RESUMEN

The concentration of platinum group elements (PGE) in the environment has increased significantly in the last 20 years mainly due to their use as catalysts in automotive catalytic converters. The quantitation of these metals in different environmental compartments is, however, challenging due to their very low concentrations and the presence of interfering matrix constituents when inductively coupled plasma-mass spectrometry (ICP-MS) is used for analysis. Previously, the research focus was on the analysis of platinum (Pt) and rhodium (Rh). However, due to the increasing use of palladium (Pd) in automotive catalytic converters, quantitation of this element in airborne particulate matter (PM) is also needed. Compared to Pt and Rh, measurements of Pd using ICP-MS are plagued by greater molecular interferences arising from elements such as copper (Cu), zinc (Zn) strontium (Sr), yttrium (Y), and zirconium (Zr). The aim of this study was to evaluate the applicability of reductive co-precipitation procedures using both mercury (Hg) and tellurium (Te) for the pre-concentration of Pd from airborne PM. Furthermore, helium (He) was tested as a collision gas for isotope dilution-inductively coupled plasma-quadrupole-mass spectrometry (ID-ICP-Q-MS) to measure Pd in the Hg and Te precipitates. Airborne PM samples (PM10) were collected from Neuglobsow (Brandenburg, north-eastern Germany) and Deuselbach (Rhineland-Palatinate, south-western Germany), considered to represent background levels, and from the city Frankfurt am Main (Hesse, Germany), a high-traffic area. Samples were first digested with aqua regia in a high-pressure asher (HPA) at 320 degrees C and 130 bar prior to the application of reductive co-precipitation procedures. The method was validated with road dust reference material BCR-723 and the CANMET-CCRMP reference material TDB-1 and WPR-1. In airborne PM collected at the background areas Neuglobsow and Deuselbach, Pd was detected with median concentrations values of 0.5 and 0.6 pg/m3, respectively. Much higher median concentration values of 14.8 pg Pd/m3 (detection limit = 0.01 pg Pd/m3) were detected in samples collected in the city of Frankfurt am Main. Results have shown that Hg co-precipitation depletes the concentrations of interfering matrix constituents by at least one order of magnitude more, compared to Te co-precipitation, making it a more effective method for the isolation and pre-enrichment of Pd from airborne PM prior to analysis. The use of a He gas flow of 120 ml/min in the plasma further minimized interferences, particularly those arising from CuAr+, YO+, and ZrO+ during the determination of Pd. The results demonstrate that Hg co-precipitation and the use of He collision gas, in combination with isotope dilution, are highly effective methods for the quantitation of Pd in airborne PM using ICP-MS.

Asunto(s)

RESUMEN

Increases in platinum group element (PGE) concentrations in ambient air and dust since the introduction of automotive catalytic converters in 1988 is a cause of concern. Until now, data derived from engine-test bench experiments have provided the basis for the assessment of human health risks associated with PGE exposure. Such experiments have provided valuable information regarding emission data that has been used to estimate ambient exposure concentrations. However, these data are not necessarily representative of typical environmental PGE exposure levels and conditions. Data on measured environmental concentrations is needed to provide a more adequate basis for the assessment of exposure and related risks. Twenty air and airborne-dust samples were provided by the Umweltbundesamt (Federal Environmental Agency, Germany) in the years 1988, 1989, 1992, 1997, and 1998. The samples were collected in Frankfurt/Main and the adjacent city of Offenbach. For this, 11 to 80 m3 of air were filtered over a 24-72 h period using a vacuum. Glass-fiber filters were used to collect samples. Sample platinum and rhodium concentrations were determined using adsorptive voltammetry. Although the number of samples collected in different years is limited, the results indicate a trend toward continuous increases in ambient concentrations of these metals between 1988 and 1998. Specifically, there were 46- and 27-fold increases in Pt and Rh concentrations, respectively. Despite these observed increases, the Pt concentrations measured (i.e., 147 pg/m3 on average, with a maximum of 246 pg/m3 in 1998) fell far below 15,000 pg/m3, which has been suggested as a guidance value (i.e., exposure at this level would be expected to be without appreciable health risk). The results of a particle-size distribution analysis of one sample (8-step impactor) that was collected 150 m away from a street show that approximately 75% of Pt and 95% of Rh occurs in association with large particulate matter of > 2 microns, with concentrations reaching a maximum in particles of 4.7 to 5.8 microns. The remaining 25% of Pt and 5% of Rh is present in fine particulate matter of < 2 microns. An approximate 10% of Pt and < 38% of Rh in airborne particles was found to be soluble in 0.1 molar HCl. Further, the results indicate that most of the emitted PGE particles from automotive catalytic converters, particularly those bound to fine particulate matter, are capable of being airborne. As a result, PGEs are not only present in areas close to emissions (e.g., roads), but can be transported over longer distances.

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RESUMEN

Soil samples from the area of Hanau (Hessen, Germany) were analyzed for anthropogenic platinum-group elements (PGE). The results confirm the existence of two different sources for anthropogenic PGE: 1. automotive catalysts, and 2. PGE-processing plants. Both sources emit qualitatively and quantitatively different PGE spectra and PGE interelemental ratios (especially the Pt/Rh ratio). Elevated PGE values which are due to automotive catalysts are restricted to a narrow-range along roadside soil, whereas those due to PGE-processing plants display a large-area dispersion. The emitted PGE-containing particles in the case of automotive catalysts are subject to transport by wind and water, whereas those from PGE-processing plants are preferably transported by wind. This points to a different aerodynamic particle size. Pt, Pd, and Rh concentrations along motorways are dependent on the amount of traffic and the driving characteristics.