Assessing the potential of inorganic anions (Cl-, NO3-, SO42- and PO43-) to increase the bioaccessibility of emitted palladium in the environment: Experimental studies with soils and a Pd model substance.

Palladium (Pd) emitted from vehicles equipped with exhaust catalytic converters has been accumulating at a greater rate relative to other platinum group elements (PGE) in the last 10-20 years. Little is known, however, regarding the various environmental factors and conditions which are likely to modulate the chemical behavior and bioaccessibility of this element post-emission. To meet data needs, soils and a Pd model substance were treated with solutions containing common anions (Cl-, NO3-, SO42- und PO43-) to shed light on the geochemical behavior of emitted Pd under ambient conditions. As part of this, the particle surface chemistry of treated residues (insoluble phase) and solutions (soluble phase) was examined using XPS to assess the chemical transformation of Pd in the presence of inorganic anions. The results show that Pd is the most soluble in the presence of anionic species, followed by rhodium (Rh) and platinum (Pt). Pd in field-collected samples was found to be considerably more soluble than the metallic Pd in the model substance, Pd black, when treated with anionic species. The results also demonstrate that the solubility of Pd black is strongly dependent on solution pH, concentration and the duration of reaction. The outer 3-4 atomic layers of metallic Pd was determined via XPS to be partially oxidized when treated with anion solutions, with the degree being dependent on anion type. The concentration of dissolved O2 in solution was found to have little impact on the transformation of metallic Pd. Given the ubiquitous nature of the anions examined, we can expect that Pd will become more bioaccessible post-emission.

Platinum group element and cerium concentrations in roadside environments in Toronto, Canada.

Platinum (Pt), palladium (Pd) and rhodium (Rh) are accumulating globally in the environment, due to their use as catalysts to control automotive exhaust emissions. While environmental increases in platinum metal concentrations have been well documented for a number of countries, published data for Canada have been missing to date. The aim of this study is to examine the concentrations of Pt, Pd and Rh, as well as Ce, in soils and dust as a function of traffic volume in Toronto, Ontario. Soils and road and underpass dust were collected from two sites with medium and high volumes of traffic. Samples were acid digested and co-precipitated with Hg (for Pd) and Te (for Pt and Rh), prior to measurement using ICP-Q-MS. Palladium occurred at the highest levels in samples, followed by Pt and Rh. Median concentrations for all soil samples were 63 µg Pd/kg, 8.7 µg Pt/kg, 1.7 µg Rh/kg and 41 mg Ce/kg. The results support existing data regarding PGE accumulation trends in urban and roadside environments, due to their use as catalysts in automotive catalytic converters. This study also confirms a shift toward the heavier use of Pd as the catalyst of choice in recent years, as reflected in the higher concentrations measured for this metal relative to Pt and Rh. The results highlight a need to continue monitoring the accumulation of PGE, most notably Pd, in urban environments.

Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid.

Risk assessments of platinum group metal (PGE) emissions, notably those of platinum (Pt), palladium (Pd) and rhodium (Rh), have been mostly based on data regarding the metallic forms used in vehicular exhaust converters, known to be virtually biologically inert and immobile. To adequately assess the potential impacts of PGE, however, data on the chemical behaviour of these metals under ambient conditions post-emission is needed. Complexing agents with a high affinity for metals in the environment are hypothesized to contribute to an increased bioaccessibility of PGE. The purpose of this study is to examine the modulating effects of the organic complexing agents, L-methionine and citric acid, on the geochemical behavior of Pd in soils and model substances (Pd black and PdO). Batch experimental tests were conducted with soils and model substances to examine the impacts of the concentration of complexing agents, pH and length of extraction period on Pd solubility and its chemical transformation. Particle surface chemistry was examined using X-ray photoelectron spectroscopy (XPS) on samples treated with solutions under various conditions, including low and high O2 levels. Pd was observed to be more soluble in the presence of organic complexing agents, compared to Pt and Rh. Pd in soils was more readily solubilized with organic complexing agents compared to the model substances. After 7 days of extraction, L-methionine (0.1 M) treated soil and Pd black samples, for instance, had mean soluble Pd fractions of 12.4 ± 5.9% and 0.554 ± 0.024%, respectively. Surface chemistry analyses (XPS) confirmed the oxidation of metallic Pd surfaces when treated with organic complexing agents. The type of organic complexing agent used for experimental purposes was observed to be the most important factor influencing solubility, followed by solution pH and time of extraction. The results demonstrate that metallic Pd can be transformed into more bioaccessible species in the presence of organic complexing agents which are ubiquitous in the environment.

Metal and metalloid accumulation in cultivated urban soils: A medium-term study of trends in Toronto, Canada.

This study aims to examine the elemental enrichment patterns in low to medium traffic areas over a three year period in Toronto, Canada. Soils were sampled at three locations with different volumes of traffic between 2010 and 2013. A range of elements, including V, Cr, Mn, Cu, Cd, As, Sb and Pb, were measured in acid digested samples using ICP-MS. While the concentrations of Cd, Sb and Pb were found to be relatively low, a significant, albeit small increase in their levels over time was determined for all sites. For the low traffic areas, median Cd, Sb and Pb concentrations increased from 0.18mg Cd/kg, 0.14mg Sb/kg and 12mg Pb/kg in 2010 to 0.38mg Cd/kg, 0.21mg Sb/kg and 15mg Pb/kg in 2012, respectively. For the medium traffic site, the respective levels of Cd and Sb rose from 0.19mg Cd/kg and 0.14mg Sb/kg in 2010 to 0.49mg Cd/kg and 0.28mg Sb/kg in 2012. Median Pb concentrations at the medium traffic site were comparable to those at the low traffic sites (13mg/kg in 2010 and 15mg/kg in 2012). Principal Component Analysis (PCA) revealed the existence of two components (rotated), which explained 77% of the variance for all sites: 1. PC1 with large loadings of V, Cr, Co and Cu that likely originate from the commercial soil originally used for monitoring purposes, and 2. PC2 with high correlations between Cd, Sb and Pb, attributed to traffic sources of emissions. The resuspension and transport of more mobile fractions of contaminated dust and soil particles is hypothesized to be contributing to an elemental enrichment of soils located in low traffic areas.

The influence of ethylenediamine tetra acetic acid (EDTA) on the transformation and solubility of metallic palladium and palladium(II) oxide in the environment.

The environmental occurrence of elevated concentrations of platinum (Pt), palladium (Pd) and rhodium (Rh) from automotive catalytic converters has been well-documented. Limited information exists regarding their chemical behavior post-emission, however, especially in the presence of commonly occurring complexing agents. The purpose of this study is to examine the influence of ethylenediamine tetra acetic acid (EDTA) on the possible environmental transformation and solubility of Pd by conducting batch experiments using metallic palladium (Pd black) and palladium(ii) oxide (PdO). Changes in the particle surface chemistry of treated samples were analyzed using X-ray Photoelectron Spectroscopy (XPS) and Transition Electron Microscopy/Energy Dispersive X-ray Spectrometry (TEM/EDX) techniques. Metallic palladium was partially transformed into PdOx (x < 1), while PdO remained largely unaffected. The pH of EDTA solutions was observed to modulate Pd solubility, with Pd black demonstrating a higher solubility compared to PdO. Solubility was also found to increase with a corresponding increase in the strength of EDTA solution concentrations, as well as with the length of extraction time. The overall solubility of Pd remained relatively low for most samples (<1 wt%). A dissolution rate of 2.01 ± 0.17 nmol m(-2) h(-1) was calculated for Pd black in 0.1 M EDTA (pH 7). In contrast to previously held assumptions about the environmental immobility of Pd, small amounts of this element emitted in metallic form are likely to be soluble in the presence of complexing agents such as EDTA.

Metal translocation patterns in Solanum melongena grown in close proximity to traffic.

The purpose of this study is to examine tissue patterns of metal (Cr, Ni, Cu, Cd, and Pb) concentrations in Solanum melongena cultivated in close proximity to traffic to help elucidate associated elemental deposition and soil-to-root and root-to-shoot transfers. Plants were cultivated in a commercial soil mix at three sites in Toronto, Canada. Metal concentrations were determined on microwave-digested bulk and rhizosphere soil and tissue samples per ICP-MS, along with two standard reference materials (NIST #1570a and #2709a). Unwashed and washed S. melongena samples were also analyzed, along with Origanum vulgare plants from the same sites, to assess the effectiveness of washing in reducing metal concentrations. The tissue distribution of Cr, Ni, Cu, and Pb demonstrated variability as a function of traffic proximity. Copper was found to easily translocate to roots in soils susceptible to waterlogging, while Cd had the highest soil-to-root and root-to-shoot translocation. The translocation of Cd was highest at the roadside site, due to a greater relative enrichment of this metal in the rhizosphere of S. melongena plants. Washing O. vulgare leaves was more effective in removing metal-associated particles compared to S. melongena samples. Cadmium uptake is of greatest concern given its toxicity and translocation potential.

Traffic-related trace element fate and uptake by plants cultivated in roadside soils in Toronto, Canada.

This research examines traffic-related trace element emissions and their uptake by plants grown in urban roadside environments in Toronto, Canada. Oregano (Origanum vulgare), beets (Beta vulgaris) and eggplants (Solanum melongena) were cultivated at four locations with variable traffic-related metal inputs in 2010. The top 30 cm of soil at the medium-traffic location was first replaced with a triple mix soil (topsoil, compost and peat) to control for pre-existing contamination. The same soil was used to cultivate at the two no/low traffic locations. Soil at the heavy traffic location was not remediated. Soil, plant tissue and plant rhizosphere samples were collected for the analysis of a range of traffic-related metal(loids) using ICP-MS, including Cr, Mn, Cu, Ni, Cd, As, Sb and Pb. Samples were digested with HNO(3) and HCl using a microwave-assisted digestion procedure and then treated with HF prior to analysis. Two certified reference materials, San Joaquin soil (NIST 2709a) and trace elements in spinach leaves (NIST 1570a), were used for QA/QC purposes. Metal(loid) concentrations and accumulation over time were highly variable at the medium traffic site where the soil was replaced. Mn (p<0.10), As (p<0.10) and Sb (p<0.01) concentrations significantly increased in bulk soils from May to November 2010, while Ce (p<0.01) and Cd (p<0.10) levels decreased. For instance, median As concentrations increased from 4.39 to 8.40 mg/kg over this period. Metals were found to be more bioaccessible to O. vulgare grown in the new soil at the medium traffic volume site, compared to the aged soil at the heavy traffic location. Several elements, most notably Cd, were also found to accumulate in the root zone of sampled S. melongena. Metal concentrations in S. melongena rhizosphere were better predictors of plant tissue levels, providing evidence that soil quality guidelines based on total metal concentrations for bulk soils are inadequate.

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.

Platinum group elements (Pt, Pd, Rh) in airborne particulate matter in rural vs. urban areas of Germany: concentrations and spatial patterns of distribution.

This study examines platinum group element concentrations (PGE) (i.e. platinum (Pt), palladium (Pd) and rhodium (Rh)) and their spatial distribution in airborne particulate matter fractions (PM) of human health concern in urban and rural areas of Germany. Fractionated airborne dust and PM(10), PM(2.5) and PM(1) samples were collected along a busy road in Frankfurt am Main from July 2008 to April 2010. PM(10) was also sampled in Deuselbach and Neuglobsow between January 2008 and July 2009 to examine their concentrations at rural locations and potential for long-range transport. Pt, Pd and Rh were isolated and pre-enriched in samples using a combination of Te and Hg co-precipitation methods. Concentrations were determined using isotope dilution ICP-Q-MS (in collision mode with He). The highest airborne PGE concentrations were measured in PM(10) from Frankfurt (e.g. 12.4pg Pt/m(3) (mean)), while the rural locations of Deuselbach and Neuglobsow exhibited the lowest levels (e.g. 2pg Pt/m(3) (mean)). PGE concentrations were observed to decline with increasingly smaller PM size fractions from PM(10) to PM(1). All size fractions generally contained higher levels of Pd compared to Pt and Rh, an element of greater concern due to its solubility. PM(2.5) collected in Frankfurt had a mean of 16.1pg Pd/m(3), compared to 9.4pg/m(3) for Pt. PGE concentrations also demonstrated a distinct seasonal relationship, with the greatest levels occurring in winter. Compared to a previous study in 2002, PGE concentrations in fractionated airborne dust have significantly increased over time. Elevated PGE levels were also measured for PM(10) sampled in Neuglobsow and Deuselbach, which could not be attributed to local emission sources. Using the diagnostic meteorological model, CALMET, trajectory analyses confirmed our hypothesis that PGE are being transported over longer distances from other areas of Europe.

Airborne particulate matter, platinum group elements and human health: a review of recent evidence.

Environmental concentrations of the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) have been on the rise, due largely to the use of automobile catalytic converters which employ these metals as exhaust catalysts. It has generally been assumed that the health risks associated with environmental exposures to PGE are minimal. More recent studies on PGE toxicity, environmental bioavailability and concentrations in biologically relevant media indicate however that environmental exposures to these metals may indeed pose a health risk, especially at a chronic, subclinical level. The purpose of this paper is to review the most recent evidence and provide an up-to-date assessment of the risks related to environmental exposures of PGE, particularly in airborne particulate matter (PM). This review concludes that these metals may pose a greater health risk than once thought for several reasons. First, emitted PGE may be easily mobilised and solubilised by various compounds commonly present in the environment, thereby enhancing their bioavailability. Second, PGE may be transformed into more toxic species upon uptake by organisms. The presence of chloride in lung fluids, for instance, may lead to the formation of halogenated PGE complexes that have a greater potential to induce cellular damage. Third, a significant proportion of PGE found in airborne PM is present in the fine fraction that been found to be associated with increases in morbidity and mortality. PGE are also a concern to the extent that they contribute to the suite of metals found in fine PM suspected of eliciting a variety of health effects, especially in vulnerable populations. All these factors highlight the need to monitor environmental levels of PGE and continue research on their bioavailability, behaviour, speciation and associated toxicity to enable us to better assess their potential to elicit health effects in humans.

Changes in palladium, platinum, and rhodium concentrations, and their spatial distribution in soils along a major highway in Germany from 1994 to 2004.

Soil samples were collected along the highway A5 from the major junctions Frankfurter Kreuz to Darmstäder Kreuz from July to September, 2004 and analyzed for palladium (Pd), platinum (Pt), and rhodium (Rh). The results were compared to analyses of platinum group elements (PGE) in soils collected along this same stretch of highway in 1994. The goal of this study is to detect any changes that may have occurred in the concentration and environmental distribution patterns of these metals over this 10 year period. The concentrations of Pd in soils along the highway were found to be about 15 times higher on average than those measured in 1994. Pt and Rh concentrations increased 2 and 1.6 times, respectively, during this time period. The significant rise in Pd concentrations in soils observed for the time period of analysis is likely due to its use in automobile catalytic converters in Germany since 1993. The results also show a strong positive relationship between PGE emissions and traffic density and speed. The results indicate that increases in the concentrations of Pd, Pt, and Rh in soils along the highway are not limited to the soil surface. Pt was measured as deep as 12 cm. Pd was determined at even greater depths of 12-16 cm. The presence of Pd at lower depths compared to Pt suggests that this element has a higher solubility. Pd, Pt, and Rh concentrations display a strong inverse relationship with distance from the road, with decreasing levels with increasing distance from the highway. Nonetheless, Pd and Pt were detected in a meadow as far as 50 m from the highway, a much greater distance compared to that measured for these metals in 1994. Pt concentrations were also found to significantly correlate with levels of Rh and Pd. The ratios between the PGE analyzed (Pt/Rh and Pd/Rh) display a shift toward Pt and Pd. The results clearly show that PGE concentrations have increased over time. Observed increases in Pd concentrations are particularly a cause of concern.

Concentration and distribution of heavy metals in urban airborne particulate matter in Frankfurt am Main, Germany.

Heavy metal concentrations were measured in airborne dust collected at three sites with different traffic densities from August 2001 to July 2002 in the Frankfurt am Main area. Bulk samples of particulate matter (PM) with an aerodynamic equivalent diameter of <22 microm were collected on cellulose nitrate filters using air filtration devices. Fractionated samples of PM with an aerodynamic equivalent diameter of <10 microm were collected using an eight-stage Andersen impactor. Pb, Cd, Mn, Ni, Zn, V, As, Sb, Cu, Cr, Co, and Ce were determined by inductively coupled plasma sector field mass spectrometry, Pt and Rh were determined by adsorptive voltammetry, and Pd was determined by total reflection X-ray fluorescence analysis. The results show that the highest airborne heavy metal concentrations occurred at the main street with a large volume of traffic. With the exception of Co, V, Ce, and Mn, the heavy metals had an elevated enrichment factor compared to their concentrations in the continental crust. The main street site was especially contaminated with Sb, Zn, Cu, V, and Ni. Motor vehicles are the likely source of emissions. With the exception of Cr, Cu, and Zn, most of the airborne heavy metal concentrations determined for impactor samples deviate slightly from the results for total airborne dust. Heavy metal particle size distributions can be divided into three groups. For metals such as As, Cd, Pb, and V, the main fraction can be found in fine particles with a diameter of <2.1 microm, whereas Ce, Cr, Co, and Ni occur mainly in coarse particles with a diameter of >2.1 microm. Cu, Mn, Sb, Zn, Pt, Pd, and Rh occur in high concentrations in the medium range of the impactor stages (particle diameters of 1.1-4.7 microm). Metal concentrations in fine dust particles are needed to assess the human health risks of their inhalation.

Concentration and distribution of platinum group elements (Pt, Pd, Rh) in airborne particulate matter in Frankfurt am Main, Germany.

The concentrations and distribution of platinum group elements (Pt, Pd, Rh) in airborne particulate matter were studied in a period of one year from August 2001 to July 2002 in urban and in nonurban areas. Airborne dust samples were collected as a total amount (particles with an aerodynamic diameter <22 microm) and classified using an eight-stage Andersen impactor (<10 microm) at three locations with different traffic density roads in the Frankfurt am Main and nonurban areas. Sampling at the three locations was performed simultaneously for total airborne dust and fractionated airborne dust. Pd was determined by total reflection X-ray fluorescence after Hg coprecipitation. Pt and Rh were analyzed by adsorptive striping voltammetry after HPA digestion. The results show that the PGE concentrations in airborne samples depend on the traffic density. The highest PGE concentrations in air were found in the vicinity of major roads with heavy traffic, and the lowest ones were found in the nonurban area. The presence of PGE at the sampling station relatively free of traffic in a nonurban area hints to a transport of some of the emitted PGE from the city to this station by wind. At all three sampling locations, a heterogeneous distribution of the Pd, Pt, and Rh concentrations during the sampling year can be observed. The sum of PGE concentrations in total airborne dust is comparable with the sum of impactor samples. However, the concentration of Pt and Rh in total airborne dust (<22 microm) is on average higher than in impactor samples (<10 microm). On the contrary, Pd concentration is higher in impactor samples in most cases. The airborne PGE distribution is dominated by Pt, followed by Pd and Rh. The impactor samples are dominated by Pd, followed by Pt and Rh. This fact indicates that palladium occurs mainly in relatively fine airborne particles. The main fraction of PGE is found on average in particle sizes between 1.1 and 4.7 microm. Knowledge of the size distribution of particles containing PGE is important with respect to risk assessment of human inhalation.