Mirella Miettinen

Airway Exposure to Silica-Coated TiO2 Nanoparticles Induces Pulmonary Neutrophilia in Mice

The importance of nanotechnologies and engineered nanoparticles has grown rapidly. It is therefore crucial to acquire up-to-date knowledge of the possible harmful health effects of these materials. Since a multitude of different types of nanosized titanium dioxide (TiO(2)) particles are used in industry, we explored their inflammatory potential using mouse and cell models. BALB/c mice were exposed by inhalation for 2 h, 2 h on 4 consecutive days, or 2 h on 4 consecutive days for 4 weeks to several commercial TiO(2) nanoparticles, SiO(2) nanoparticles, and to nanosized TiO(2) generated in a gas-to-particle conversion process at 10 mg/m(3). In addition, effects of in vitro exposure of human macrophages and fibroblasts (MRC-9) to the different particles were assessed. SiO(2)-coated rutile TiO(2) nanoparticles (cnTiO(2)) was the only sample tested that elicited clear-cut pulmonary neutrophilia. Uncoated rutile and anatase as well as nanosized SiO(2) did not induce significant inflammation. Pulmonary neutrophilia was accompanied by increased expression of tumor necrosis factor-alpha (TNF-alpha) and neutrophil-attracting chemokine CXCL1 in the lung tissue. TiO(2) particles accumulated almost exclusively in the alveolar macrophages. In vitro exposure of murine and human macrophages to cnTiO(2) elicited significant induction of TNF-alpha and neutrophil-attracting chemokines. Stimulation of human fibroblasts with cnTiO(2)-activated macrophage supernatant induced high expression of neutrophil-attracting chemokines, CXCL1 and CXCL8. Interestingly, the level of lung inflammation could not be explained by the surface area of the particles, their primary or agglomerate particle size, or radical formation capacity but is rather explained by the surface coating. Our findings emphasize that it is vitally important to take into account in the risk assessment that alterations of nanoparticles, e.g., by surface coating, may drastically change their toxicological potential.

Development of a highly controlled gas-phase nanoparticle generator for inhalation exposure studies.

We have developed a gas-phase nanoparticle generator that produces stable and well-defined size distributions for TiO2. The online analyses of the gas-phase compounds and total number concentration of the generated particles as well as the off-line analysis of the filter samples confirmed the stability of the production. The major advantage of this reactor is that the test substance is directly in the aerosol phase, and thus no preprocessing is needed. This eliminates the physicochemical changes between bulk and administrated material during storing or processing. This system is easy to adjust to different experimental setups and precursors. As a result, well-characterized nanomaterials for inhalation exposure studies can be produced. At mass concentration of 30 mg/Nm3, the count mean diameter was 126 nm (geometric SD 1.6), mass mean diameter was 161 nm (2.0), mass median aerodynamic diameter was 125 nm, and the concentrations of harmful gas-phase by-products remained low. The produced powder consisted of crystals of anatase (77 vol%) and brookite (23 vol%), and its specific surface area was 69 m2/g.

Films of Graphene Nanomaterials Formed by Ultrasonic Spraying of Their Stable Suspensions

Graphene, a two-dimensional carbon allotrope, exhibits excellent optoelectronic properties. The assembly of graphene into films provides a platform to deepen the study of its interaction with varying surfaces, to engineer devices, and to develop functional materials. A general approach to produce graphene films consists of preparing a dispersion and laying it on a substrate of choice, followed by solvent evaporation. Here, we report the preparation of stable suspensions of new types of graphene nanomaterials namely, graphene nanoflowers (GNFs) and multi-layer graphene (MLG) flakes, in ethanol, N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP). Sprayable suspensions of both GNFs and MLG were prepared in DMF/ethanol, which showed high stability, without addition of any surfactant. The stable suspensions were used to deposit micrometer-thick MLG/GNF films on glass substrates. Calculations of initial droplet size and of timescale of droplet evaporation are performed and possible thermophoretic effects on droplet deposition discussed as well. Coating glass substrates with a methacrylic acid–methyl methacrylate (MA) copolymer prior to the deposition significantly improved the adhesion of the nanomaterials to the substrate. With the MA coating, a substrate coverage of nearly 100% was achieved at 14-min spraying time for 0.05 wt% GNF and 0.1 wt% MLG suspensions. Raman spectra of the GNF and MLG films reveal that the films were made of MLG in which the individual graphene layers rotated from each other as in turbostratic graphene. This work provides a general approach to prepare graphene nanomaterial suspensions and to create films for a variety of applications. The spraying process applied in the current work is highly scalable and allows control of film characteristics through process parameters. Copyright 2015 American Association for Aerosol Research

Physicochemical Characterization of Aerosol Generated in the Gas Tungsten Arc Welding of Stainless Steel.

OBJECTIVES Exposure to stainless steel (SS) welding aerosol that contain toxic heavy metals, chromium (Cr), manganese (Mn), and nickel (Ni), has been associated with numerous adverse health effects. The gas tungsten arc welding (GTAW) is commonly applied to SS and produces high number concentration of substantially smaller particles compared with the other welding techniques, although the mass emission rate is low. Here, a field study in a workshop with the GTAW as principal welding technique was conducted to determine the physicochemical properties of the airborne particles and to improve the understanding of the hazard the SS welding aerosols pose to welders. METHODS Particle number concentration and number size distribution were measured near the breathing zone (50cm from the arc) and in the middle of the workshop with condensation particle counters and electrical mobility particle sizers, respectively. Particle morphology and chemical composition were studied using scanning and transmission electron microscopy and energy-dispersive X-ray spectroscopy. RESULTS In the middle of the workshop, the number size distribution was unimodal with the geometric mean diameter (GMD) of 46nm. Near the breathing zone the number size distribution was multimodal, and the GMDs of the modes were in the range of 10-30nm. Two different agglomerate types existed near the breathing zone. The first type consisted of iron oxide primary particles with size up to 40nm and variable amounts of Cr, Mn, and Ni replacing iron in the structure. The second type consisted of very small primary particles and contained increased proportion of Ni compared to the proportion of (Cr + Mn) than the first agglomerate type. CONCLUSIONS The alterations in the distribution of Ni between different welding aerosol particles have not been reported previously.

PM2.5 concentration and composition in the urban air of Nanjing, China: Effects of emission control measures applied during the 2014 Youth Olympic Games

Industrial processes, coal combustion, biomass burning (BB), and vehicular transport are important sources of atmospheric fine particles (PM2.5) and contribute to ambient air concentrations of health-hazardous species, such as heavy metals, polycyclic aromatic hydrocarbons (PAH), and oxygenated-PAHs (OPAH). In China, emission controls have been implemented to improve air quality during large events, like the Youth Olympic Games (YOG) in August 2014 in Nanjing. In this work, six measurement campaigns between January 2014 and August 2015 were undertaken in Nanjing to determine the effects of emission controls and meteorological factors on PM2.5 concentration and composition. PAHs, OPAHs, hopanes, n‑alkanes, heavy metals, and several other inorganic elements were measured. PM2.5 and potassium concentrations were the highest in May-June 2014 indicating the prevalence of BB plumes in Nanjing. Emission controls substantially reduced concentrations of PM2.5 (31%), total PAHs (59%), OPAHs (37%), and most heavy metals (44-89%) during the YOG compared to August 2015. In addition, regional atmospheric transport and meteorological parameters partly explained the observed differences between the campaigns. The most abundant PAHs and OPAHs were benzo[b,k]fluoranthenes, fluoranthene, pyrene, chrysene, 1,8‑naphthalic anhydride, and 9,10‑anthracenedione in all campaigns. Carbon preference index and the contribution of wax n‑alkanes indicated mainly biogenic sources of n‑alkanes in May-June 2014 and anthropogenic sources in the other campaigns. Hopane indexes pointed to vehicular transport as the major source of hopanes, but contribution of coal combustion was detected in winter 2015. The results provide evidence to the local government of the impacts of the air protection regulations. However, differences between individual components were observed, e.g., concentrations of potentially more harmful OPAHs decreased less than concentrations of PAHs. The results suggest that the proportions of hazardous components in the PM2.5 may also change considerably due to emission control measures.