Accumulation Of Platinum Group Elements Research Articles

Elimination of interferences in the determination of platinum, palladium and rhodium by diffusive gradients in thin films (DGT) and inductively coupled plasma mass spectrometry (ICP MS) using selective elution

The analysis of platinum (Pt), palladium (Pd) and rhodium (Rh) in aquatic samples by the diffusive gradients in thin films (DGT) technique using chelating resins, specific designed for the accumulation of PGEs, namely Purolite S914, S920 and Italmatch Chemicals IONQUEST® MPX-317. may however, still be influenced by the accumulation of other elements such (Cu, Zn, Pb, etc.) which will be extracted simultaneously by the hot aqua regia extraction and interfere with the Inductively Coupled Plasma Mass Spectrometry (ICPMS) analysis of the Platinum Group Elements (PGEs). Selective extractions were investigated to release the interfering elements without loss of the Platinum Group Elements (PGEs) from the resin gels. . A rinse with deionized water removes over 95% of Sr and Rb and a second rinse with 0.05 mol L−1 H2SO4 can be used to as a common eluent to remove an important fraction of the interfering elements from S920 and S914 without loss of PGEs but this results in loss of around 15% of the PGEs from MPX-317. It was shown that selective extractions can be used to remove specific interferences from each resin gel.

Development of the diffusive gradients in thin films technique (DGT) for platinum (Pt), palladium (Pd), and rhodium (Rh) in natural waters

The Diffusive Gradients in Thin Films (DGT) technique was developed for the first time for the platinum group elements (PGEs) platinum (Pt), palladium (Pd), and rhodium (Rh). Different chelating resins, specific designed for the accumulation of PGEs, namely Purolite S914, S920, S985, Italmatch Chemicals IONQUEST® MPX-317 and MP-102, were compared. The method development involved several different steps: 1) selection of an appropriate diffusive gel, 2) comparison of resins for the PGEs in terms of kinetics of uptake, 3) development of an efficient elution method for the PGEs from the resin gel, 4) Determination of diffusion coefficients for the PGEs in the diffusive gel, 5) Investigation of the influence of pH, ionic strength and dissolved organic matter on the diffusion coefficients and 6) study the selectivity of the tested resins gels in terms of potential interferences on the determination by ICPMS.Pt, Pd and Rh showed a linear accumulation over time for all resins and diffusion coefficients were independent of pH. The diffusion coefficient for Pt increased with increasing ionic strength (>0.5 M NaCl), but not for Pd and Rh. The interference study showed that Sr was the most important interferent for Rh and Pd and must be removed prior to analysis. The resins Purolite S914, Purolite S920, and Italmatch Chemicals IONQUEST® MPX-317 showed the best performance in terms of detection limits and separation of interferences. Using optimized procedures, the concentrations of Pt, Pd and Rh can be quantified at pg L−1 levels in natural waters for a 14 day deployment time.

Variation of platinum group elements (PGE) in airborne particulate matter (PM2.5) in the Beijing urban area, China: A case study of the 2014 APEC summit

Platinum (Pt), palladium (Pd) and rhodium (Rh) are accumulating globally in the environment due to their use as catalysts to control automotive exhaust emissions. The aim of this study was to evaluate the effect of emission control measures on the changes in platinum group elements (PGE) concentrations in airborne particulate matter (atmospheric particulate mat-ter of aerodynamic diameter ≤2.5 μm, PM2.5) during the 2014 Asia-Pacific Economic Cooperation (APEC) Summit held in Beijing. Airborne samples were collected from Beijing urban areas with high volumes of traffic. Samples were treated using microwave-assisted digestion procedures, and the concentrations of PGE were determined by inductively coupled plasma mass spectrometry (ICP-MS).The PGE concentration during the APEC summit decreased by 35.13% and 35.21%, compared with before and after the summit, respectively, which were smaller than the corresponding decreases in the PM2.5 concentrations (∼53.9% and 50.5%, respectively). The results provide data regarding PGE accumulation trends in the urban atmospheric environments, which is ascribed to their use as catalysts in automotive catalytic converters. The results highlight the need to continue monitoring the accumulation of PGE, most notably Pd, in the urban atmospheric environment.

Accumulation of Platinum Group Elements in Hydrogenous Fe–Mn Crust and Nodules from the Southern Atlantic Ocean

Distribution of platinum group elements (Ru, Pd, Pt, and Ir) and gold in hydrogenous ferromanganese deposits from the southern part of the Atlantic Ocean has been studied. The presented samples were the surface and buried Fe–Mn hydrogenous nodules, biomorphous nodules containing predatory fish teeth in their nuclei, and crusts. Platinum content varied from 47 to 247 ng/g, Ru from 5 to 26 ng/g, Pd from 1.1 to 2.8 ng/g, Ir from 1.2 to 4.6 ng/g, and Au from less than 0.2 to 1.2 ng/g. In the studied Fe–Mn crusts and nodules, Pt, Ir, and Ru are significantly correlated with some redox-sensitive trace metals (Co, Ce, and Tl). Similar to cobalt and cerium behaviour, ruthenium, platinum, and iridium are scavenged from seawater by suspended ferromanganese oxyhydroxides. The most likely mechanism of Platinum Group Elements (PGE) accumulation can be sorption and oxidation on δ-MnO2 surfaces. The obtained platinum fluxes to ferromanganese crusts and to nodules are close and vary from 35 to 65 ng∙cm−2∙Ma−1. Palladium and gold do not accumulate in hydrogenous ferromanganese deposits relative to the Earth’s crust. No correlation of Pd and Au content with major and trace elements in nodules and crusts have been identified.

Levels of platinum group elements and rare-earth elements in wild mushroom species growing in Poland

Due to limited data-describing abilities of mushrooms to accumulate platinum group elements (PGEs) and rare-earth elements (REEs), the aim of this study was to determine, by inductively coupled plasma optical emission spectrometry followed by microwave-assisted sample digestion by nitric acid, the content of these elements in 20 mushroom species (10 above ground and 10 growing on wood), mostly edible, collected near a busy trunk road. The highest content of PGEs in above-ground mushroom species was observed in Lepista gilva and Suillus bovinus fruit bodies (0.38 ± 0.05 and 0.37 ± 0.03 mg kg−1 DW, respectively), while in mushrooms growing on wood, the highest content was observed in Pleurotus ostreatus (0.35 ± 0.04 mg kg−1 DW). The mean content of PGEs for both these groups was 0.23 ± 0.08 and 0.26 ± 0.07 mg kg−1 DW, respectively. The highest content of REEs in Suillus luteus and Tricholoma equestra was 5.03 ± 0.50 and 2.18 ± 0.56 mg kg−1 DW, respectively, but within mushrooms growing on wood in Ganoderma applanatum fruiting bodies it was 4.19 ± 0.78 mg kg−1 DW. Mean contents of REEs were 1.39 ± 1.21 and 1.61 ± 0.97 mg kg−1 DW in above-ground species and species growing on wood, respectively. Generally, the group of mushroom species growing on wood was capable of slightly higher accumulation of both REEs and PGEs. No limits have been established for both the groups until now.

Extra- and intra-cellular accumulation of platinum group elements by the marine microalga, Chlorella stigmatophora

To better understand the marine biogeochemistry of the platinum group elements (PGE), Rh(III), Pd(II) and Pt(IV) were added in combination and at ppb concentrations to cultures of the marine microalga, Chlorella stigmatophora, maintained in sea water at 15 °C and under 60 μmol m−2 s−1 PAR. The accumulation of PGE was established in short-term (24-h) exposures, and under varying conditions of algal biomass and PGE concentration, and in a longer-term exposure (156-h) by ICP-MS analysis of sea water and nitric acid digests and EDTA washes of the alga. In short-term exposures, and under all conditions, the extent of accumulation by C. stigmatophora was in the order: Rh > Pd >> Pt; and Pd was internalised (or resistant to EDTA extraction) to a considerably greater extent than Rh and Pt. Accumulation isotherms were quasi-linear up to added PGE concentrations of 30 μg L−1 and all metals displayed a significant reduction in accumulation on a weight-normalised basis with increasing density (biomass) of C. stigmatophora, an effect attributed to the production of exudates able to stabilise metals in sea water through complexation. In the longer-term exposure, kinetic constraints on the reactivities of Rh and, in particular, Pt, resulted in final degrees of accumulation and internalisation by C. stigmatophora that were greatest for Rh and similar between Pd and Pt. Among the PGE, therefore, Rh is predicted to participate in biological removal and transport processes in the marine environment to the greatest extent while decoupling in the biogeochemistries of Pd and Pt is predicted in shorter-term or more transient processes.

Accumulation and distribution characteristics of platinum group elements in roadside dusts in Beijing, China

The concentrations, distribution, and accumulation of platinum group elements (PGEs) were investigated in roadside dusts collected in four different foundational areas in Beijing during February to May 2010. The results showed that PGE levels in all samples were above the average upper crust values, with mean concentrations of 57.5 ng · g(-1) Pd, 28.2 ng · g(-1) Pt, and 9.8 ng · g(-1) Rh, respectively. Palladium concentration has increased rapidly in recent years. The rank of PGE levels in four different functional regions for roadside dusts was: heavy density traffic area > residential area > educational area > tourism area. Palladium, Pt, and Rh concentrations in dusts showed strong positive correlations, indicating a common traffic-related source of these metals. Meanwhile, PGEs in these samples were not correlated with other traffic-related metals except for Cr. The average PGE ratios of road dusts from Beijing were consistent with those in Germany and Western Australia, but lower than those in the United States and Mexico, indicating that various catalyst productions were used in different countries. In addition, grain-size partitioning of PGEs in dusts indicated that concentrations of PGEs differed from one particle size to another. The coarse fraction had higher PGE concentrations than the fine fraction in roadside dusts. These results showed that autocatalyst PGE contamination estimates in the environment would be significantly underestimated if only a fine-grain size fraction (<0.063 mm) is analyzed.

ORIGIN OF PLATINUM-GROUP MINERALS IN MAFIC AND ULTRAMAFIC ROCKS: FROM DISPERSED ELEMENTS TO NUGGETS

Based on the studies of paragenetic assemblages of platinum-group minerals (PGM) from placers and chromitite ores associated with zonal-ring dunite intrusions in the Aldan Shield, on the Siberian platform, a novel model for the PGM formation is offered, which implies separation of a Cr-rich oxide liquid with significant concentration of the platinum-group elements (PGE) from a picritic magma. The presence of PGM alloys in sulfide-poor chromitite ores from layered intrusions and zonal gabbro–dunite massifs indicates that PGE mineralization is genetically related not just to sulfide formation but to chromite formation as well. A hypothetical (MgO + FeO + CaO) – SiO2 – (Cr2O3 + Fe2O3 + Al2O3) triangular diagram shows that fractional crystallization of olivine results in the enrichment of the residual melt in Cr, PGE, a range of metals, and easily fusible and volatile elements, and in magma separation into a light silicate-rich liquid and a dense PGE–Cr-rich oxide liquid. In fluid-saturated magma, a Cr-enriched oxide melt completely separates from a silicate melt, its crystallization temperature is lower, and the solubility of PGE is higher. It is likely that the presence of PGE in the Cr-rich oxide liquid takes the form of sybotactic domains, clusters surrounded by ligands of easily fusible and volatile elements, which prevents the PGE from removal via an untimely crystallization from the melt as micronuggets. Crystallization of a PGE-, Cr-rich oxide melt can be traced in the schematic chromite – Os – Pt ternary diagram proposed, which shows a wide field of immiscibility existing between chromite and the PGE. Owing to the low solubility of PGE in chromite, crystallization of the Cr-rich melt results in accumulation of PGE in the interstitial liquid. With IPGE prevailing over PPGE, the crystallization trend does not reach the immiscibility field, ending in synchronous crystallization of chromite and small grains of Pt–Ru–Ir–Os alloys. In case of Pt dominance, the crystallization trend reaches the immiscibility field, Pt gradually accumulates in the residual melt, with final crystallization occurring at a triple eutectic point, which creates favorable conditions for the formation of large Pt nuggets from tens of grams to a few kilograms in weight, which are characteristic only of PGE–chromite deposits of the Uralian–Alaskan and Aldanian types.

Accumulation of platinum group elements by the marine gastropod Littorina littorea

The accumulation and trophic transfer of the platinum group elements (PGE): Rh, Pd and Pt; have been studied in short-term (5 day) exposures conducted in aquaria containing the marine macroalga, Ulva lactuca, and/or the grazing mollusc, Littorina littorea. Metals added to sea water (to concentrations of 20 μg L −1) were taken up by U. lactuca in the order Rh, Pt > Pd and by L. littorea in the order Pd ≥ Pt ≥ Rh, with greatest metal accumulation in the latter generally occurring in the visceral complex and kidney. When fed contaminated alga, accumulation of Rh and Pd by L. littorea, relative to total available metal, increased by an order of magnitude, while accumulation of Pt was not readily detected. We conclude that the diet is the most important vector for accumulation of Rh and Pd, while accumulation of Pt appears to proceed mainly from the aqueous phase.

Concentrations of anthropogenic Pt and Pd in urban roadside soils in Xuzhou, China

The potential accumulation of platinum group elements (PGE) in the environment from automobile catalysts is high in urban areas, with the major sinks being roadside soils. Therefore, this investigation presented the detailed study on characterized concentrations of Pt and Pd and their enrichment ratios in urban roadside soils in Xuzhou, China in March 2003. Data from 21 roadside topsoil samples analyzed by inductively coupled plasma-mass spectrometer (ICP-MS) illustrated that the medians of concentrations of Pt and Pd were 2.9 and 2.8 ng/g, respectively. Hierarchical clustering analysis indicated that Pt and Pd were mainly from traffic emissions. Compared to unpolluted soils, computation of Pt and Pd enrichment ratios suggested that the Xuzhou roadside soils had average enrichment factors of 3.53 for Pt (in range of 1.22–5.73) and of 3.37 for Pd (in range of 1.35–4.46). Lower Pt/Pd ratios (in range of 0.35–2.86) in relation to similar studies in other countries were observed, which might be due to the different Pt/Pd ratios in Chinese automobile catalytic converters. Moreover, fine fraction (<250 μm) contained higher concentrations of Pt and Pd compared to the coarse fraction (250–500 μmm).

Mars chronology: assessing techniques for quantifying surficial processes

Currently, the absolute chronology of Martian rocks, deposits and events is based mainly on crater counting and remains highly imprecise with epoch boundary uncertainties in excess of 2 billion years. Answers to key questions concerning the comparative origin and evolution of Mars and Earth will not be forthcoming without a rigid Martian chronology, enabling the construction of a time scale comparable to Earth's. Priorities for exploration include calibration of the cratering rate, dating major volcanic and fluvial events and establishing chronology of the polar layered deposits. If extinct and/or extant life is discovered, the chronology of the biosphere will be of paramount importance. Many radiometric and cosmogenic techniques applicable on Earth and the Moon will apply to Mars after certain baselines (e.g. composition of the atmosphere, trace species, chemical and physical characteristics of Martian dust) are established. The high radiation regime may pose a problem for dosimetry-based techniques (e.g. luminescence). The unique isotopic composition of nitrogen in the Martian atmosphere may permit a Mars-specific chronometer for tracing the time-evolution of the atmosphere and of lithic phases with trapped atmospheric gases. Other Mars-specific chronometers include measurement of gas fluxes and accumulation of platinum group elements (PGE) in the regolith. Putting collected samples into geologic context is deemed essential, as is using multiple techniques on multiple samples. If in situ measurements are restricted to a single technique it must be shown to give consistent results on multiple samples, but in all cases, using two or more techniques (e.g. on the same lander) will reduce error. While there is no question that returned samples will yield the best ages, in situ techniques have the potential to be flown on multiple missions providing a larger data set and broader context in which to place the more accurate dates.

Source characterisation of atmospheric platinum group element deposition into an ombrotrophic peat bog

Platinum, palladium, rhodium, iridium and osmium were found to be enriched relative to their expected natural concentrations in peat samples from Thoreau's Bog, an ombrotrophic peat bog in Concord, Massachusetts. The source of osmium into the bog was determined from its isotopic composition (187Os/188Os). Osmium is composed of 4% lithogenic osmium from atmospheric soil dust, 41% of anthropogenic osmium and 55% of osmium from a non-lithogenic, non anthropogenic source, with rain being a likely candidate for the latter. Significant anthropogenic and rain contributions are also expected for iridium. In contrast, platinum, palladium and rhodium are almost exclusively anthropogenic. The larger enrichments of platinum, palladium and rhodium indicate that automobile catalysts are the source of platinum group elements to Thoreau's bog. The bog is located approximately 300 m from a major road and, therefore, the occurrence of platinum elements is evidence for regional dispersion of these metals. The absence of a clear trend following the introduction of catalysts indicates that platinum group elements are not quantitatively conserved in peat with downward leaching and plants playing an important role in the accumulation of platinum group elements.