other than H2S/HS–, such as S3–, would be required to account for Pt hydrothermal mobility. Our results provide a basis for more systematic future studies, using combined approaches, of the role of hydrothermal fluids in the behavior of platinum group elements in nature.

Sheared and Granular Peridotites from the Udachnaya–East Kimberlite (Yakutia): Mineralogy, Chemistry, and PGE Patterns

Abstract —Mantle xenoliths of fresh sheared and granular peridotites from the Udachnaya kimberlite pipe (Yakutian kimberlite province, Siberia, Russia) are studied in terms of mineralogy, chemistry, and behavior of platinum-group elements (PGE), with a focus on difference between the two types of peridotites and on the role of PGEs in their origin. The analyzed samples of sheared and granular peridotites differ in mineral-liquid equilibrium temperatures and pressures: 1230–1350 °C, 56–67 kbar inferred for the former and 750–1300 °C, 30–67 kbar for the latter. The contents of major oxides, trace elements, and PGEs differ both between sheared and granular peridotites and within each group. Some sheared and all granular peridotites are enriched in incompatible elements, have low percentages of clinopyroxene and contain garnet rich in middle rare-earth elements (MREE). These features result from interaction of the peridotites with melts and related fluids of presumably carbonate compositions containing incompatible elements in high abundances. Sheared peridotites were more strongly enriched and gained more Ca, Al, and Ti than the granular variety. On the other hand, granular peridotites have higher light REE (LREE) and lower heavy REE (HREE) enrichment, which may record compositional difference of metasomatic agents. Metasomatism acted in two stages: first silicate agents caused LREE enrichment and HREE depletion of melts and then the fractionated melts percolated through the mantle and affected the compositions of granular peridotites and, partly, sheared peridotites. The two types of peridotites differ also in PGE patterns, with largely variable Os–Pt concentrations in granular peridotite. This difference may be due to uneven distribution of the Os–Ir and Pt–Os–Ir intermetallic compounds, which formed as sulfide melting residue in the lithospheric mantle. Sheared peridotites show almost uniform Os–Pt distribution and are enriched in Pd, Re, and partly Pt. The enrichment possibly occurred during metasomatism when the percentages of garnet and clinopyroxene increased while sulfide phases precipitated into interstitials.

Platinum Group Elements in the South Transbaikalian Basanites (First Data)

Abstract —Study of the behavior and distribution of platinum group elements (PGE), along with other data, is necessary for geodynamic reconstructions. There are almost no PGE data for Transbaikalia, one of the large regions of Russia. This work presents the first data on the contents and behavior of PGE in the Cenozoic intraplate alkali basaltoids of southern Transbaikalia. The total PGE contents are 20–40 ppb. The PGE pattern of the studied basanites is similar to those of mafic OIB, including the Hawaiian ones, and rocks of large igneous provinces: tholeiitic basalts of the Siberian Platform and basaltoids of the West Siberian Plate. Based on this similarity and on the intraplate location of the South Transbaikalian basanites, we have concluded that the basanitic melts formed under mantle plume impact.

Environmental chemical behaviors of platinum group elements in aquatic environment

The concentrations of platinum group elements (PGE) in aquatic environment have been increasing due to human activity. It is generally assumed that anthropogenic PGE behaves in inert manner and does not pose a hazard to the environment. However, PGE might easily be mobilized and transformed into more toxic forms, enhanced their bioavailability in the aquatic environment. Based on 79 literatures, this paper summarized the research about the PGE in aquatic environment, outlined the environmental behavior of PGE, introduced the source distribution and changes of flux into the sea of PGE, discussed the toxicological response of aquatic organisms, and analysed the Speciation and influence factors of PGE. The purpose of this review was to attract more attention to the effect of PGE. In addition, in view of the existing research results and limitations, the future research directions of PGE were also outlined.

Implications of nano- and micrometer-size platinum-group element minerals in base metal sulfides of the Yangliuping Ni-Cu-PGE sulfide deposit, SW China

The concentrations of platinum-group elements (PGE) and semimetal elements (As, Sb, Se, Te and Bi) in the base metal sulfides from the Yangliuping deposit were determined using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS). Mass balance calculation reveals that the base metal sulfides only contain <40 wt% Os, <15 wt% Ir, <25 wt% Pd and negligible Pt, Rh and As, as solid solution. Such PGE percentages in the base-metal sulfides as solid solution are evidently lower than in the sulfides from the Jinchuan, Noril'sk and Sudbury NiCu-(PGE) sulfide deposits. Euhedral shape and similar chemical composition of the nanometer-size PGE-arsenides and sulfarsenides in the base-metal sulfides suggest that they crystallized from the sulfide melt before the crystallization of monosulfide solid solution (MSS) and intermediate solid solution (ISS). It is proposed that the nanometer-size PGE-arsenides and sulfarsenides formed from PGE-As molecular or polymolecular clusters in the sulfide liquid at high temperature. The PGE-As molecular or polymolecular clusters prevent As and PGE from partitioning into the base metal sulfide lattice and tend to form discrete nanometer-size PGE-arsenides and sulfarsenides. Thus, semimetal elements, particularly As, play an important role on behaviour of PGE during solidification of magmatic sulfide liquids.

Migration behavior of platinum group elements in natural and technogeneous systems

Data were summarized on the speciation of the main platinum group elements (PGE) platinum, palladium, and rhodium in aqueous media, forms of their input into the environment, and mechanisms of accumulation by natural sorptive phases. In some cases, the results obtained for PGE were compared with those for gold. Data on PGE speciation in a number of natural environments were analyzed. It was found that the main factor controlling the migration ability of PGE (Pd > Pt»Rh) is the formation of stable compounds with dissolved organic matter, hydroxyl, and thiosulfate ions and nanometer-sized particles. The transport of dissolved PGE species by marine, riverine, and technogeneous suspended materials was evaluated as an alternative way of an increase in PGE mobility. Significant differences were revealed in the migration behavior of platinum, palladium, and rhodium indicating the dominance of palladium dissipation in a dissolved state. The possibility of the prediction of PGE accumulation and dissipation in technogeneous systems was demonstrated.

The pH-dependent release of platinum group elements (PGEs) from gasoline and diesel fuel catalysts: Implication for weathering in soils

Powdered samples of new and old gasoline catalysts (Pt, Pd, Rh) and new and old diesel (Pt) catalysts were subjected to a pH-static leaching procedure (pH 2–9) coupled with thermodynamic modeling using PHREEQC-3 to verify the release and mobility of PGEs (platinum group elements). PGEs were released under acidic conditions, mostly exhibiting L-shaped leaching patterns: diesel old: 5.47, 0.005, 0.02; diesel new: 68.5, 0.23, 0.11; gasoline old: 0.1, 11.8, 4.79; gasoline new 2.6, 25.2, 35.9 in mg kg−1 for Pt, Pd and Rh, respectively. Only the new diesel catalyst had a strikingly different leaching pattern with elevated concentrations at pH 4, probably influenced by the dissolution of the catalyst carrier and washcoat. The pH-static experiment coupled with thermodynamic modeling was found to be an effective instrument for understanding the leaching behavior of PGEs under various environmental conditions, and indicated that charged Pt and Rh species may be adsorbed on the negatively charged surface of kaolinite or Mn oxides in the soil system, whereas uncharged Pd and Rh species may remain mobile in soil solutions.

A method for determination of PGE–Re concentrations and Os isotopic compositions in environmental materials

Automobile catalyst emissions not only result in increasing environmental concentrations of Pt, Pd, and Rh, but also Os, Ir, and Ru. Little is known about the behavior of platinum-group elements (PGE) and Re in the environment and their potential risk to humans and, as such, the monitoring of Os, Ir, Ru, and Re concentrations in environmental samples is necessary. We present an improved procedure for determination of PGE-Re concentrations and Os-187/Os-188 ratios of the environmental reference material BCR-723 by isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) and negative thermal ionization mass spectrometry (N-TIMS), respectively. The sample is digested with inverse aqua regia in a Carius tube. After Os separation by CCl4 solvent extraction, separation and purification of PGE and Re from sample matrix elements is sequentially performed by a two-stage tandem column setup using cation exchange and N-benzoyl-N-phenylhydroxylamine (BPHA) extraction resin. Elution of 0.1 mol L-1 HCl efficiently removes interfering elements such as Zr, Hf, Mo, and Cd in the final purified sample prior to ID-ICP-MS determination of PGE and Re. Analyses of BCR-723 yield reproducible results and well-defined average Pt, Pd, Os, Ir, Ru, and Re concentrations of 79.8 +/- 6.0, 4.6 +/- 0.8, 0.37 +/- 0.04, 0.23 +/- 0.12, 1.1 +/- 0.3, and 6.5 +/- 0.1 ng g(-1), respectively (95% confidence level; n = 10). The Os-187/Os-188 ratio of this standard was determined to be 0.537 +/- 0.022 (95% confidence level; n = 10). These are the first comprehensive PGE and Re concentrations and Os isotopic compositions reported for BCR-723 and provide a well-characterized standard for assessing the data quality of autocatatyst PGE measurements and related research on environmental materials. The method was successfully employed in the determination of PGE and Re concentrations and Os isotopic compositions in urban road dust samples.

Migration of platinum, palladium, and gold in the water systems of platinum deposits

In order to explore the behavior of platinum group elements in the ecosystems of mineral deposits, the migration characteristics of platinum and palladium were determined in the pH range typical of surface waters. Model sorption experiments on the precipitation of platinum and palladium on iron oxyhydroxide in the presence of major natural inorganic and organic ligands showed that platinum interacts most actively with an iron oxyhydroxide (ferrihydrite) precipitate within the whole pH range, both in the absence and presence of natural organic substances, whereas palladium is preferentially bound to dissolved, suspended, and sedimentary humic substances. The thermodynamic calculation of coexisting platinum and palladium species is qualitatively consistent with experimental data on the character of accumulation and migration of these elements. The obtained data suggest that the migration of platinum and palladium into highly colored waters in the zones of platinum group element deposits results in their extensive deposition on natural geochemical barriers.

A Review of the Behaviour of Platinum Group Elements within Natural Magmatic Sulfide Ore Systems

The largest and most significant type of geological deposit of platinum group elements (PGEs) is that associated with magmatic base metal sulfide minerals in layered mafic or ultramafic igneous intrusions. The common association of PGEs with sulfide minerals is a result of processes of magmatic and sulfide liquid segregation and fractionation. The mineralogical nature of the ores is dependent on a number of factors during sulfide liquid fractionation. The most significant of these with regard to the mineralogy of the two most important metals, platinum and palladium, is the presence and concentration of semimetals such as bismuth and tellurium within the mineralising sulfide liquid. Whereas rhodium, iridium, osmium and ruthenium are almost always present in solid solution within the resultant base metal sulfide minerals; should sufficient semimetals be present, Pd and especially Pt will form discrete minerals (such as platinum bismuthides) around the margins of, and possibly away from, the sulfides.

HRTEM-AEM-HAADF-STEM study of platinum-group elements within a mantle-derived Cr spinel (Lherz; North-Eastern Pyrenees, France)

As platinum group elements (PGE) like Ru, Os, Ir and Rh have appropriate charge and ionic radii to substitute the major cations in the spinel structure, Cr-spinel is one of the potential minerals that can fractionate such elements during the partial melting and fractional crystallization. However, whether PGE occur in solid solution or are physically collected as poly-metallic clusters of atoms on spinel grain boundaries is a central issue for PGE geochemistry. A PGE-bearing Cr-spinel separated from one harzburgite sample from Lherz has been analyzed by Transmission, Analytical and Scanning-Transmission Electron Microscopy (TEM-AEM-STEM). Our analyses did not reveal any exsolution/cluster feature at the nanometric scale, except for Ir, which is concentrated as Ir-bearing lamellar rutile, about 100 nm width. Rutile appears to have enhanced unmixing of Ir from the spinel structure. The D Cr spinel/silicate melt partition coefficients estimated from the Lherz Cr-spinel (Ir = 32 ± 0.7; Os = 28 ± 6; Ru = 12.5 ± 2; Pt = 1.5 ± 0.2; Pd = 0.2 ± 0.05) may be appropriate for modelling the behavior of PGE in sulfur-undersaturated melting processes of the shallow upper mantle, while being lower than those derived from experiments and natural ultramafic melts.

Platinum-group element systematics in Mid-Oceanic Ridge basaltic glasses from the Pacific, Atlantic, and Indian Oceans

The concentrations of Ir, Ru, Pt and Pd have been determined in 29 Mid-Oceanic Ridge basaltic (MORB) glasses from the Pacific ( N = 7), the Atlantic ( N = 10) and the Indian ( N = 11) oceanic ridges and the Red Sea ( N = 1) spreading centers. The effect of sulfide segregation during magmatic differentiation has been discussed with sample suites deriving from parental melts produced by high (16%) and low (6%) degrees of partial melting, respectively. Both sample suites define positive and distinct covariation trends in platinum-group elements (PGE) vs. Ni binary plots. The high-degree melting suite displays, for a given Ni content, systematically higher PGE contents relative to the low-degree melting suite. The mass fraction of sulfide segregated during crystallization (X sulf ), the achievement of equilibrium between sulfide melt and silicate melts (R eff ), and the respective proportions between fractional and batch crystallization processes (S b ) are key parameters for modeling the PGE partitioning behavior during S-saturated MORB differentiation. Regardless of the model chosen, similar sulfide melt/silicate melt partition coefficients for Ir, Ru, Pt and Pd are needed to model the sulfide segregation process, in agreement with experimental data. When corrected for the effect of magmatic differentiation, the PGE data display coherent variations with partial melting degrees. Iridium, Ru and Pt are found to be compatible in nonsulfide minerals whereas the Pd behaves as a purely chalcophile element. The calculated partition coefficients between mantle sulfides and silicate melts (assuming a PGE concentration in the oceanic mantle at ∼0.007 × CI-chondritic abundances) increase from Pd (∼10 3) to Ir (∼10 5). This contrasting behavior of PGE during S-saturated magmatic differentiation and mantle melting processes can be accounted for by assuming that Monosufide Solid Solution (Mss) controls the PGE budget in MORB melting residues whereas MORB differentiation processes involve Cu-Ni-rich sulfide melt segregation.

Geochemistry and mineralogy of platinum-group elements at Hartley Platinum Mine, Zimbabwe

The behaviour of platinum-group elements (PGE) in the exogenic cycle was examined in profiles of oxidized Main Sulfide Zone (MSZ) ores, in which the general metal distribution patterns of the pristine MSZ are grossly preserved. However, at similar Pt grades, significant proportions of Pd have been lost from the system. This indicates that Pd is more mobile than Pt and is dispersed in the supergene environment. Sperrylite and cooperite/braggite are stable in the oxidized MSZ. In contrast, the (Pt,Pd)-bismuthotellurides, common in pristine MSZ ores, have disintegrated, and ill-defined (Pt,Pd)-oxides or (Pt,Pd)-hydroxides have formed. The assemblage of detrital PGM present in the Makwiro River close to the Hartley Platinum Mine indicates further mineralogical changes. Sperrylite largely remains stable whereas most cooperite/braggite grains have been partly altered or completely destroyed. Grains of Pt-Fe alloy are ubiquitous in the alluvial sediments. Most likely, these grains are neo-formations that formed either from pre-existing, unstable PGM or via a solution stage under low-temperature conditions.

The behaviour of platinum-group elements in basalts from the East Greenland rifted margin

The continental flood basalts of the East Greenland volcanic rifted margin were extruded during continental breakup above the ancestral Iceland mantle plume at 55 Ma. Three distinct magma types, the low-Ti, high-Ti and very high-Ti series (LTS, HTS and VHTS respectively), are found intercalated in the ~6-km-thick Plateau Lava sequence. Incompatible trace elements indicate that the LTS are derived from a more depleted mantle source compared to HTS and VHTS. The LTS is characterised by increasing Cu (105 to 248 ppm) and Pd (7 to 24 ppb), constant Cu/Pd ratio (~10,000), and decreasing Ir (1.1 to <0.05 ppb) and Ru (1.8 to <0.3 ppb) concentrations during magmatic differentiation (16 to 7 wt% MgO). The constant Cu/Pd ratio reflects silicate- and chromite-dominated fractionation without concurrent segregation of sulphide. S-undersaturated differentiation is also indicated in the HTS, which also displays increasing Pd (6–16 ppb) and decreasing Ir concentrations (1 to <0.05 ppb) during differentiation, and the Cu/Pd ratios for the entire series average 21,000. However, some HTS samples have elevated Cu/Pd ratios (up to 33,000). Cu/Pd ratios in the HTS do not correlate with MgO, and this is interpreted to reflect varying Cu/Pd ratios of HTS parental magmas rather than S-saturated differentiation. During S-undersaturated differentiation of the LTS and HTS, Pt/Pd ratios decrease from 1.3 to 0.11 and 1.1 to 0.2 respectively, which indicates that Pd is much more incompatible than Pt during S-undersaturated differentiation. The VHTS consists exclusively of highly evolved samples with low MgO (6.6–6.1 wt%) and Pd/Ir ratios 98–228. Here, Cu/Pd ratios increase from 17,500 to 35,000 with decreasing Cr concentrations which indicate that these magmas experienced silicate fractionation with concurrent segregation of sulphide. The LTS represent melting of a depleted source and show high PGE concentrations and constant Cu/Pd ratios during S-undersaturated differentiation. Melting of a normal depleted upper mantle source generates S-saturated melts (MORB), and the depleted LTS source is therefore considered an extraordinary S-poor component within the ancestral Iceland plume. Of the three series, the VHTS contain the largest contribution from enriched mantle portions. The VHTS have similar PGE but much higher Nb concentrations for instance compared to the most evolved LTS and HTS samples, indicating that the enriched source contributes Nb but not PGE.

The recovery of platinum-group elements from the UG-2 chromitite, Bushveld Complex - a mineralogical perspective

¶The behaviour of platinum-group elements (PGE) during milling and flotation of the UG-2 chromitite layer is still poorly understood. The PGE in the UG-2 chromitite occur primarily in discrete platinum-group mineral phases, varying from sulphide assemblages (predominantly cooperite, braggite, malanite and laurite) to assemblages comprising a significant component of alloys (such as Pt-Fe alloy) or various telluride, bismuthinide, bismuthotelluride, arsenide and sulpharsenide phases. The mode of occurrence of platinum-group minerals ranges from being predominantly associated with base-metal sulphides (either locked within, or at the grain boundaries of, sulphide minerals) to being predominantly associated with gangue minerals (locked in chromite or silicate, or at grain boundaries of chromite and silicate grains). During milling, more than 50% of the platinum-group mineral grains in the samples investigated were liberated from the ore matrix. During flotation tests, most of the platinum-group mineral grains that remained associated with gangue reported to the flotation tailings, and those associated with liberated base-metal sulphides to the flotation concentrates. Because of their small grain size (generally less than ∼10 μm), the response of the liberated platinum-group mineral grains was more difficult to predict. It was found that most of these grains did report to the flotation concentrates, albeit at a slower rate than the base-metal sulphides. The flotation behaviour of these grains was determined both by grain size and type of mineral, with coarser braggite, cooperite, and to a lesser extent malanite being the fastest floating species.

Behaviour of Platinum-group elements in the subcontinental mantle of eastern Australia during variable metasomatism and melt depletion

Increasing recognition of complexities in the Platinum-group element (PGE) and Re concentration patterns in mantle samples are challenging the view of chondritic relative abundances in the upper mantle. To investigate the possible causes of PGE abundance variations, a suite of east Australian, mantle-derived, spinel peridotite xenoliths, ranging from fertile lherzolites to depleted harzburgites, and including apatite ± phlogopite ± amphibole bearing samples, have been analysed for their whole rock PGE and Re abundances. Whole rock abundances for 21 samples, combined with mineral separate analyses of 2 xenoliths, are presented to constrain the distribution of the PGEs and Re, their inherent heterogeneity at difference scales, and their behaviour during both melt extraction and metasomatism. Fertile (>2.9 wt% Al 2O 3) xenoliths have broadly chondritic relative PGE abundances, with the significant exception of positive Rh anomalies and variable negative Os anomalies. The high Rh abundances cannot be attributed to melt extraction or metasomatism. Bulk mineral separate PGE-Re analyses of 2 fertile xenoliths indicate less than 6% of the whole rock PGE budget resides in either silicate or oxide (spinel) phases. The remainder of the PGEs, and at least 80% of the whole rock Re budget, are sited in acid-leachable sulfides and less soluble trace phases such as PGE-sulfides or alloys. Individual PGEs partition into different trace phases resulting in small scale heterogeneity of both PGE ratios and concentrations on the order of 8%–20%. Although these trace phases may be present within the mantle, it is more likely at least some exsolved from monosulfide solid solutions at low temperatures. Ir and Rh abundances are consistent with compatible behaviour during melt extraction, whereas Ru, Pt and Pd abundances are consistent with slightly incompatible behaviour and can be modeled by assuming all reside in sulfides within the mantle, with D sulf Ru ∼ D sulf Pt > D sulf Pd. Comparison of PGE abundances between ‘dry’ xenoliths and modally metasomatised xenoliths, suggests the PGEs are not significantly mobilised during interaction with carbonate melts or during metasomatism leading to hydrous mineral growth. Given the problems of various types of secondary alteration processes, including melt extraction and surficial alteration that commonly affect xenoliths, and as within-locality heterogeneity is on a comparable order to any proposed regional heterogeneity, it may be premature to define significant regional differences, or ‘primary’ non-chondritic PGE patterns in lithospheric peridotites.

The behaviour of platinum-group elements during magmatic differentiation in Hawaiian tholeiites.

Concentrations of platinum-group elements (PGEs) and gold in basalts from Kilauea and Mauna Loa, Hawaii, were determined by ICP-MS, using an improved fire-assay and tellurium coprecipitation technique for preconcentrating the metals. Major and trace elements, together with Pb-Sr isotope compositions of basalt samples confirmed that these samples are typical Hawaiian tholeiites. The abundances of the PGEs and Au in Hawaiian tholeiites are rather constant during magmatic differentiation processes, whereas MORBs show strong fractionation of those elements. The distinctive behaviour of these PGEs in Hawaiian tholeiites cannot be explained solely via. fractionation of those elements by separation of crystallizing phases such as chromite, olivine and clinopyroxene. Oversaturation of sulfur and separation of sulfides from magmas are required for elucidating PGEs and Au concentrations in Hawaiian tholeiites.