Transient absorption spectroscopy (TAS) has been used to study the interfacial electron-transfer reaction between photogenerated electrons in nanocrystalline titanium dioxide (TiO(2)) films and molecular oxygen. TiO(2) films from three different starting materials (TiO(2) anatase colloidal paste and commercial anatase/rutile powders Degussa TiO(2) P25 and VP TiO(2) P90) have been investigated in the presence of ethanol as a hole scavenger. Separate investigations on the photocatalytic oxygen consumption by the films have also been performed with an oxygen membrane polarographic detector. Results show that a correlation exists between the electron dynamics of oxygen consumption observed by TAS and the rate of oxygen consumption through the photocatalytic process. The highest activity and the fastest oxygen reduction dynamics were observed with films fabricated from anatase TiO(2) colloidal paste. The use of TAS as a tool for the prediction of the photocatalytic activities of the materials is discussed. TAS studies indicate that the rate of reduction of molecular oxygen is limited by interfacial electron-transfer kinetics rather than by the electron trapping/detrapping dynamics within the TiO(2) particles.

The risk associated with the inhalation of platinum group element (PGE) emissions from vehicle exhaust catalysts (VECs) has been investigated by extracting road dust and milled auto catalyst with simulated lung fluids. Gamble's solution (representative of the interstitial fluid of the deep lung) and artificial lysosomal fluid (ALF) (representative of the more acidic environment within the lung) were employed as extraction fluids. The highest PGE release was observed in ALF, implying that inhaled particles would have to be phagocytized before significant amounts of PGEs dissolve. The greatest percentage (up to 88%) of PGEs was released from road dust, possibly due to the presence of mobile PGE species formed in the roadside environment. Pt showed the highest absolute bioavailability, due to its greater concentration in the environmental samples. Pd and Rh had higher percentage of release, however, because of their more soluble nature. From the toxicological perspective, the results demonstrate potential health risks due to the likely formation of PGE-chloride complexes in the respiratory tract, such species having well-known toxic and allergenic effects on human beings and living organisms.

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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