Relevance of aerosol dynamics and dustiness for personal exposure to manufactured nanoparticles

Production and handling of manufactured nanoparticles (MNP) may result in unwanted worker exposure. The size distribution and structure of MNP in the breathing zone of workers will differ from the primary MNP produced. Homogeneous coagulation, scavenging by background aerosols, and surface deposition losses are determinants of this change during transport from source to the breathing zone, and to a degree depending on the relative time scale of these processes. Modeling and experimental studies suggest that in MNP production scenarios, workers are most likely exposed to MNP agglomerates or MNP attached to other particles. Surfaces can become contaminated by MNP, which constitute potential secondary sources of airborne MNP-containing particles. Dustiness testing can provide insight into the state of agglomeration of particles released during handling of bulk MNP powder. Test results, supported by field data, suggest that the particles released from powder handling occur in distinct size modes and that the smallest mode can be expected to have a geometric mean diameter >100 nm. The dominating presence of MNP agglomerates or MNP attached to background particles in the air during production and use of MNP implies that size alone cannot, in general, be used to demonstrate presence or absence of MNP in the breathing zone of workers. The entire respirable size fraction should be assessed for risk from inhalation exposure to MNP.     

Hydrolysis and stability of thin pulsed plasma polymerised maleic anhydride coatings

The stability of plasma polymerised layers has become important because of their widespread use. This study explored the hydrolysis and degradation stability of coatings of plasma polymerised maleic anhydride. Coatings made with different plasma parameters were exposed to aqueous media of different pH as a function of time. ATR-FTIR was used for structure analysis and a toluidine blue staining method allowed quantitative analysis of the hydrolysis of anhydride groups to acid groups. Coatings with constant thickness were obtained at different plasma powers and layers with varying thickness were obtained at constant plasma power by adjusting the polymerisation time. The results show that the hydrolysis resistance of the modified layer is determined by the power used in the plasma polymerisation, while changes in the chemistry of the modified layer are insignificant.     

Geometrical linear responses and directional energy derivatives for energetically degenerate MCSCF electronic functions

Summary For state-averaged multiconfigurational self consistent field (SA-MCSCF) wave functions, second-order geometrical response equations are derived that allow the determination of first-order configuration amplitude response for equally weighted, energetically degenerate states. The first-order response equations obtained in earlier work do not suffice to determine these particular responses parameters. To formulate such a derivation in a well defined manner, it is found that a specific linear combination of the degenerate states must be formed; this specific combination of states then defines how state energies and wave functions evolve as one passes through the surface intersection. The linear combination among the degenerate states is dependent upon the molecular distortion for which the responses are to be evaluated. Expressions for first- and second-order directional energy derivatives for these energetically degenerate wave functions are also derived. All the equations obtained are computationally tractable and expressed in terms of quantities that result from optimizing the SA-MCSCF wave functions and from solving the first- and part of the second-order geometrical response equations.     

Particle release and control of worker exposure during laboratory-scale synthesis,handling and simulated spills of manufactured nanomaterials in fume hoods

Fume hoods are one of the most common types of equipment applied to reduce the potential of particle exposure in laboratory environments. A number of previous studies have shown particle release during work with nanomaterials under fume hoods. Here, we assessed laboratory workers’ inhalation exposure during synthesis and handling of CuO, TiO₂ and ZnO in a fume hood. In addition, we tested the capacity of a fume hood to prevent particle release to laboratory air during simulated spillage of different powders (silica fume, zirconia TZ-3Y and TiO₂). Airborne particle concentrations were measured in near field, far field, and in the breathing zone of the worker. Handling CuO nanoparticles increased the concentration of small particles (<?58 nm) inside the fume hood (up to 1?×?10⁵ cm^?3). Synthesis, handling and packaging of ZnO and TiO₂ nanoparticles did not result in detectable particle release to the laboratory air. Simulated powder spills showed a systematic increase in the particle concentrations inside the fume hood with increasing amount of material and drop height. Despite powder spills were sometimes observed to eject into the laboratory room, the spill events were rarely associated with notable release of particles from the fume hood. Overall, this study shows that a fume hood generally offers sufficient exposure control during synthesis and handling of nanomaterials. An appropriate fume hood with adequate sash height and face velocity prevents 98.3% of particles release into the surrounding environment. Care should still be made to consider spills and high cleanliness to prevent exposure via resuspension and inadvertent exposure by secondary routes.