Platinum (Pt), palladium (Pd) and rhodium (Rh) are emitted by vehicle exhaust catalysts (VECs) and their concentrations have increased significantly in various environmental compartments, including airborne particulate matter, soil, roadside dust, vegetation, rivers and oceanic environments, over the last two decades as the use of VECs has increased. However, data on the chemical speciation of the platinum-group elements (PGEs) and their bioavailabilities are limited. In this paper, the thermodynamic computer model, HSC, has been used to predict the interactions of Pt, Pd and Rh with different inorganic ligands and to estimate the thermodynamic stability of these species in the environment. Eh–pH diagrams for the PGEs in aqueous systems under ambient conditions (25°C and 1 bar) in the presence of Cl, N and S species have been prepared. The results indicate that Pt, Pd and Rh can form complexes with all of the inorganic ions studied, suggesting that they are capable of mobilizing the PGEs as aqueous complexes that can be transported easily in environmental and biological systems and that are able to enter the food chain. Hydroxide species can contribute to the transport of PGEs in oxidizing environments such as road-runoff waters, freshwater, seawater and soil solutions, whereas bisulphide complexes could transport Pt and Pd in reducing environments. Ammonia species appear to be significant under near-neutral to basic oxidizing conditions. Chloride species are likely to be important under oxidizing, acidic and saline environments such as seawater and road-runoff waters in snowmelt conditions. Mixed ammonia–chloride species may also contribute to the transport of Pt and Pd in highly saline solutions.

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