INDUCED PLASMA SPECTROSCOPY; HEAVY-METAL AEROSOLS; X-RAY-FLUORESCENCE; PARTICULATE MATTER; ELEMENTAL COMPOSITION; NANOMATERIALS; WORKPLACES; APPRAISAL; RELEASE; COBALT

Exposure assessment is a key step in the evaluation of the risk induced by the handling of engineered nanomaterials. It is a very complex task, because several properties of nanoparticles are assumed to have an effect on their hazards. For exposure monitoring at the workplace, real-time onsite measurements are commonly implemented to measure the particles size and number density, whereas the sampled material is subsequently analysed by electron microscopy. A complementary approach would consist in doing onsite chemical analysis of the filter samples, in order to routinely monitor a potential chronic exposure. Laser-induced breakdown spectroscopy (LIBS) has distinctive advantages for this purpose. Therefore, this work aims at evaluating the performances of LIBS to assess the exposure to airborne carbon nanotubes (CNTs) at the workplace. As carbon is a ubiquitous element in the environment, our strategy was to target metal impurities in CNTs, aluminum and iron in our case. Then, we proceeded in three steps. First, we optimized the choice of the filter type to get the lowest detection limit for both elements. Secondly, this filter was used to quantitatively measure deposited CNTs. Eventually, we conducted an onsite measurement campaign in an industrial CNT production plant to evaluate the exposure in a real situation. We demonstrated that we could reach a detection limit for CNTs compliant with the current NIOSH recommendation of 1 mu g m(-3), and that the detected CNTs during the onsite campaign in areas accessible to workers were at an extremely low concentration, several orders of magnitude lower than this recommendation.

chemometrics; ion recombination; laser-induced breakdown spectroscopy; LIBS; MCR-ALS; mean field-independent components analysis; MFICA; molecular formation; multivariate curve resolution-alternating least squares; temporal evolution;ARTIFICIAL NEURAL-NETWORKS; QUANTITATIVE-ANALYSIS; TEMPORAL EVOLUTION; WAVELET-TRANSFORM; ABSORPTION-SPECTROSCOPY; ANALYTICAL-CHEMISTRY; CHEMOMETRIC METHODS; LIBS; IDENTIFICATION; OPTIMIZATION

Laser-induced breakdown spectroscopy (LIBS) is an analytical technique allowing the determination of elemental concentrations in a variety of matrices in the solid, liquid, and gaseous phases. Because of the inherent complexity of the signal and to the high dimensionality of experimental data, chemometrics has been more and more applied in LIBS to perform samples identification or quantitative measurements. But multivariate methods can also be used for the description and physical interpretation of the plasma, particularly to exploit the temporal dimension of the LIBS signal, which is usually neglected in spectrochemical measurements. In this work, time-resolved spectra of a pure aluminum sample were treated with 2 methods, mean field-independent components analysis and multivariate curve resolution-alternating least squares, applying non-negativity constraints for scores and components in both cases. Results obtained were compared with reference univariate measurements of the emission of the species of interest (ions, neutral atoms, and molecules). The interpretation of scores and components provided a physical description of phenomena that take place between species in the plasma, like ionic recombination and molecules formation. Overall, mean field-independent components analysis and multivariate curve resolution-alternating least squares yield equivalent solutions with our dataset. This new approach is very promising for the treatment of time-resolved data obtained by LIBS.

We propose a new technique suitable for on-line monitoring of gas phase synthesis of nanoparticles. It is based on aerodynamic focusing of nanoparticles followed by Laser-Induced Breakdown Spectroscopy (LIBS) under vacuum. The laser crosses a beam of particles at low pressure so that the plasma-produced photons to be analyzed are emitted only from the particles. Unlike previous experiments, the background from interaction with the gaseous component is totally eliminated from the collected spectra. Vacuum allows also for easier spectra collection in the UV range. Moreover, as the nanoparticle beam is highly collimated, the optical interface windows are not obstructed by particle deposition and the system can be kept running for hours.