Clare L.S. Wiseman

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.

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.

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.

Analytical methods for assessing metal bioaccessibility in airborne particulate matter: A scoping review

In contrast to the existence of standardized methods to assess metal bioaccessibility via the gastrointestinal route, there are no widely-accepted, established in vitro testing protocols to measure elemental solubility in the human lung. This may be attributed, in part, to the difficulty associated with simulating the lungs complex in vivo conditions. The purpose of this review is two-fold: (1) to determine how the bioaccessibility of metals associated with ambient particulate matter (PM) in the human lung has been assessed in the literature, and (2) examine the suitability and biological relevance of applied methods for the measurement of metal bioaccessibility employed to date. The review revealed that limited attention has been paid to the development and application of biologically-relevant in vitro methods to measure elemental solubility in ambient PM as a proxy for bioaccessibility in the human lung. Few studies (n=14) used synthetic lung fluids to simulate in vivo conditions, with only half extracting samples at a biologically-relevant temperature of 37°C. There was limited evidence suggesting that the use of water is less effective as a leaching agent compared to simulated lung fluids. In sum, this scoping review highlights a critical need to develop standardized methods for the systematic assessment of elemental bioaccessibility via the respiratory route. Priority should be placed on the validation of biologically-relevant methods, including the use of leaching agents and extraction parameters used, which allow for testing to be conducted in a reliable, yet cost efficient, manner.

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 Gambles 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 Gambles 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 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.

Urban Airborne Particulate Matter

Urban airborne particulate matter , Urban airborne particulate matter , کتابخانه مرکزی دانشگاه علوم پزشکی تهران

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.

Platinum Metals in the Environment

Platinum group elements (PGE, i.e. Pt, Pd, Rh, Ir, Ru, Os) are among the least abundant elements in the Earth’s continental crust. PGE concentrations in urban and roadside environments are, however, increasing as a result of anthropogenic emissions. Automobile catalysts are generally considered the main PGE source into the urban and roadside environments. We argue that most studies to date have been carried out with a presumption of potential sources, and this bias may have masked additional, yet unidentified PGE sources. Comparison of environmental records at urban locations suggests that PGE emissions reflect contributions from several sources, including automobile catalysts, industry and medical treatment centers. Coal combustion may also contribute to urban PGE fluxes. Environmental records at remote locations support contributions from such diverse sources. Estimates of PGE emissions, however uncertain, indicate that these diverse sources contribute significantly to the global PGE budget at the Earth’s surface.

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.