Analysis of Palladium Concentrations in Airborne Particulate Matter with Reductive Co-Precipitation, He Collision Gas and ID-ICP-Q-MS

Abstract

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 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 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 °C and 130 bar prior to the application of reductive co-precipitation procedures. The method was validated with road dust reference material BCR723 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 show 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. This work adapted from Alsenz et al. in Anal Bioanal Chem 395:1919–1927, 2009.