Sébastien Bau

Characterizing the effective density and primary particle diameter of airborne nanoparticles produced by spark discharge using mobility and mass measurements (tandem DMA/APM)

Nanoparticles are increasingly used in a wide variety of industries. As yet, their health effects are incompletely characterized. Effective density is among the key characteristics of airborne nanoparticles due to its role in particle deposition in the human respiratory tract and in the conversion of number distributions to mass distributions. Because it cannot be measured directly, different methods have been developed to accede to this parameter. The approach chosen in this study is based on the tandem measurement of airborne nanoparticles electrical mobility and mass (tandem differential mobility analyzer/aerosol particle mass analyzer), which major advantage lies in the absence of hypothesis contrary to the tandem differential mobility analyzer/electrical low pressure impactor (DMA/ELPI). The methodology was first applied to spherical model particles to validate the associated data treatment and protocol. In particular, the influence of APM rotational velocity and airflow rate were investigated with regards to the separation of multiply charged particles and electrometer signal. It emerged from experimental data that a compromise between separation efficiency and detection limit shall be found, depending on the nanoparticles to characterize. Accounting for their wide use in different domains, airborne nanoparticles of constantan®, copper, graphite, iron, silver and titanium, produced by spark discharge appear to be representative of ultrafine particles stemming from different industrial processes. In addition to their effective density, the mass-mobility exponents and primary particle diameters were determined for these particles, and found to agree well with published data.

Response of three instruments devoted to surface-area for monodisperse and polydisperse aerosols in molecular and transition regimes

An increasing number of experimental and theoretical studies focus on airborne nanoparticles (NP) in relation with many aspects of risk assessment. Indeed, our understanding of the hazards, the actual exposures in the workplace and the limits of engineering controls and personal protective equipment with regard to NP are still under development. Several studies have already identified surface-area as an important determinant of low solubility nanoparticles toxicity. As a consequence, the concept that surface-area could be a relevant metric for characterizing exposure to low solubility airborne NP has been proposed [1]. To provide NP surface-area concentration, some direct-reading instruments have been designed, based on diffusion charging. The actual available instruments providing airborne NP surface-area concentration are studied in this work: LQ1-DC (Matter Engineering), AeroTrak™ 9000 (TSI) and NSAM (TSI model 3550). Their performances regarding monodisperse carbon NP have been investigated by Bau et al. [2]. This work aims at completing the instruments characterization regarding monodisperse NP of other chemical composition (aluminium, copper, silver) and studying their performances against polydisperse aerosols of NP.

Experimental study of the response functions of direct-reading instruments measuring surface-area concentration of airborne nanostructured particles

An increasing number of experimental and theoretical studies focus on airborne nanoparticles (NP) in relation with many aspects of risk assessment to move forward our understanding of the hazards, the actual exposures in the workplace, and the limits of engineering controls and personal protective equipment with regard to NP. As a consequence, generating airborne NP with controlled properties constitutes an important challenge. In parallel, toxicological studies have been carried out, and most of them support the concept that surface-area could be a relevant metric for characterizing exposure to airborne NP [1]. To provide NP surface-area concentration measurements, some direct-reading instruments have been designed, based on attachment rate of unipolar ions to NP by diffusion. However, very few information is available concerning the performances of these instruments and the parameters that could affect their responses. In this context, our work aims at characterizing the actual available instruments providing airborne NP surface-area concentration. The instruments (a- LQ1-DC, Matter Engineering; b-AeroTrak™ 9000, TSI; c- NSAM, TSI model 3550;) are thought to be relevant for further workplace exposure characterization and monitoring. To achieve our work, an experimental facility (named CAIMAN) was specially designed, built and characterized.

Inter-comparison of personal monitors for nanoparticles exposure at workplaces and in the environment

Personal monitors based on unipolar diffusion charging (miniDiSC/DiSCmini, NanoTracer, Partector) can be used to assess the individual exposure to nanoparticles in different environments. The charge acquired by the aerosol particles is nearly proportional to the particle diameter and, by coincidence, also nearly proportional to the alveolar lung-deposited surface area (LDSA), the metric reported by all three instruments. In addition, the miniDiSC/DiSCmini and the NanoTracer report particle number concentration and mean particle size. In view of their use for personal exposure studies, the comparability of these personal monitors was assessed in two measurement campaigns. Altogether 29 different polydisperse test aerosols were generated during the two campaigns, covering a large range of particle sizes, morphologies and concentrations. The data provided by the personal monitors were compared with those obtained from reference instruments: a scanning mobility particle sizer (SMPS) for LDSA and mean particle size and a ultrafine particle counter (UCPC) for number concentration. The results indicated that the LDSA concentrations and the mean particle sizes provided by all investigated instruments in this study were in the order of ±30% of the reference value obtained from the SMPS when the particle sizes of the test aerosols generated were within 20-400nm and the instruments were properly calibrated. Particle size, morphology and concentration did not have a major effect within the aforementioned limits. The comparability of the number concentrations was found to be slightly worse and in the range of ±50% of the reference value obtained from the UCPC. In addition, a minor effect of the particle morphology on the number concentration measurements was observed. The presence of particles >400nm can drastically bias the measurement results of all instruments and all metrics determined.

On the Importance of Density in ELPI Data Post-Treatment

This study compared number and mass concentrations obtained using two reference devices, a scanning mobility particle sizer (SMPS) and a tapered element oscillating microbalance (TEOM), with those calculated from raw electrical low-pressure impactor (ELPI) data. ELPI data post-treatment was performed assuming a mobility-dependent effective density and three constant densities: an average effective density, the raw material density, and the standard density (i.e., 1 g/cm3). For the mass concentration, whatever the density considered, the ELPI-determined value was close to the reference. For the number concentration, results indicate good agreement between SMPS and ELPI number concentrations when considering effective density and, to a lesser extent, average effective density. In contrast, with the raw material density or standard density, large uncertainties in number concentration measurements were produced. A good estimation of number concentration was obtained based on ELPI data when assuming a standard density only when there was fortuitous agreement between the number tested aerosol size distribution and its mobility-dependent effective density. Thus, contrary to what some authors recommend, a standard density cannot be universally used. Copyright

A modular tool for analyzing cascade impactors data to improve exposure assessment to airborne nanomaterials

Cascade impactors are widely used to provide particle size distributions for the study of aerosols in workplaces and ambient air. In the frame of exposure assessment to airborne particles, one of their main advantages is the possibility to perform further off-line analysis (e.g. electron microscopy, physical-chemical characterization by XRD, ICP-MS, etc.) on the collected samples according to particle size. However, the large channel width makes the particle size distributions not enough size-resolved. Furthermore, in spite of the sharpness of the collection efficiency curves, the existence of an overlap between stages renders data interpretation difficult. This work aim was to develop a modular program allowing the inversion of data stemming from cascade impactors based on the mass (or any quantity) collected on each impaction stage. Through a precise description of the collection efficiency curves of the different stages, the software provides a continuous curve (from 100 to 1000 points) using the Markowski method, and more particularly the Twomey iterative algorithm, according to several publications about inverse problems in cascade impactors. An additional option consists in determining the experimental error at each point of the inverse curve, performed by realizing several consecutive inversions. The inversion procedure was first tested and optimized for the case of the SIOUTAS personal sampler. Validation of the calculation was performed considering theoretical aerosols. Then, the software was used for two sets of data obtained during field measurement campaigns.

CAIMAN: a versatile facility to produce aerosols of nanoparticles

This work aims at presenting a nanoparticle generation non-transportable facility in aerosol phase called CAIMAN (acronym for Characterization of Instruments Measuring Aerosols of Nanoparticles) and its performances. This facility delivers primary nanoaerosols from electrodes made of C, Al, Cu (and mixtures containing Be), Ag, Constantane (a mixture of Cu-55wt% and Ni-45wt%) particles at known concentrations, sizes, shapes and mean charge levels. It is also capable to deliver well-known particle mixture containing combinations of the primary nanoaerosols and particles representatives of background aerosols (in the present work NaCl). The output of the CAIMAN facility is very consistent over long time intervals when operating under similar conditions. It indicates that repeatability is also one of the important assets of the facility.

Dustiness of 14 carbon nanotubes using the vortex shaker method

The handling of carbon nanotube (CNT) powders is a plausible scenario during the course of the CNT life-cycle. However, related exposure data remain limited. In this context, information about the dustiness of CNT is therefore of great interest, for example for control banding or exposure modelling. Here, we investigate the dustiness of fourteen CNT powders using the Vortex Shaker (VS) method. The central component of the VS method is a stainless steel cylindrical tube, continuously shaken in a circular orbital motion, in which a small volume (0.5 cm3) of the powder to be tested is placed. All samples were obtained through the NANoREG Nanomaterials Information and Web-Order system. The test procedure that we have developed is based on four principal components: (i) a respirable cyclone for gravimetric sampling, (ii) a CPC as a reference instrument for number concentration measurement, (iii) an MPS for collection of particles for EM observations/analysis, and (iv) an ELPI for size-resolved aerosol measurement. In this paper, the data were evaluated using two parameters: (i) the mass-based dustiness index in the respirable fraction; and (ii) the number-based dustiness index in the respirable fraction. The results indicate that the method leads to relatively accurate mass- and number-based dustiness indices. The indices obtained span wide ranges, of 2 and 3 orders of magnitude variation for mass and number respectively, suggesting a corresponding significant difference in terms of potential exposure. EM observations reveal that airborne CNTs are mostly released as bundles of different shapes ranging from a few tens of nanometers up to tens of micrometers in size.

Performance study of portable devices for the real-time measurement of airborne particle number concentration and size (distribution)

The aim of this experimental study was to investigate the performance of both portable and transportable devices devoted to the real-time measurement of airborne particle number concentration and size (distribution). Electrical mobility spectrometers (SMPS, FMPS, Nanoscan) as well as diffusion chargers (DiSCmini, Nanotracer) were studied. Both monodisperse and polydisperse aerosols were produced within the CAIMAN facility to challenge the instruments. The monodisperse test aerosols were selected in the 15-400 nm diameter range using a differential mobility analyser (DMA), and presented number concentrations of between 6.102 and 2.105 cm−3. The polydisperse test aerosols presented modal diameters of between 8 and 270 nm and number concentrations between 4.103 to 106 cm−3. The behavior of the different devices is expressed as (1) the ratio of the reported diameter to the reference diameter, and (2) the ratio of the reported number concentration to the reference concentration. These results are displayed as boxplots to better represent the statistical distribution of the experimental results. For the group of electrical mobility spectrometers, a good agreement between SMPS and FMPS and the reference was demonstrated. A slight tendency for the Nanoscan to underestimate particle size distribution for particles above around 100 nm was observed. The data reported for the group of diffusion chargers demonstrate that all, except the Nanotracer, show a tendency to underestimate particle diameter, by a factor around −40% to −10%. In the case of particle concentration, larger deviations were observed.

Sampling Efficiency and Performance of Selected Thoracic Aerosol Samplers

Measurement of worker exposure to a thoracic health-related aerosol fraction is necessary in a number of occupational situations. This is the case of workplaces with atmospheres polluted by fibrous particles, such as cotton dust or asbestos, and by particles inducing irritation or bronchoconstriction such as acid mists or flour dust. Three personal and two static thoracic aerosol samplers were tested under laboratory conditions. Sampling efficiency with respect to particle aerodynamic diameter was measured in a horizontal low wind tunnel and in a vertical calm air chamber. Sampling performance was evaluated against conventional thoracic penetration. Three of the tested samplers performed well, when sampling the thoracic aerosol at nominal flow rate and two others performed well at optimized flow rate. The limit of flow rate optimization was found when using cyclone samplers.