Enhanced Deposition by Electrostatic Field-Assistance Aggravating Diesel Exhaust Aerosol Toxicity for Human Lung Cells.

Air pollution is associated with increased risk of cardiovascular and pulmonary diseases, but conventional air quality monitoring gives no information about biological consequences. Exposing human lung cells at the air-liquid interface (ALI) to ambient aerosol could help identify acute biological responses. This study investigated electrode-assisted deposition of diesel exhaust aerosol (DEA) on human lung epithelial cells (A549) in a prototype exposure chamber. A549 cells were exposed to DEA at the ALI and under submerged conditions in different electrostatic fields (EFs) and were assessed for cell viability, membrane integrity, and IL-8 secretion. Qualitative differences of the DEA and its deposition under different EFs were characterized using scanning mobility particle sizer (SMPS) measurements, transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS). Upon exposure to DEA only, cell viability decreased and membrane impairment increased for cells at the ALI; submerged cells were unaffected. These responses were enhanced upon application of an EF, as was DEA deposition. No adverse effects were observed for filtered DEA or air only, confirming particle-induced responses. The prototype exposure chamber proved suitable for testing DEA-induced biological responses of cells at the ALI using electrode-assisted deposition and may be useful for analysis of other air pollutants.

An electrical conductivity based method of determining the particle deposition rate in air-liquid interface devices.

A new in-situ method of determining the particle deposition rate onto cell cultures inside air-liquid interface devices is described. It is based on depositing a surrogate aerosol of salt particles onto the water filled wells of a culture plate while measuring the resulting change in electrical conductivity of the solution in situ, in order to derive the accumulated particle mass. For evaluation purposes, the wells of a six-well cell culture plate were equipped with custom designed electrodes and calibrated with a series of commercially available standard solutions. After the necessary corrections prescribed by theory, the calibration resulted in an accuracy and comparability between cells of ±3% in terms of measured conductivity. The method was then applied to a specific ALI device consisting essentially of the calibrated six-well culture plate inside an electrostatic cross-flow precipitator, and tested with submicron NaCl aerosol of defined size distribution produced by nebulization of a salt solution. 2h of particle accumulation were sufficient to accumulate between 30 and 10 µg of salt per well, depending on the location in the precipitator. Resulting deposition rates varied narrowly between the wells by about 2 ng min(-1) cm(-2). Factors affecting the overall accuracy and reproducibility are discussed.

Size-dependent ROS production by palladium and nickel nanoparticles in cellular and acellular environments - An indication for the catalytic nature of their interactions.

Palladium and nickel nanoparticles with variable but narrowly defined primary particle sizes in the range of 4-27 nm were investigated toward their catalytic activity and their ability to produce reactive oxygen species (ROS). The agglomerate size in the gas phase was between 50 and 150 nm, after transfer into solution probably larger. The catalytic activity was measured on the basis of CO oxidation to CO2. The formation of ROS was determined after transferring the particles into phosphate buffered saline (PBS), via the 2',7'-dichlorofluorescein method in a cell-free environment and with THP-1 cells. Activities were normalized with regard to catalyst surface area to enable a meaningful comparison of size effects. The solubility was measured for both materials and found to be 2 µg/ml for Ni and below the detection limit of 0.8 µg/ml for Pd. In the concentration range of about 4-250 µg/ml both materials induced a significant production of ROS in both acellular and cellular environments, with palladium being more active than nickel by several orders of magnitude. On an equal surface area concentration basis, both acellular and cellular ROS production showed a pronounced dependence on the primary particle size, with a maximum in the vicinity of 12 nm. The surface-specific catalytic activity also had a maximum at that size range. The correlation of these size effects is both surprising and - in combination with the poor solubility of palladium and nickel in PBS solution - a strong argument in favor of a particulate, catalytic mechanism for ROS production.

Film Growth Rates and Activation Energies for Core-Shell Nanoparticles Derived from a CVD Based Aerosol Process.

Silica core-shell nanoparticles of about 60-120 nm with a closed outer layer of bismuth or molybdenum oxide of 1-10 nm were synthesized by an integrated chemical vapor synthesis/chemical vapor deposition process at atmospheric pressure. Film growth rates and activation energies were derived from transmission electron microscopy (TEM) images for a deposition process based on molybdenum hexacarbonyl and triphenyl bismuth as respective coating precursors. Respective activation energies of 123 ± 10 and 155 ± 10 kJ/mol are in good agreement with the literature and support a deposition mechanism based on surface-induced removal of the precursor ligands. Clean substrate surfaces are thus prerequisite for conformal coatings. Integrated aerosol processes are solvent-free and intrinsically clean. In contrast, commercial silica substrate particles were found to suffer from organic residues which hinder shell formation, and require an additional calcination step to clean the surface prior to coating. Dual layer core-shell structures with molybdenum oxide on bismuth oxide were synthesized with two coating reactors in series and showed similar film growth rates.

Functionality based detection of airborne engineered nanoparticles in quasi real time: a new type of detector and a new metric.

A new type of detector which we call the Catalytic Activity Aerosol Monitor (CAAM) was investigated towards its capability to detect traces of commonly used industrial catalysts in ambient air in quasi real time. Its metric is defined as the catalytic activity concentration (CAC) expressed per volume of sampled workplace air. We thus propose a new metric which expresses the presence of nanoparticles in terms of their functionality - in this case a functionality of potential relevance for damaging effects - rather than their number, surface, or mass concentration in workplace air. The CAAM samples a few micrograms of known or anticipated airborne catalyst material onto a filter first and then initiates a chemical reaction which is specific to that catalyst. The concentration of specific gases is recorded using an IR sensor, thereby giving the desired catalytic activity. Due to a miniaturization effort, the laboratory prototype is compact and portable. Sensitivity and linearity of the CAAM response were investigated with catalytically active palladium and nickel nano-aerosols of known mass concentration and precisely adjustable primary particle size in the range of 3-30 nm. With the miniature IR sensor, the smallest detectable particle mass was found to be in the range of a few micrograms, giving estimated sampling times on the order of minutes for workplace aerosol concentrations typically reported in the literature. Tests were also performed in the presence of inert background aerosols of SiO2, TiO2, and Al2O3. It was found that the active material is detectable via its catalytic activity even when the particles are attached to a non-active background aerosol.

Sliding/rolling phobic droplets along a fiber: measurement of interfacial forces.

Phobic droplet-fiber systems possess complex geometries, which have made full characterization of such systems difficult. This work has used atomic force microscopy (AFM) to measure droplet-fiber forces for oil droplets on oleophobic fibers over a range of fiber diameters. The work adapted a previous method and a theoretical model developed by the authors for philic droplet-fiber systems. A Bayesian statistical model was also used to account for the influence of surface roughness on the droplet-fiber force. In general, it has been found that the force required to move a liquid droplet along an oleophobic filter fiber will be less than that required to move a droplet along an oleophilic fiber. However, because of the effects of pinning and/or wetting behavior, this difference may be less than would otherwise be expected. Droplets with a greater contact angle (~110°) were observed to roll along the fiber, whereas droplets with a lesser contact angle (<90°) would slide.

An aerosol-process for the synthesis of nanostructured molybdenum oxide catalysts by integrated chemical vapour synthesis/chemical vapour deposition at atmospheric pressure.

We report the synthesis of composite nanoparticles by an integrated CVS/CVD process at atmospheric pressure. Iron oxide and silica support particles were generated by chemical vapour synthesis (CVS), using Fe(CO)5 and Si(OC2H5)4 and were directly coated in the aerosol state with molybdenum oxide by chemical vapour deposition of Mo(CO)6. Depending on the CVS temperature hematite (600 degrees C) or maghemite (1500 degrees C) iron oxide phases were determined by XRD and FTIR. Core-shell structures with a coating thickness in the lower nm range were obtained for CVD temperatures below 150 degrees C. Complete encapsulation of the core particles and uniform elemental distribution is shown by TEM and EELS measurements. Higher CVD temperatures lead to unwanted homogenous decomposition of the molybdenum precursor. Additional aerosol temperature treatment was used to reach further oxidation and the formation of a mixed oxide shell, indicated by FTIR measurements. The results show the potential of the process for the synthesis of structured core-shell nanoparticles.

Risk assessment of engineered nanomaterials and nanotechnologies--a review.

With the increasing utilization of engineered nanomaterials (ENM), the potential exposure of workers to ENM is likely to increase significantly. Very little is known though, of the risks posed by ENM to human health, in particular concerning those characteristics that are technologically attractive: small size, high surface to mass ratio, and surface reactivity. ENM risk assessment is hampered by a lack of exposure as well as toxicity data specific to the multitude of ENM being developed. An economical approach to this problem urgently calls for intelligent testing strategies to capture essential features of ENM, thereby allowing over-arching ENM risk assessment. The data gaps of ENM risk assessment include (1) ENM aerosol standards and agreement on ENM key metrics; (2) dependable exposure scenarios, affordable monitoring technologies, exposure data and models; and (3) biomedical data on ENM translocation and toxicity, and associated testing strategies (which must be linked to the exposure scenarios). The special features of ENM do not, however, create a need to amend the current overall approach to the risk assessment of chemicals.

Oxidation of polystyrene aerosols by VUV-photolysis and/or ozone.

Aerosols of submicron polystyrene particles were oxidized by either vacuum-ultraviolet (VUV) irradiation in the presence of molecular oxygen (O(2)) and/or by ozone (O(3)). Different degrees of oxidation and oxidative degradation were reached by VUV-photolysis depending on radiant energy, O(2) and H(2)O concentrations in the bulk gas mixture as well as on particle diameter. The same functionalization was obtained by exposing the aerosol to O(3), however, oxidation, in particular oxidative degradation, was less efficient. The evolution of hydroxyl and carbonyl functions introduced was quantified by ATR-FTIR spectroscopy of filtered particles, and oxidative degradation of the polymer particles was confirmed by determining size and number of aerosol particles before and after oxidation. Efficiency analyses are based on the results of an O(3) actinometry and on an evaluation of the rate of absorbed photons by the aerosol particles in function of their size.

Automated phase correction via maximization of the real signal.

Due to improved quantification capabilities and enhanced signal-to-noise ratio (SNR), phase-corrected real reconstruction in magnetic resonance imaging is superior to the common magnitude reconstruction, especially at low SNR. This requires the development of an automated phase-correction algorithm. Existing methods are not well suited for multiple unconnected regions of very low SNR. For this situation, a method based on the real-signal maximization is implemented, in which the experimental image phase is approximated by a three-dimensional polynomial of up to third order. The presented implementation was successfully applied to data originating from different samples and pulse sequences.

Fragmentation and bond strength of airborne diesel soot agglomerates.

BACKGROUND: The potential of diesel soot aerosol particles to break up into smaller units under mechanical stress was investigated by a direct impaction technique which measures the degree of fragmentation of individual agglomerates vs. impact energy. Diesel aerosol was generated by an idling diesel engine used for passenger vehicles. Both the aerosol emitted directly and aerosol that had undergone additional growth by Brownian coagulation ("aging") was investigated. Optionally a thermo-desoption technique at 280 degrees C was used to remove all high-volatility and the majority of low-volatility HC adsorbates from the aerosol before aging. RESULTS: It was found that the primary soot agglomerates emitted directly from the engine could not be fragmented at all. Soot agglomerates permitted to grow additionally by Brownian coagulation of the primary emitted particles could be fragmented to a maximum of 75% and 60% respectively, depending on whether adsorbates were removed from their surface prior to aging or not. At most, these aged agglomerates could be broken down to roughly the size of the agglomerates from the primary emission. The energy required for a 50% fragmentation probability of all bonds within an agglomerate was reduced by roughly a factor of 2 when aging "dry" agglomerates. Average bond energies derived from the data were 0.52*10-16 and 1.2*10-16 J, respectively. This is about 2 orders of magnitude higher than estimates for pure van-der-Waals agglomerates, but agrees quite well with other observations. CONCLUSION: Although direct conclusions regarding the behavior of inhaled diesel aerosol in contact with body fluids cannot be drawn from such measurements, the results imply that highly agglomerated soot aerosol particles are unlikely to break up into units smaller than roughly the size distribution emitted as tail pipe soot.

Detachment of liquid droplets from fibres--experimental and theoretical evaluation of detachment force due to interfacial tension effects.

The detachment of barrel-shaped oil droplets from metal, glass and polymer fibres was examined using an atomic force microscope (AFM). The AFM was used to detach the droplets from the fibres while measuring the force-distance relationship. A novel fibre-droplet interfacial tension model was applied to predict the force required to draw the droplet away from its preferential axisymmetric position on the fibre, and also to predict the maximal force required to detach the droplet. The model assumes that the droplet retains a spherical shape during detachment, i.e., that droplet distortion is negligible. This assumption was found to be reasonably accurate for small radius oil droplets (<10 microm), however less accurate for larger droplets (>25 microm). However, it was found that the model produced a good agreement with the maximal detachment force measured experimentally--regardless of droplet size and degree of deformation--even though the model could not predict droplet extension beyond a length of one droplet radius.

MRI as a key tool for understanding and modeling the filtration kinetics of fibrous media.

Applying MRI techniques to low-density fibrous filter media provides us with unique information about the initial structure and deposited mass within the same filter sample. This now enables us to obtain the necessary link between structure and deposition for validation and further enhancement of modeling filtration kinetics. However, additional work is needed before achieving a realistic understanding of filtration kinetics.

Collision Kinetics and Electrostatic Dispersion of Airborne Submicrometer Fractal Agglomerates.

Collision and electrostatic dispersion rates of airborne submicrometer TiO(2) agglomerates were measured and compared with the classical collision theory for spheres as well as with models accounting for the agglomerate structure in terms of the fractal dimension and electrostatic effects such as Coulomb and van der Waals interactions. According to the authors' knowledge, this is the first time that the agglomerate fractal dimension and electrostatic effects have been considered simultaneously in determining the collision frequency function of agglomerates. The observed enhancement in the collision frequency of agglomerates was found mainly to be a result of electrostatic particle interactions. Nonspherical particle shape has only a comparatively small influence on the collision probability, on the order of 10-20%. Electrostatic dispersion coefficients of agglomerates were found to be similar to those of spheres. Copyright 2001 Academic Press.