Mobility Of Platinum Group Elements Research Articles

The solubility of platinum in magmatic brines: Insights into the mobility of PGE in ore-forming environments

Several field-based studies have proposed that late-stage magmatic aqueous brines may be responsible for the transportation and redistribution of platinum-group elements (PGE) in mafic–ultramafic igneous systems. We experimentally studied the solubility of Pt in high-temperature aqueous brines as a function of oxygen fugacity (ƒO2), temperature (T), pH and total chloride concentration (Cltotal) in a S-free system. Experiments were conducted at 800–1000 °C and 200 MPa in an externally-heated rapid-quench Molybdenum-Hafnium Carbide (MHC) pressure vessel assembly. We employed the synthetic fluid inclusion (SFI) technique to trap and sample pre-equilibrated, high-salinity brines in quartz cylinders subjected to in situ fracturing during experimental run conditions. Platinum solubility was observed to have a positive correlation with ƒO2, temperature, fluid acidity and Cltotal (salinity). A log Pt versus log ƒO2 diagram derives a weighted-error linear regression slope (m) = 0.48 ± 0.04 which demonstrates that Pt is present in the 2+ oxidation state over the studied ƒO2 range. At relatively oxidizing conditions, 1.44 log units above the Ni-NiO oxygen buffer (NNO+1.44), aqueous brines (containing 63 NaCl eq. wt.%) with a mildly acidic fluid composition (pH = 6.03) can dissolve up to ∼100 µg/g Pt at 900 °C and 200 MPa. Aqueous brines with identical fluid compositions yield a solubility of 4–13 µg/g Pt under more reducing conditions (NNO–0.41 to NNO–1.42). Thermodynamic model calculations suggest that both PtCl2 and PtCl3− are the dominant Pt(II)-chloride complexes which facilitate the transport of Pt in high-temperature aqueous vapors and brines. In fluid compositions with Cltotal >32 m (mol/kg H2O), PtCl3− complex is expected to be the dominant Pt species. In natural mafic–ultramafic systems, high-salinity, orthomagmatic aqueous brines may be important transporting agents if such magmatic fluids can participate in the dissolution of Pt-enriched base-metal sulfides or react with discrete insoluble Pt phases imposing a relatively high activity of Pt (i.e., Pt3Fe). Furthermore, precipitation of Pt from aqueous brines is promoted by a decrease in ƒO2, temperature, acidity and Cltotal.

Critical Metal Particles in Copper Sulfides from the Supergiant Río Blanco Porphyry Cu–Mo Deposit, Chile

Porphyry copper–molybdenum deposits (PCDs) are the world’s most important source of copper, molybdenum and rhenium. Previous studies have reported that some PCDs can have sub-economic to economic grades of critical metals, i.e., those elements that are both essential for modern societies and subject to the risk of supply restriction (e.g., platinum group elements (PGE), rare earth elements (REE), In, Co, Te, Ge, Ga, among others). Even though some studies have reported measured concentrations of Pd and Pt in PCDs, their occurrence and mineralogical forms remain poorly constrained. Furthermore, these reconnaissance studies have focused predominantly on porphyry Cu–Au deposits, but very limited information is available for porphyry Cu–Mo systems. In this contribution, we report the occurrence of critical metal (Pd, Pt, Au, Ag, and Te) inclusions in copper sulfides from one of the largest PCDs in the world, the supergiant Río Blanco-Los Bronces deposit in central Chile. Field emission scanning electron microscope (FESEM) observations of chalcopyrite and bornite from the potassic alteration zone reveal the presence of micro- to nano-sized particles (<1–10 μm) containing noble metals, most notably Pd, Au, and Ag. The mineralogical data show that these inclusions are mostly tellurides, such as merenskyite ((Pd, Pt) (Bi, Te)2), Pd-rich hessite (Ag2Te), sylvanite ((Ag,Au)Te2) and petzite (Ag3AuTe2). The data point to Pd (and probably Pt) partitioning in copper sulfides during the high-temperature potassic alteration stage, opening new avenues of research aimed at investigating not only the mobility of PGE during mineralization and partitioning into sulfides, but also at exploring the occurrence of critical metals in porphyry Cu–Mo deposits.

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.

Abundances of platinum group elements in native sulfur condensates from the Niuatahi-Motutahi submarine volcano, Tonga rear arc: Implications for PGE mineralization in porphyry deposits

Some porphyry Cu–Au deposits, which are enriched in Pd, are potentially an economic source of Pd. Magmatic volatile phases are thought to transport the platinum group elements (PGEs) from the porphyry source magma to the point of deposition. However, the compatibilities of the PGEs in magmatic volatile phases are poorly constrained. We report PGE and Re contents in native sulfur condensates and associated altered dacites from the Niuatahi-Motutahi submarine volcano, Tonga rear arc, in order to determine the compatibility of PGEs and Re in magmatic volatile phases, and their mobility during secondary hydrothermal alteration. The native sulfur we analyzed is the condensate of a magmatic volatile phase exsolved from the Niuatahi-Motutahi magma. The PGEs are moderately enriched in the sulfur condensates in comparison to the associated fresh dacite, with enrichment factors of 11–285, whereas Au, Cu and Re are strongly enriched with enrichment factors of ∼20,000, ∼5000 and ∼800 respectively. Although the PGEs are moderately compatible into magmatic volatile phases, their compatibility is significantly lower than that of Au, Cu and Re. Furthermore, the compatibility of PGEs decrease in the order: Ru>Pt>Ir>Pd. This trend is also observed in condensates and sublimates from other localities.PGE mineralization in porphyry Cu–Au deposits is characterized by substantially higher Pd/Pt (∼7–60) and Pd/Ir (∼100–10,500) than typical orthomagmatic sulfide deposits (e.g. Pd/Pt ∼0.6 and Pd/Ir ∼20 for the Bushveld). It has previously been suggested that the high mobility of Pd, relative to the other PGEs, may account for the preferential enrichment of Pd in porphyry Cu–Au deposits. However, the low compatibility of Pd in the volatile phase relative to the other PGEs, shown in this study, invalidates this explanation. We suggest that the PGE geochemistry of Pd-rich Cu–Au deposits is principally derived from the PGE characteristics of the magma from which the ore-forming fluid exsolved. Pd-rich porphyry Cu–Au deposits are associated with highly oxidized magmas. Prior to sulfide saturation Pd, Au and Cu behave as incompatible elements and concentrate in the melt with fractional crystallization, whereas Pt is depleted by early crystallization of a Pt-rich alloy and the other PGEs by the co-crystallization of the Pt-rich alloy and Cr spinel. As a consequence the Pd/Pt and Pd/Ir in the evolving melt and the magmatic volatile phases that exsolve from that melt, increase with increased fractionation. The high Pd content and high Pd/Pt (∼7–60) of Cu–Au porphyry ores therefore require the parent magma to have undergone extensive sulfide-undersaturated fractional crystallization prior to volatile exsolution.Our study also showed that the altered dacites contain PGE abundances that are similar to those of fresh dacites although Pt and Rh are slightly enriched in the altered dacites, which indicates low mobility of PGEs during secondary hydrothermal alteration.

In Vitro Investigations of Platinum, Palladium, and Rhodium Mobility in Urban Airborne Particulate Matter (PM10, PM2.5, and PM1) Using Simulated Lung Fluids

Environmental concentrations of platinum group elements (PGE) have been increasing since the introduction of automotive catalytic converters to control harmful emissions. Assessments of the human health risks of exposures to these elements, especially through the inhalation of PGE-associated airborne particulate matter (PM), have been hampered by a lack of data on their bioaccessibility. The purpose of this study is to apply in vitro methods using simulated human lung fluids [artificial lysosomal fluid (ALF) and Gamble's solution] to assess the mobility of the PGE, platinum (Pt), palladium (Pd), and rhodium (Rh) in airborne PM of human health concern. Airborne PM samples (PM(10), PM(2.5), and PM(1)) were collected in Frankfurt am Main, Germany. For comparison, the same extraction experiments were conducted using the standard reference material, Used Auto Catalyst (monolith) (NIST 2557). Pt and Pd concentrations were measured using isotope dilution ICP-Q-MS, while Rh was measured directly with ICP-Q-MS (in collision mode with He), following established matrix separation and enrichment procedures, for both solid (filtered residues) and extracted sample phases. The mobilized fractions measured for PGE in PM(10), PM(2.5), and PM(1) were highly variable, which can be attributed to the heterogenic nature of airborne PM and its composition. Overall, the mobility of PGE in airborne PM samples was notable, with a mean of 51% Rh, 22% Pt, and 29% Pd present in PM(1) being mobilized by ALF after 24 h. For PM(1) exposed to Gamble's solution, a mean of 44% Rh, 18% Pt, and 17% Pd was measured in solution after 24 h. The mobility of PGE associated with airborne PM was also determined to be much higher compared to that measured for the auto catalyst standard reference material. The results suggest that PGE emitted from automotive catalytic converters are likely to undergo chemical transformations during and/or after being emitted in the environment. This study highlights the need to conduct bioaccessibility experiments using samples collected in the field to enable an adequate assessment of risk.

PGE-rich Podiform Chromitites in the Al 'Ays Ophiolite Complex, Saudi Arabia: An Example of Critical Mantle Melting to Extract and Concentrate PGE

The Al ‘Ays ophiolite complex in Saudi Arabia is an example of an ophiolite that contains anomalous concentrations of all six platinum group elements (PGE) in podiform chromitite with maximum values of 2,570 ppb Pt, 6,870 ppb Pd, 840 ppb Rh, 5,800 ppb Ru, 6,200 ppb Ir, and 3,300 ppb Os. Smooth chondrite-normalized PGE profiles indicate igneous PGE ratios. These suggest that in situ alteration of the PGM caused only minor mobility of PGE during secondary modification of the mineralogy. Thus the geochemistry of the igneous concentration processes can be examined despite the mineralogical changes caused by subsequent alteration. Three main types of PGE mineralization are observed that are defined by their relative abundances of individual PGE. Type 1 has Ru > both Pt and Pd, with negative-slope chondrite-normalized profiles. Type 2 has Ru < either Pt or Pd, (Pt+Pd)/Ir ratios of 1 to 5, and convex upward chondrite-normalized profiles. Type 3 has Ru < either Pt or Pd, (Pt+Pd)/Ir ratios of 5 to 60, positive-slope chondrite-normalized profiles and is associated with elevated Cu and Ni concentrations. The unaltered centers of chromite grains in the chromitite within this complex have an unusually large range of composition; for example, Cr2O3 varies from 39 to 69 wt percent. PGE mineralization types 1, 2, and 3 are related to the composition of the chromite. Type 1 occurs across the range of chromitite compositions from 39 to 69 wt percent Cr2O3, type 2 occurs in chromitite having a range of 53 to 61 wt percent Cr2O3 , and type 3 occurs in chromitite having a range of 39 to 51 wt percent Cr2O3. The PGE form a great variety of platinum group minerals (PGM) and they differ among the three types of PGE mineralization. Type 1 is characterized by euhedral Os, Ir, and Ru (IPGE) alloys and laurite, both commonly enclosed in chromite, as well as members of the irarsite hollingworthite solid-solution series and Pt-IPGE-bearing PGM, both commonly interstitial to the chromite grains. Type 2 PGE enrichment is characterized by IPGE-, Pt- and Rh-bearing PGM. Type 3 PGE enrichment hosts predominantly Pd- and Pt-bearing PGM associated with Ni- and Cu-bearing minerals. Where exposed to the serpentinization process, the PGM are altered to alloys, arsenides, antimonides, and oxides that form irregular shapes or may form pseudomorphs of former PGM. They are commonly associated with Ni- and Cu-bearing minerals, including ruthanian pentlandite, millerite, arsenides, and PGE-bearing awaruite. Mantle melting and subsequent crystallization were at an optimum to concentrate PGE in the Al ‘Ays ophiolite complex. Crystallization of IPGE, commonly prior to chromite crystallization and latterly with some Pt and Rh, occurred across the range of chromitite composition. Crystallization of Pd with some remaining Pt occurred during sulfur saturation in chromitite formed from a more evolved magma. We propose that this crystallization was from a magma that was enriched in PGE because the degree of mantle melting was just sufficient to extract the PGE, but not dilute them in a melt that includes further mantle melting. This feature is likely to be common to other PGE-rich ophiolite complexes such as in Shetland in the United Kingdom, Leka in Norway, Thetford in Canada, Pindos in Greece, Tropoja in Albania and in New Caledonia. If equilibrium partial melting had continued in Al ‘Ays, then the magma would have been diluted by subsequent PGE-poor melt. This would have prevented sulfur saturation until much higher in the sequence, producing Pt- and Pd-bearing base metal sulfides in the crustal wehrlite and gabbro, as has occurred in the Cyprus and Oman ophiolites.

Potential Mobilization of Platinum-Group Elements by Siderophores in Surface Environments

The emission of platinum-group elements (PGEs) from catalytic converters has led to increased environmental abundances of Pt, Pd, and Rh; however, little is known about the environmental effects and fate of these metals. Organic ligands found in soils have the potential to increase the mobility of PGEs and potentially increase the bioavailability of the metals. Here, we assessed the abilities of microbially produced iron-chelating ligands (siderophores) to complex with the PGEs. Batch experiments using the synthetic siderophore desferrioxamine-B (DFO-B) and powdered metal or oxide forms of Pt, Pd, or Rh showed that DFO-B enhances the solubility of Pt and Pd due to the formation of Pt- and Pd-DFO-B aqueous complexes, with estimated minimum stability constants on the order of 10(17-18) and 10(20-24), respectively. Dissolution rates for Pd are comparable to other mineral dissolution rates with DFO-B. DFO-B had little to no effect on the dissolution of Rh metal or Rh2O3. Our results indicate that siderophores have the potential to increase the mobility of Pt and Pd in environments with limited activities of free trivalent cations. These results have implications for the fate of catalytic converter-emitted Pt and Pd, and support the need for further Pt and Pd toxicity and bioaccumulation studies.