Physical chemical characterization of nanomaterials is critical to assessing quality control during production, evaluating the impact of material properties on human health and the environment, and developing regulatory frameworks for their use. We have investigated a set of 29 nanomaterials from four metal oxide families (aluminum, copper, titanium and zinc) with a focus on the measurands that are important for the basic characterization of dry nanomaterials and the determination of the dose metrics for nanotoxicology. These include crystalline phase and crystallite size, measured by powder X-ray diffraction, particle shape and size distributions from transmission electron microscopy, and specific surface area, measured by gas adsorption. The results are compared to the nominal data provided by the manufacturer, where available. While the crystalline phase data are generally reliable, data on minor components that may impact toxicity is often lacking. The crystal and particle size data highlight the issues in obtaining size measurements of materials with broad size distributions and significant levels of aggregation, and indicate that reliance on nominal values provided by the manufacturer is frequently inadequate for toxicological studies aimed at identifying differences between nanoforms. The data will be used for the development of models and strategies for grouping and read-across to support regulatory human health and environmental assessments of metal oxide nanomaterials.
Toxicological effects of metal-oxide-engineered nanomaterials (ENMs) are closely related to their distinct physical–chemical properties, especially solubility and surface reactivity. The present study used five metal-oxide ENMs (ZnO, MnO2, CeO2, Al2O3, and Fe2O3) to investigate how various biologically relevant media influenced dissolution behaviour. In both water and cell culture medium (DMEM), the metal-oxide ENMs were more soluble than their bulk analogues, with the exception that bulk-MnO2 was slightly more soluble in water than nano-MnO2 and Fe2O3 displayed negligible solubility across all tested media (regardless of particle size). Lowering the initial concentration (10 mg/L vs. 100 mg/L) significantly increased the relative solubility (% of total concentration) of nano-ZnO and nano-MnO2 in both water and DMEM. Nano-Al2O3 and nano-CeO2 were impacted differently by the two media (significantly higher % solubility at 10 mg/L in DMEM vs. water). Further evaluation of simulated interstitial lung fluid (Gamble’s solution) and phagolysosomal simulant fluid (PSF) showed that the selection of aqueous media significantly affected agglomeration and dissolution behaviour. The solubility of all investigated ENMs was significantly higher in DMEM (pH = 7.4) compared to Gamble’s (pH 7.4), attributable to the presence of amino acids and proteins in DMEM. All ENMs showed low solubility in Gamble’s (pH = 7.4) compared with PSF (pH = 4.5), attributable to the difference in pH. These observations are relevant to nanotoxicology as increased nanomaterial solubility also affects toxicity. The results demonstrated that, for the purpose of grouping and read-across efforts, the dissolution behaviour of metal-oxide ENMs should be evaluated using aqueous media representative of the exposure pathway being considered.
Road dust is an important source of resuspended particulate matter (PM) but information is lacking on the chemical composition of the ultrafine particle fraction (UFP; <0.1 µm). This study investigated metal concentrations in UFP isolated from the “dust box” of sweepings collected by the City of Toronto, Canada, using regenerative-air-street sweepers. Dust box samples from expressway, arterial and local roads were aerosolized in the laboratory and were separated into thirteen particle size fractions ranging from 10 nm to 10 µm (PM10). The UFP fraction accounted for about 2% of the total mass of resuspended PM10 (range 0.23–8.36%). Elemental analysis using ICP-MS and ICP-OES revealed a marked enrichment in Cd, Cr, Zn and V concentration in UFP compared to the dust box material (nano to dust box ratio ≥ 2). UFP from arterial roads contained two times more Cd, Zn and V and nine times more Cr than UFP from local roads. The highest median concentration of Zn was observed for the municipal expressway, attributed to greater volumes of traffic, including light to heavy duty vehicles, and higher speeds. The observed elevated concentrations of transition metals in UFP are a human health concern, given their potential to cause oxidative stress in lung cells.
1 December 2018 in Science of The Total Environment