Distribution of Platinum and Palladium between Dissolved, Nanoparticulate, and Microparticulate Fractions of Road Dust.

Ageing processes of vehicle catalytic converters inevitably lead to the release of Pt and Pd into the environment, road dust being the main sink. Though Pt and Pd are contained in catalytic converters in nanoparticulate metallic form, under environmental conditions, they can be transformed into toxic dissolved species. In the present work, the distribution of Pt and Pd between dissolved, nanoparticulate, and microparticulate fractions of Moscow road dust is assessed. The total concentrations of Pt and Pd in dust vary in the ranges 9-142 ng (mean 35) and 155-456 (mean 235) ng g-1, respectively. The nanoparticulate and dissolved species of Pt and Pd in dust were studied using single particle inductively coupled plasma mass spectrometry. The median sizes of nanoparticulate Pt and Pd were 7 and 13 nm, respectively. The nanoparticulate fraction of Pt and Pd in Moscow dust is only about 1.6-1.8%. The average contents of dissolved fraction of Pt and Pd are 10.4% and 4.1%, respectively. The major fractions of Pt and Pd (88-94%) in road dust are associated with microparticles. Although the microparticulate fractions of Pt and Pd are relatively stable, they may become dissolved under changing environmental conditions and, hence, transformed into toxic species.

Intrinsic catalytic activity of rhodium nanoparticles with respect to reactive oxygen species scavenging: implication for diminishing cytotoxicity.

Noble metal nanoparticles (NPs) and their hybrids have demonstrated a strong potential to mimic the catalytic activity of natural enzymes and diminish oxidative stress. There is a large space to explore the intrinsic catalytic activity of Rh NPs with respect to reactive oxygen species (ROS) scavenging. We found that Rh NPs can quench H2O2, •OH, O2•-, 1O2 and inhibit lipid peroxidation under physiological conditions. In vitro cell experiments proved that Rh NPs have great biocompatibility and protect cells from oxidative damage caused by H2O2. This study can provide important insights that could inform future biological applications.

Platinum and rhodium in Tagus estuary, SW Europe: sources and spatial distribution.

The spatial distribution of Pt and Rh was assessed in Tagus estuary and their sources discussed. Both elements were analysed in superficial sediment samples (n = 72) by adsorptive cathodic stripping voltammetry. Concentrations varied within the following ranges: 0.18-5.1 ng Pt g-1 and 0.02-1.5 ng Rh g-1. Four distinct areas were established: "reference"; waste- and pluvial water discharge; motorway bridges and industrialised areas. The calculated reference median concentrations were 0.55 ng Pt g-1 and 0.27 ng Rh g-1. Linear relationships were found between Pt and Al, Fe and LOI, whereas Rh depicted scattered patterns. The highest concentrations were found nearby industrialised areas and a motorway bridge, corresponding to the enrichment of 10 and 6 times the background of Pt and Rh, respectively. The main sources of contamination to the Tagus estuary derived from historical and present industrial activities and from automotive catalytic converters. Large variations of Pt/Rh ratio (0.48-39) point to different sources, reactivity and dilution effects.

Determination of Ultra-trace Rhodium in Water Samples by Graphite Furnace Atomic Absorption Spectrometry after Cloud Point Extraction Using 2-(5-Iodo-2-Pyridylazo)-5-Dimethylaminoaniline as a Chelating Agent.

A highly sensitive method based on cloud point extraction (CPE) separation/preconcentration and graphite furnace atomic absorption spectrometry (GFAAS) detection has been developed for the determination of ultra-trace amounts of rhodium in water samples. A new reagent, 2-(5-iodo-2-pyridylazo)-5-dimethylaminoaniline (5-I-PADMA), was used as the chelating agent and the nonionic surfactant TritonX-114 was chosen as extractant. In a HAc-NaAc buffer solution at pH 5.5, Rh(III) reacts with 5-I-PADMA to form a stable chelate by heating in a boiling water bath for 10 min. Subsequently, the chelate is extracted into the surfactant phase and separated from bulk water. The factors affecting CPE were investigated. Under the optimized conditions, the calibration graph was linear in the range of 0.1-6.0 ng/mL, the detection limit was 0.023 ng/mL for rhodium and relative standard deviation was 3.67% (c = 1.0 ng/mL, n = 11)．The method has been applied to the determination of trace rhodium in water samples with satisfactory results.

Determination of Platinum Group Elements in Particulate Matter by Inductively Coupled Plasma Mass Spectrometry.

This study examined a method for determination of rhodium (Rh), palladium (Pd) and platinum (Pt) in particulate matter using standard solutions, model samples and certified reference materials (NIST 1648a and ERM CZ120). The method was based on microwave digestion followed by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the stability of the standard solution mixture of Rh, Pd and Pt was better when chlorides were present in the solution. A membrane filter and one type of quartz filter were the most adequate for analyzing platinum group elements (PGE). Respective limits of detection for Rh, Pd and Pt were 0.028, 0.503 and 0.0265 pg/m3 with a membrane filter and 0.478, 4.530 and 0.070 pg/m3 for one type of quartz filters. The sample matrix had no significant effects on the determination of three PGEs.

Column preconcentration and electrothermal atomic absorption spectrometric determination of rhodium in some food and standard samples.

In the present work, an electrothermal atomic absorption spectrometric method has been developed for the determination of ultra-trace amounts of rhodium after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol/tetraphenylborate ion associated complex at the surface of alumina. Several factors affecting the extraction efficiency such as the pH, type of eluent, sample and eluent flow rates, sorption capacity of alumina and sample volume were investigated and optimized. The relative standard deviation for eight measurements of 0.1 ng/mL of rhodium was ±6.3%. In this method, the detection limit was 0.003 ng/mL in the original solution. The sorption capacity of alumina and the linear range for Rh(III) were evaluated as 0.8 mg/g and 0.015-0.45 ng/mL in the original solution, respectively. The proposed method was successfully applied for the extraction and determination of rhodium content in some food and standard samples with high recovery values.

Leaves of Phragmites australis as potential atmospheric biomonitors of Platinum Group Elements.

The increasing emissions of Platinum Group Elements (PGEs), namely Pt, Pd and Rh, may pose a significant risk to ecosystem processes and human health. A periodic assessment of PGEs distribution in the environment is thus of the utmost importance for the implementation of timely measures of mitigation. Although several studies have quantified PGEs in different life forms such as mammals, birds, fish, crustaceans, algae, mosses and even human beings, data about vascular plants need further surveys. This study aimed to test the suitability of the grass Phragmites australis (common reed) as a biomonitor of PGEs atmospheric pollution. The results showed that Pd and Pt concentrations in leaves are significantly higher in urban areas. In particular, Pd showed the highest range of values in line with current studies that consider palladium as the main element of traffic-related pollution. Overall, the leaves of Phragmites australis reflected the different gradient of PGEs emissions, and may thus be considered as potential biomonitors of atmospheric pollution.

Biomonitoring of airborne platinum group elements in urban traffic police officers.

In the present study, an attempt was made to study the levels of platinum (Pt), palladium (Pd), and rhodium (Rh) in respirable suspended particulate matter samples and respective blood samples of occupationally exposed traffic personnel in selected sites of Hyderabad city. The maximum concentration of platinum group elements in air dust samples of Hyderabad city were as follows: Pt = 1,416 µg/m(3), Pd = 1,024 µg/m(3), and Rh = 1,352 µg/m(3). The blood samples of occupationally exposed personnel of Hyderabad city showed Pt as high as 6.65, Pd as high as 2.15, and Rh as high as 4.95 µg/l. The results showed an important aspect of bioaccumulation tendency of these metals with increase in age and years of occupational exposure.

Separation and preconcentration of trace amounts of rhodium using a dispersive liquid-liquid microextraction method and its determination by flame atomic absorption spectrometry.

A sensitive and selective method for the determination of low levels of rhodium (Rh) in environmental samples is needed. In the proposed method, an extracting solvent with a lower toxicity and density than the other solvents typically used in dispersive liquid-liquid microextraction was used to extract trace amounts of Rh from aqueous samples. Rh ions were complexed with 1-(2-pyridylazo)-2-naphthol in the pH range of 3.2-4.7 and extracted with dispersive liquid-liquid microextraction. The type and volume of the extracting solvent and dispersive solvent, centrifugation time, pH, amount of the chelating agent, and sample ionic strength were carefully studied. Under the optimal conditions, the LOD and RSD were 0.36 ng/mL (3Sb/m, n = 7) and +/-2.0% (n = 7), respectively. The calibration curve was linear in the range of 4.0-800 ng/mL. The method was applied to the determination of Rh in well and tap water, and spiked recoveries were in the range of 96-103.7%.

Complex anthropogenic sources of platinum group elements in aerosols on Cape Cod, USA.

Platinum group elements (PGE) of anthropogenic origin have been reported in rainwater, snow, roadside soil and vegetation, industrial waste, and urban airborne particles around the world. As recent studies have shown that PGE are bioavailable in the environment and pose health risks at chronic levels, the extent of PGE pollution is of global concern. In this study, we report PGE concentrations and osmium isotope ((187)Os/(188)Os) ratios of airborne particles (particulate matter, PM10) collected in Woods Hole, a small coastal village on Cape Cod, Massachusetts, U.S.A. The sampling site is more than 100 km away from the nearest urban centers (Boston, Providence) and has no large industrial emission center within a 30 km radius. The study reveals that, although PGE concentrations in rural airborne particulate matter are orders of magnitude lower than in urban aerosols, 69% of the total osmium is of anthropogenic origin. Anthropogenic PGE signatures in airborne particles are thus not restricted to large cities with high traffic flows and substantial industries; they can also be found in rural environments. We further conclude that the combination of Pt/Rh concentration ratios and (187)Os/(188)Os composition can be used to trace PGE sources. The Pt/Rh and (187)Os/(188)Os composition of Woods Hole aerosols indicate that the anthropogenic PGE fraction is primarily sourced from ore smelting processes, with possible minor contributions from fossil fuel burning and automobile catalyst-derived materials. Our results further substantiate the use of (187)Os/(188)Os in source apportionment studies on continental scales.

Platinum Group Element distribution in water and marine biota from two impacted estuarine environments (Douro and Ave estuaries, Portugal).

Platinum Group Elements (PGEs) are contaminants of emerging environmental concern considering their continuous increasing use and subsequent release in the environment. While recent field studies provided PGE levels in seawater, scarce knowledge still exists regarding PGE contamination in marine organisms, especially for rhodium (Rh). Water, macroalgae and mussels were sampled along two representative urbanized estuarine systems and adjacent coastal areas (Douro and Ave estuaries, Portugal). Rhodium and platinum (Pt) concentrations were quantified through both stripping voltammetry and mass spectrometry in collected samples. Spatial mapping of PGE contamination was, to a certain extent, correlated with proxies of urban effluents. The use of Pt/Rh ratios reflected the dominant influence of PGE traffic emissions along the Douro and inputs from various sources (including industries) on the Ave Estuary. Macroalgae and mussels PGE concentrations reflected urban pressure, amplifying environmental signals, and supporting their relevant use as bioindicators of PGE contamination in estuarine/coastal systems.

Identification of platinum and palladium particles emitted from vehicles and dispersed into the surface environment.

Platinum, palladium, and rhodium are emitted from vehicle catalytic converters. Until now, the form of precious metal particles in road dust and urban waste has not been identified. This study has located, imaged, and analyzed these particles in road dust and gully waste. Two fragments of catalytic converter have been observed in road dust. They are 40-80 µm in size and covered in many minute particles (<0.3 µm) of either platinum with minor rhodium or palladium. One fragment identified in gully sediment is smaller, 25 µm in diameter, hosting only one attached particle of palladium with minor rhodium. As fragments are washed off roads they begin to disintegrate and the precious metals become detached. Also precious metal-bearing particles have been located in incinerated sewage ash including a 20 µm diameter cluster of <3 µm sized platinum particles that may be the remains of a catalytic converter fragment that has survived incineration. The form of these precious metal-bearing particles described here reveals that as they are dispersed from roads they are likely to be present predominantly as two particle sizes. Either they are attached to larger fragments of catalytic converter or they are released as individual detached tiny <0.3 µm to nanoparticle sizes.

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.

Stripping voltammetric determination of palladium, platinum and rhodium in freshwater and sediment samples from South African water resources.

Stripping voltammetry as technique has proved to be very useful in the analysis of heavy and other metal ions due to its excellent detection limits and its sensitivity in the presence of different metal species or interfering ions. Recent assessments of aquatic samples have shown increased levels of platinum group metals (PGMs) in aquatic ecosystems, caused by automobile exhaust emissions and mining activities. The development of an analytical sensor for the detection and characterisation of PGMs were investigated, since there is an ongoing need to find new sensing materials with suitable recognition elements that can respond selectively and reversibly to specific metal ions in environmental samples. The work reported shows the successful application of another mercury-free sensor electrode for the determination of platinum group metals in environmental samples. The work reported in this study entails the use of a glassy carbon electrode modified with a bismuth film for the determination of platinum (Pt(2+)), palladium (Pd(2+)) or rhodium (Rh(2+)) by means of adsorptive cathodic stripping voltammetry. Optimised experimental conditions included composition of the supporting electrolyte, complexing agent concentration, deposition potential, deposition time and instrumental voltammetry parameters for Pt(2+), Pd(2+) and Rh(2+) determination. Adsorptive differential pulse stripping voltammetric measurements for PGMs were performed in the presence of dimethylglyoxime (DMG) as complexing agent. The glassy carbon bismuth film electrode (GC/BiFE) employed in this study exhibit good and reproducible sensor characteristics. Application of GC/BiFE sensor exhibited well-defined peaks and highly linear behaviour for the stripping analysis of the PGMs in the concentration range between 0 and 3.5 µg/L. The detection limit of Pd, Pt and Rh was found to be 0.12 µg/L, 0.04 µg/L and 0.23 µg/L, respectively for the deposition times of 90 s (Pd) and 150 s (for both Pt and Rh). Good reproducibility was also observed and the practical applicability of the sensor was demonstrated with the analysis of environmental water and sediment samples.

First study on anthropogenic Pt, Pd, and Rh levels in soils from major avenues of São Paulo City, Brazil.

Over the last years, investigations on the increase of platinum (Pt), palladium (Pd), and rhodium (Rh) levels in urban environments of big cities all over the world - especially to catalytic converters emissions - have been grown up enormously. São Paulo City is the 6th largest megacity in the world having about 20 million inhabitants and an ever increasing seven million motor vehicle fleet. In spite of this, there has never been an investigation regarding Pt, Pd, and Rh levels in the city. In the present study, Pt, Pd, and Rh concentrations were determined in soils adjacent to seven main high-density traffic avenues in the metropolitan region of São Paulo City. Inductively coupled plasma mass spectrometry was employed - after ultrasound-assisted aqua regia leaching - as analytical technigue. The results showed concentration levels up to 378 ng g(-1) for Pd, 208 ng g(-1) for Pt, and 0.2 to 45 ng g(-1) for Rh. These levels are much higher than those considered for the geochemical background of soils, indicating a catalytic converter source. Due to the different Pt/Pd/Rh ratio in Brazilian automobile catalytic converters, lower levels of Pt/Pd ratios compared with other similar studies were observed. The obtained results are the first data for monitoring Pt, Pd, and Rh pollution in São Paulo City soils.

Tracking changes in rhodium nanoparticles in the environment, including their mobility and bioavailability in soil.

The goals of the undertaken studies included assessment of the mobility of Rh nanoparticles (Rh NPs) and ionic forms (Rh(III)) in soil, optimization of the digestion procedure of environmental samples containing Rh NPs, and comparison of Rh NPs and Rh(III) uptake and bioaccumulation by hydroponically cultivated plants. Mass spectrometry with inductively coupled plasma (ICP MS) was used to determine the total content of Rh in solutions obtained after the processes of digestion and extraction. Transmission Electron Microscopy (TEM) supported the investigation of Rh NPs decomposition and proved the presence of uptaken nano forms in plant tissues. Adsorptive stripping voltammetry (AdSV) allowed to distinguish ionic and metallic forms of Rh, based on the fact that Rh NPs are electrochemically inactive. A two-step digestion procedure with H2SO4 and HNO3 was proposed for efficient decomposition of Rh NPs. Based on single extractions with selected extractants, it was found that independently of its chemical form Rh is substantially immobilized in soil. The mobility of Rh(III) and Rh NPs was below 38% and 0.02%, and the accumulation factor in leaves equaled 0.2 and 4.4, respectively.

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Platinum group metals (PGMs) present a variety of forms in the environment, and analysis of speciation is essential for identifying their ecological risk. Here, we reviewed the methods for the morphological analysis of three major PGMs (platinum, palladium and rhodium) in the environment, including chemical sequential extraction, hyphenated techniques for instruments, computer simulations. We outlined the types, characteristics and applications of these methods, elaborated the weaknesses, and provided prospects for future development. Among them, chemical sequential extraction is universally applied in the morphological analysis of solid-phase samples, with diverse extraction conditions and procedures proposed in the current study. However, it has not been well standardized. The hyphenated techniques for instruments have significant advantages for the determination of elemental forms in solution, of which capillary electrophoresis system can separate similar substances with the same electrophoresis ability. Liquid chromatography systems have better performance in terms of separation capacity and detection limit. The computer simulations further expand the access to morphological analysis, enabling complex morphological calculations. It was proposed to combine multiple methods in the future to continuously improve the accuracy of analytical techniques by complementing and optimizing each other.

A 50-year record of platinum, iridium, and rhodium in Antarctic snow: volcanic and anthropogenic sources.

Antarctic snow preserves an atmospheric archive that enables the study of global atmospheric changes and anthropogenic disturbances from the past. We report atmospheric deposition rates of platinum group elements (PGEs) in Antarctica during the last ∼ 50 years based on determinations of Pt, Ir, and Rh in snow samples collected from Queen Maud Land, East Antarctica to evaluate changes in the global atmospheric budget of these noble metals. The 50-year average PGE concentrations in Antarctic snow were 17 fg g(-1) (4.7-76 fg g(-1)) for Pt, 0.12 fg g(-1) (<0.05-0.34 fg g(-1)) for Ir, and 0.71 fg g(-1) (0.12-8.8 fg g(-1)) for Rh. The concentration peaks for Pt, Ir, and Rh were observed at depths corresponding to volcanic eruption periods, indicating that PGEs can be used as a good tracer of volcanic activity in the past. A significant increase in concentrations and crustal enrichment factors for Pt and a slight enhancement in enrichment factors for Rh were observed after the 1980s. This suggests that there has been large-scale atmospheric pollution for Pt and probably for Rh since the 1980s, which may be attributed to the increasing emissions of these metals from anthropogenic sources such as automobile catalysts and metal production processes.

Emerging contaminants (Rh, Pd, and Pt) in surface sediments from a Brazilian subtropical estuary influenced by anthropogenic activities.

The concentrations of Platinum (Pt), Rhodium (Rh) and Palladium (Pd) were evaluated from a highly impacted estuary in Brazil influenced by industrial pole, highway traffic and sewage outfall. The Santos-São Vicente region presents important economic activities derived from a largest harbor of Latin America and an industrial pole surrounded by intensive highway traffic. Values of Rh varied from 0.08 to 1.7 ng g-1 with highest values at stations impacted by domestic waste. Pt ranged from 0.15 to 40.3 ng g-1 with highest concentrations located close to the ferryboat traffic. Pd levels varied from 1.05 to 22.0 ng g-1 with values >5 ng g-1 in 50% of the stations. The spatial distribution of PGEs was not always directly associated with muddy sediments, because high PGE levels found even in sandy sediments. Pollution indexes, including anthropogenic factor (AF), geoaccumulation index (Igeo), Enrichment factor (EF), and Pollution Load Index (PLI) were used for evaluating contaminant potential. Based on EF, Igeo, and PLI, 50% of samples of the sediments from Santos-São Vicente Estuarine System (SSV) were classified with significant to strong PGE contamination. All stations on the Santos Channel (SC), São Vicente Channel (SVC) and Bertioga Channel (BC) had AF higher than 80% in at least one of PGE elements, as showed in station 2A, which presented AF <50% for Rh and Pd and 86% for Pt. Despite high anthropogenic enrichment, no correlations among PGE elements were observed in surface sediments. Only two stations presented Pd/Pt, Pt/Rh, and Pd/Rh typical ratios of auto catalyst (st. 14 and Piaçaguera) both located in the vicinity of highways. This could be due to the PGE deposition process in road dust, soil, and water as well as the biogeochemical cycling of PGEs involving organic metallic and inorganic complexes formed in the estuarine and seawaters.

Platinum group elements contamination in soils: Review of the current state.

Platinum group elements (PGE: Ru, Rh, Pd, Os Ir, Pt) are rare metals with low abundance in the continental crust. The elements of the palladium subgroup of PGE (PPGE: Pt, Pd, Rh) have been exploited more and more over the last thirty years for their physicochemical properties such as high melting point, high resistance to corrosion, mechanical strength and ductility. This led to emerging environmental contamination in different media such as air, road dust, soil, sediment, vegetation, and snow. The aim of this review is to summarize the available data on soil contamination by PPGE and its potential environmental impact. In this paper, the environmental issue of PPGE is discussed with regard to their anthropogenic emission and fate, which includes speciation, possible transformations into bioavailable forms and toxicity. Soil contamination by PPGE is described taking into account urban and non-urban areas. The analytical determination process is also discussed.