Lawrence Berkeley National Laboratory

Carbonaceous nanomaterials represent a significant portion of ultra-fine airborne particulate matter, and iron is the most abundant transition metal in air particles. Owing to their high surface area and atmospheric oxidation, carbon nanoparticles (CNP) are enriched with surface carbonyl functional groups and act as a host for metals and small molecules. Using a synthetic model, concentration-dependent changes in the chemical speciation of iron adsorbed on oxidized carbon surfaces were investigated by a combination of X-ray and electron microscopic and spectroscopic methods. Carbon K-edge absorption spectra demonstrated that the CNP surface was enriched with carboxylic acid groups after chemical oxidation but that microporosity was unchanged. Oxidized CNP showed a high affinity for sorption of Fe(iii) from solution (75-95% uptake) and spectroscopic measurements confirmed a 3+ oxidation state of Fe on CNP irrespective of surface loading. The bonding of adsorbed Fe(iii) at variable loadings was determined by iron K-edge X-ray absorption spectroscopy. At low loadings (3 and 10 μmol Fe m-2 CNP), mononuclear Fe was octahedrally coordinated to oxygen atoms of carboxylate groups. As Fe surface coverage increased (21 and 31 μmol Fe m-2 CNP), Fe-Fe backscatters were observed at interatomic distances indicating iron (oxy)hydroxide particle formation on CNP. Electron-donating surface carboxylate groups on CNP coordinated and stabilized mononuclear Fe(iii). Saturation of high-affinity sites may have promoted hydroxide particle nucleation at higher loading, demonstrating that the chemical form of reactive metal ions may change with surface concentration and degree of CNP surface oxidation. Model systems such as those discussed here, with controlled surface properties and known chemical speciation of adsorbed metals, are needed to establish structure-activity models for toxicity assessments of environmentally relevant nanoparticles.