Strategies to Assess Occupational Exposure to Airborne Nanoparticles: Systematic Review and Recommendations.

In many industrial sectors, workers are exposed to manufactured or unintentionally emitted airborne nanoparticles (NPs). To develop prevention and enhance knowledge surrounding exposure, it has become crucial to achieve a consensus on how to assess exposure to airborne NPs by inhalation in the workplace. Here, we review the literature presenting recommendations on assessing occupational exposure to NPs. The 23 distinct strategies retained were analyzed in terms of the following points: target NPs, objectives, steps, "measurement strategy" (instruments, physicochemical analysis, and data processing), "contextual information" presented, and "work activity" analysis. The robustness (consistency of information) and practical aspects (detailed methodology) of each strategy were estimated. The objectives and methodological steps varied, as did the measurement techniques. Strategies were essentially based on NPs measurement, but improvements could be made to better account for "contextual information" and "work activity". Based on this review, recommendations for an operational strategy were formulated, integrating the work activity with the measurement to provide a more complete assessment of situations leading to airborne NP exposure. These recommendations can be used with the objective of producing homogeneous exposure data for epidemiological purposes and to help improve prevention strategies.

Towards a surface metric to measure the dustiness of nanomaterial powders.

The relevance of dustiness methods is increasingly recognized in the preliminary exposure evaluation of workers handling nanomaterials in powder form, and should also be transposed to the assessment of environmental risk in the future. The methods currently recommended in the European standards are mainly based on determining a mass-based dustiness index [mg kg-1], whereas surface area is regularly put forward as a more appropriate determinant to assess the pulmonary toxicity of nanoparticles. In this study, we describe an operational methodology leading us to propose a surface metric to determine the dustiness index [m2 kg-1] of nanoparticulate matter. To this end, we demonstrate the equivalence between the external specific surface area of a nanopowder and that of its aerosol with five nanomaterials produced and used on an industrial scale, and covering a range of external specific surface areas from 35 to 230 m2 g-1. Compared to the conventional mass-based dustiness index, the surface-based dustiness index (1) is more discriminating, covering an additional order of magnitude, and (2) has an impact on the powder ranking with potential consequences on the preventive measures to be implemented. Finally, our proposal has the potential to be included in future revisions of European standards for workplace exposure and dustiness measurement, provided that further experimental results on surface-based dustiness indices support these preliminary data.

What does ergonomics have to do with nanotechnologies? A case study.

Despite recent concerns for workers' health, exposure situations to nanoparticles can occur in numerous workplaces. Understanding how exposures occur considering human work in these transformations remains a crucial issue of nanotechnologies. The objective of this article is to understand exposure situations to nanoparticles, their determinants and the resources to act on them. This understanding was achieved by specific measurement of nanoparticles aerosols, combined with an analysis of work activity (actions performed and physical strain) in a rubber industry. The presentation of real time measurements, associated with the video of work situations, during confrontation interviews becomes a means of making exposing work activities visible, to analyze and transform them from the points of view formulated by the company's stakeholders. In this way, characterized "typical exposure situations" serve to trigger discussions and open up new spaces for debate highlighting how innovation affects work and gives rise to enhanced prevention projects.

Identification of nanomaterials by the volume specific surface area (VSSA) criterion: application to powder mixes.

We demonstrate the relevance of the Volume Specific Surface Area (VSSA) parameter to identify the nanoparticulate character of powder mixes based on either spherical constituent particles with bimodal size distributions (TiO2), or fiber-like constituent particles with unimodal size distributions (sepiolite and sepiolite-based pigments). These new results indicate that VSSA could reasonably be proposed as an optional criterion in the future for the definition of nanomaterials based on the European Commission recommendation, provided certain requirements are fulfilled.

Toward an operational methodology to identify industrial-scaled nanomaterial powders with the volume specific surface area criterion.

Nanoparticulate powders are increasingly found in the workplace. Inhalation exposure to airborne nanoparticles (NPs) is possible throughout the life-cycle of the powders. As the toxicity of NPs has never been demonstrated, it remains essential to evaluate the risks associated with NPs in order to propose preventative measures. The first step of a risk assessment strategy consists in the identification of the 'nano' nature of a material, which suffers from a lack of an operational methodology. Here, we present a simplified and operational strategy relying on the volume specific surface area (VSSA) for nanomaterial identification, based on the recommendation stemming from the European Commission and previous work on this topic from the European Project Nanodefine. The proposed strategy was tested on a set of 15 representative industrial powders (TiO2, SiO2, CuO, and ZnO), covering a wide range of properties, and previous published data. The VSSA classification was validated via a comparison with the particle size obtained by transmission electron microscopy (TEM). It was evidenced that the VSSA is in accordance with particle size for nanomaterial powder classification. The proposed methodology involves relatively accessible methods such as thermogravimetric analysis, nitrogen adsorption and helium pycnometry and limits the detection of false negatives. Moreover, it does not imply systematic confirmation of the results with the reference particle size criterion. Our results suggest that the VSSA is a promising parameter to be used for risk assessment and should be further investigated on powder mixings to confirm its relevancy to define nanomaterial powders.

Qualitative and Semiquantitative Assessment of Exposure to Engineered Nanomaterials within the French EpiNano Program: Inter- and Intramethod Reliability Study.

The relatively recent development of industries working with nanomaterials has created challenges for exposure assessment. In this article, we propose a relatively simple approach to assessing nanomaterial exposures for the purposes of epidemiological studies of workers in these industries. This method consists of an onsite industrial hygiene visit of facilities carried out individually and a description of workstations where nano-objects and their agglomerates and aggregates (NOAA) are present using a standardized tool, the Onsite technical logbook. To assess its reliability, we implemented this approach for assessing exposure to NOAA in workplaces at seven workstations which synthesize and functionalize carbon nanotubes. The prediction of exposure to NOAA using this method exhibited substantial agreement with that of the reference method, the latter being based on an onsite group visit, an expert's report and exposure measurements (Cohen kappa = 0.70, sensitivity = 0.88, specificity = 0.92). Intramethod comparison of results for exposure prediction showed moderate agreement between the three evaluators (two program team evaluators and one external evaluator) (weighted Fleiss kappa = 0.60, P = 0.003). Interevaluator reliability of the semiquantitative exposure characterization results was excellent between the two evaluators from the program team (Spearman rho = 0.93, P = 0.03) and fair when these two evaluators' results were compared with the external evaluator's results. The project was undertaken within the framework of the French epidemiological surveillance program EpiNano. This study allowed a first reliability assessment of the EpiNano method. However, to further validate this method a comparison with robust quantitative exposure measurement data is necessary.

Cytotoxicity and genotoxicity of nanosized and microsized titanium dioxide and iron oxide particles in Syrian hamster embryo cells.

Potential differences in the toxicological properties of nanosized and non-nanosized particles have been notably pointed out for titanium dioxide (TiO(2)) particles, which are currently widely produced and used in many industrial areas. Nanoparticles of the iron oxides magnetite (Fe(3)O(4)) and hematite (Fe(2)O(3)) also have many industrial applications but their toxicological properties are less documented than those of TiO(2). In the present study, the in vitro cytotoxicity and genotoxicity of commercially available nanosized and microsized anatase TiO(2), rutile TiO(2), Fe(3)O(4), and Fe(2)O(3) particles were compared in Syrian hamster embryo (SHE) cells. Samples were characterized for chemical composition, primary particle size, crystal phase, shape, and specific surface area. In acellular assays, TiO(2) and iron oxide particles were able to generate reactive oxygen species (ROS). At the same mass dose, all nanoparticles produced higher levels of ROS than their microsized counterparts. Measurement of particle size in the SHE culture medium showed that primary nanoparticles and microparticles are present in the form of micrometric agglomerates of highly poly-dispersed size. Uptake of primary particles and agglomerates by SHE exposed for 24 h was observed for all samples. TiO(2) samples were found to be more cytotoxic than iron oxide samples. Concerning primary size effects, anatase TiO(2), rutile TiO(2), and Fe(2)O(3) nanoparticles induced higher cytotoxicity than their microsized counterparts after 72 h of exposure. Over this treatment time, anatase TiO(2) and Fe(2)O(3) nanoparticles also produced more intracellular ROS compared to the microsized particles. However, similar levels of DNA damage were observed in the comet assay after 24 h of exposure to anatase nanoparticles and microparticles. Rutile microparticles were found to induce more DNA damage than the nanosized particles. However, no significant increase in DNA damage was detected from nanosized and microsized iron oxides. None of the samples tested showed significant induction of micronuclei formation after 24 h of exposure. In agreement with previous size-comparison studies, we suggest that in vitro cytotoxicity and genotoxicity induced by metal oxide nanoparticles are not always higher than those induced by their bulk counterparts.

Evaluation of the diffusion size classifier (meDiSC) for the real-time measurement of particle size and number concentration of nanoaerosols in the range 20-700 nm.

In the frame of assessing exposure to nanostructured particles, the aim of this work is to study the performance of a new device devoted to the real-time measurement of nanostructured aerosol: the meDiSC (Diffusion Size Classifier, Matter Engineering, Switzerland). This instrument is based on unipolar diffusion charging of particles which are then collected successively in diffusion and filtration stages. From currents measured in these stages, the instrument is capable of determining aerosol mean size and number concentration. These data were compared to reference measurements regarding monodisperse aerosols in a range from 20 to 700 nm; the relative biases were found unsatisfying. This led us to investigate the principle of the instrument. Consequently, the charging law of the diffusion charger was experimentally established, as well as the calibration curve allowing the determination of the mean size of the particles. The latter analysis was completed by a model based on diffusion theory. Our results indicate the possibility to improve the range of size measurement up to 350 nm. Measured particle size and number concentration were also used to calculate geometric surface-area concentration; the experimental data were compared to a reference calculated surface-area concentration. The results demonstrate the possibility to evaluate this parameter within acceptable uncertainty. In a second step, the meDiSC was challenged with polydisperse aerosols. It was observed that meDiSC overestimates particle size by a factor 1.7, while particle number concentrations are found within ±40% of the reference. The model applied to polydisperse aerosols indicates that polydispersity little influences particle size up to 300 nm while geometric standard deviation remains below 1.7.

Development of a French epidemiological surveillance system of workers producing or handling engineered nanomaterials in the workplace.

OBJECTIVE: Concern has been raised about the potential impact of nanomaterials exposure on human health, and France has decided to implement a timely epidemiological surveillance tool of workers likely to be exposed to engineered nanomaterials that could accompany the development of nanotechnologies. METHODS: A comprehensive review of the toxicological and epidemiological literature has been conducted together with an exploratory study among French companies producing or handling nanoobjects. RESULTS: A double surveillance system is proposed consisting of a prospective cohort survey and repeated cross-sectional studies. The aim of the cohort is (1) to monitor long-term health effects and (2) to allow of further research. Setting-up an exposure registry is the first planned step. CONCLUSIONS: The protocol is about to be submitted to the French Government for approval and funding.

Laboratory study of selected personal inhalable aerosol samplers.

Assessment of inhalable dust exposure requires reliable sampling methods in order to measure airborne inhalable particles' concentrations. Many inhalable aerosol samplers can be used but their performances widely vary and remain unknown in some cases. The sampling performance of inhalable samplers is strongly dependent on particle size and ambient air velocity. Five inhalable aerosol samplers have been studied in two laboratory wind tunnels using polydisperse glass-beads' test aerosol. Samplers tested were IOM sampler (UK), two versions of CIP 10-I sampler, v1 and v2 (F), 37-mm closed face cassette sampler (USA), 37-mm cassette fitted up with an ACCU-CAP insert (USA), and Button sampler (USA). Particle size-dependent sampling efficiencies were measured in a horizontal wind tunnel under a 1 m s(-1) wind velocity and in a vertical tunnel under calm air, using a specific method with Coulter(R) counter particle size number distribution determinations. Compared with CEN-ISO-ACGIH sampling criteria for inhalable dust, the experimental results show fairly high sampling efficiency for the IOM and CIP 10-I v2 samplers and slightly lower efficiencies for the Button and CIP 10-I v1 samplers. The closed face cassette (4-mm orifice) produced the poorest performances of all the tested samplers. This can be improved by using the ACCU-CAP internal capsule, which prevents inner wall losses inside the cassette. Significant differences between moving air and calm air sampling efficiency were observed for all the studied samplers.

Site comparison of selected aerosol samplers in the wood industry.

Several samplers (IOM, CIP 10-I v1, ACCU-CAP, and Button) were evaluated at various wood industry companies using the CALTOOL system. The results obtained show that compared to the CALTOOL mouth, which can be considered to be representative of the exposure of a person placed at the same location under the same experimental conditions, the concentrations measured by the IOM, CIP 10-I v1, and ACCU-CAP samplers are not significantly different (respectively, 1.12, 0.94, and 0.80 compared to 1.00), the Button sampler (0.86) being close to the ACCU-CAP sampler. Comparisons of dust concentrations measured using both a closed-face cassette (CFC) and one of the above samplers were also made. In all, 235 sampling pairs (sampler + CFC) taken at six companies provided us with a comparison of concentrations measured using IOM, CIP 10-I v1, ACCU-CAP, and Button samplers with concentrations measured using a CFC. All the studied samplers collected systematically more dust than the CFC (2.0 times more for the IOM sampler, 1.84 times more for the CIP 10-I v1 sampler, 1.68 times more for the ACCU-CAP sampler, and 1.46 times more for the Button sampler). The literature most frequently compares the IOM sampler with the CFC: published results generally show larger differences compared with the CFC than those found during our research. There are several explanations for this difference, one of which involves CFC orientation during sampling. It has been shown that concentrations measured using a CFC are dependent on its orientation. Different CFC positions from one sampling session to another are therefore likely to cause differences during CFC-IOM sampler comparisons.

Aerosol sampling by annular aspiration slots.

Annular aspiration slots were studied in laboratory conditions in order to investigate their performance in sampling airborne particles. The sampling efficiency was measured in a wind tunnel as a function of particle aerodynamic diameter in various conditions of external wind speed. The geometric parameters of the annular slot and the aerodynamic conditions of sampling were optimised in order to improve the sampling efficiency. Optimal selection of these parameters led to the sampling efficiency decreasing very slightly with increasing particle size. Two semi-empirical models of sampling efficiency--in moving and calm air conditions--were derived and experimentally checked. Omnidirectional annular sampling heads are less sensitive to the external wind and their inner particle losses can be minimised. A prototype of a personal aerosol sampler for exposure assessment in occupational safety and health was designed on the basis of these models. It broadly meets the conventional efficiency for inhalable aerosol sampling.

Bioaerosol sampling by a personal rotating cup sampler CIP 10-M.

High concentrations of bioaerosols containing bacterial, fungal and biotoxinic matter are encountered in many workplaces, e.g. solid waste treatment plants, waste water treatment plants and sewage networks. A personal bioaerosol sampler, the CIP 10-M (M-microbiologic), has been developed to measure worker exposure to airborne biological agents. This sampler is battery operated; it is light and easy to wear and offers full work shift autonomy. It can sample much higher concentrations than biological impactors and limits the mechanical stress on the microorganisms. Biological particles are collected in 2 ml of liquid medium inside a rotating cup fitted with radial vanes to maintain an air flow rate of 10 l min(-1) at a rotational speed of approximately 7,000 rpm. The rotating cup is made of sterilisable material. The sampled particles follow a helicoidal trajectory as they are pushed to the surface of the liquid by centrifugal force, which creates a thin vertical liquid layer. Sterile water or another collecting liquid can be used. Three particle size selectors allow health-related aerosol fractions to be sampled according to international conventions. The sampled microbiological particles can be easily recovered for counting, incubation or further biochemical analysis, e.g., for airborne endotoxins. Its physical sampling efficiency was laboratory tested and field trials were carried out in industrial waste management conditions. The results indicate satisfactory collection efficiency, whilst experimental application has demonstrated the usefulness of the CIP 10-M personal sampler for individual bioaerosol exposure monitoring.