Occupational Exposure and Environmental Release: The Case Study of Pouring TiO2 and Filler Materials for Paint Production.

Pulmonary exposure to micro- and nanoscaled particles has been widely linked to adverse health effects and high concentrations of respirable particles are expected to occur within and around many industrial settings. In this study, a field-measurement campaign was performed at an industrial manufacturer, during the production of paints. Spatial and personal measurements were conducted and results were used to estimate the mass flows in the facility and the airborne particle release to the outdoor environment. Airborne particle number concentration (1 × 103-1.0 × 104 cm-3), respirable mass (0.06-0.6 mg m-3), and PM10 (0.3-6.5 mg m-3) were measured during pouring activities. In overall; emissions from pouring activities were found to be dominated by coarser particles >300 nm. Even though the raw materials were not identified as nanomaterials by the manufacturers, handling of TiO2 and clays resulted in release of nanometric particles to both workplace air and outdoor environment, which was confirmed by TEM analysis of indoor and stack emission samples. During the measurement period, none of the existing exposure limits in force were exceeded. Particle release to the outdoor environment varied from 6 to 20 g ton-1 at concentrations between 0.6 and 9.7 mg m-3 of total suspended dust depending on the powder. The estimated release of TiO2 to outdoors was 0.9 kg per year. Particle release to the environment is not expected to cause any major impact due to atmospheric dilution.

Blueprint for a self-sustained European Centre for service provision in safe and sustainable innovation for nanotechnology.

The coming years are expected to bring rapid changes in the nanotechnology regulatory landscape, with the establishment of a new framework for nano-risk governance, in silico approaches for characterisation and risk assessment of nanomaterials, and novel procedures for the early identification and management of nanomaterial risks. In this context, Safe(r)-by-Design (SbD) emerges as a powerful preventive approach to support the development of safe and sustainable (SSbD) nanotechnology-based products and processes throughout the life cycle. This paper summarises the work undertaken to develop a blueprint for the deployment and operation of a permanent European Centre of collaborating laboratories and research organisations supporting safe innovation in nanotechnologies. The proposed entity, referred to as "the Centre", will establish a 'one-stop shop' for nanosafety-related services and a central contact point for addressing stakeholder questions about nanosafety. Its operation will rely on significant business, legal and market knowledge, as well as other tools developed and acquired through the EU-funded EC4SafeNano project and subsequent ongoing activities. The proposed blueprint adopts a demand-driven service update scheme to allow the necessary vigilance and flexibility to identify opportunities and adjust its activities and services in the rapidly evolving regulatory and nano risk governance landscape. The proposed Centre will play a major role as a conduit to transfer scientific knowledge between the research and commercial laboratories or consultants able to provide high quality nanosafety services, and the end-users of such services (e.g., industry, SMEs, consultancy firms, and regulatory authorities). The Centre will harmonise service provision, and bring novel risk assessment and management approaches, e.g. in silico methodologies, closer to practice, notably through SbD/SSbD, and decisively support safe and sustainable innovation of industrial production in the nanotechnology industry according to the European Chemicals Strategy for Sustainability.

Assessment of functional nanomaterials in medical applications: can time mend public and occupational health risks related to the products' fate?

Surface coatings are one promising option to prevent bacterial adhesion and biofilm formation given the prevalence of antibiotic resistant bacterial strains. Titanium dioxide (TiO2) is presently considered to be the only photocatalytic material suitable for commercial use, although the toxicity risks of TiO2, particularly in its nanoparticulate form, have not been fully addressed. The aim of this study was to determine release of nanoparticles (NPs) from functional materials for medical applications and their aerosol formation. Further, the fate of the material with respect to its product lifetime was investigated. The present study examined the risk of NP exposure since released submicronic and inhalable manufactured nano-objects, their agglomeraates or aggregates containing Ti were detected. The coating of the material magnifies its emission levels when comparing the obtained product properties to those of an uncoated sample. The evolution of release tendecy with the material's time of use shows that release does not vanish upon continuous material losses induced by the release, thus the risk does not diminish with time. Consequently, this nanomaterial TiO2 needs to be avoided in healthcare settings, or, alternatively, new TiO2-deposition techniques are required to be developed.

Environmental release of engineered nanomaterials from commercial tiles under standardized abrasion conditions.

The study presented here focuses on commercial antibacterial tiles whose emissivity of (nano) particles due to abrasion has yet barely been investigated. The tiles have been characterized regarding their surface properties and composition throughout their chain-of-use, i.e. from their state of commercialization until the experimental end-of-service life. In contrast to plane standard tiles, their surfaces form hilly surfaces. In the depressions, titanium dioxide is found at the surface, thus theoretically protected by the hilly areas against abrasion on the tile's surface. Furthermore, a deposition technique has been put in place by producers allowing for coating the before mentioned commercial tiles with titanium dioxide, thus being similar to those commercially available. It consists in depositing titanium dioxide on the surface, latter one allowing fixing the first. This development allows for better understanding the future options for product formulation and thus improvement with respect to particle release. The tests reveal the aerosolization from commercial antibacterial tiles of micronic and submicronic particles in the inhalable region or particles that can subjected to be released in the environment (<10µm). The aersolization of the particles from the coated tiles was found to be significantly higher compared to the non coated tiles.

Environmental exposure to TiO2 nanomaterials incorporated in building material.

Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO2 nanomaterials (TiO2-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO2-NMs and their state during/after potential release is currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO2-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m2 of cement after 168 h of leaching. TiO2-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO2-NM release mechanism is suspected to start from freeing of TiO2-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO2-NM release was not solely related to the cement degradation rate.

Air-liquid interface exposure to aerosols of poorly soluble nanomaterials induces different biological activation levels compared to exposure to suspensions.

BACKGROUND: Recently, much progress has been made to develop more physiologic in vitro models of the respiratory system and improve in vitro simulation of particle exposure through inhalation. Nevertheless, the field of nanotoxicology still suffers from a lack of relevant in vitro models and exposure methods to predict accurately the effects observed in vivo, especially after respiratory exposure. In this context, the aim of our study was to evaluate if exposing pulmonary cells at the air-liquid interface to aerosols of inhalable and poorly soluble nanomaterials generates different toxicity patterns and/or biological activation levels compared to classic submerged exposures to suspensions. Three nano-TiO2 and one nano-CeO2 were used. An exposure system was set up using VitroCell® devices to expose pulmonary cells at the air-liquid interface to aerosols. A549 alveolar cells in monocultures or in co-cultures with THP-1 macrophages were exposed to aerosols in inserts or to suspensions in inserts and in plates. Submerged exposures in inserts were performed, using similar culture conditions and exposure kinetics to the air-liquid interface, to provide accurate comparisons between the methods. Exposure in plates using classical culture and exposure conditions was performed to provide comparable results with classical submerged exposure studies. The biological activity of the cells (inflammation, cell viability, oxidative stress) was assessed at 24 h and comparisons of the nanomaterial toxicities between exposure methods were performed. RESULTS: Deposited doses of nanomaterials achieved using our aerosol exposure system were sufficient to observe adverse effects. Co-cultures were more sensitive than monocultures and biological responses were usually observed at lower doses at the air-liquid interface than in submerged conditions. Nevertheless, the general ranking of the nanomaterials according to their toxicity was similar across the different exposure methods used. CONCLUSIONS: We showed that exposure of cells at the air-liquid interface represents a valid and sensitive method to assess the toxicity of several poorly soluble nanomaterials. We underlined the importance of the cellular model used and offer the possibility to deal with low deposition doses by using more sensitive and physiologic cellular models. This brings perspectives towards the use of relevant in vitro methods of exposure to assess nanomaterial toxicity.

Specific uptake and genotoxicity induced by polystyrene nanobeads with distinct surface chemistry on human lung epithelial cells and macrophages.

Nanoparticle surface chemistry is known to play a crucial role in interactions with cells and their related cytotoxic effects. As inhalation is a major route of exposure to nanoparticles, we studied specific uptake and damages of well-characterized fluorescent 50 nm polystyrene (PS) nanobeads harboring different functionalized surfaces (non-functionalized, carboxylated and aminated) on pulmonary epithelial cells and macrophages (Calu-3 and THP-1 cell lines respectively). Cytotoxicity of in mass dye-labeled functionalized PS nanobeads was assessed by xCELLigence system and alamarBlue viability assay. Nanobeads-cells interactions were studied by video-microscopy, flow cytometry and also confocal microscopy. Finally ROS generation was assessed by glutathione depletion dosages and genotoxicity was assessed by γ-H2Ax foci detection, which is considered as the most sensitive technique for studying DNA double strand breaks. The uptake kinetic was different for each cell line. All nanobeads were partly adsorbed and internalized, then released by Calu-3 cells, while THP-1 macrophages quickly incorporated all nanobeads which were located in the cytoplasm rather than in the nuclei. In parallel, the genotoxicity study reported that only aminated nanobeads significantly increased DNA damages in association with a strong depletion of reduced glutathione in both cell lines. We showed that for similar nanoparticle concentrations and sizes, aminated polystyrene nanobeads were more cytotoxic and genotoxic than unmodified and carboxylated ones on both cell lines. Interestingly, aminated polystyrene nanobeads induced similar cytotoxic and genotoxic effects on Calu-3 epithelial cells and THP-1 macrophages, for all levels of intracellular nanoparticles tested. Our results strongly support the primordial role of nanoparticles surface chemistry on cellular uptake and related biological effects. Moreover our data clearly show that nanoparticle internalization and observed adverse effects are not necessarily associated.

Experimental evidence of colloids and nanoparticles presence from 25 waste leachates.

The potential colloids release from a large panel of 25 solid industrial and municipal waste leachates, contaminated soil, contaminated sediments and landfill leachates was studied. Standardized leaching, cascade filtrations and measurement of element concentrations in the microfiltrate (MF) and ultrafiltrate (UF) fraction were used to easily detect colloids potentially released by waste. Precautions against CO(2) capture by alkaline leachates, or bacterial re-growth in leachates from wastes containing organic matter should be taken. Most of the colloidal particles were visible by transmission electron microscopy with energy dispersion spectrometry (TEM-EDS) if their elemental MF concentration is greater than 200 µgl(-1). If the samples are dried during the preparation for microscopy, neoformation of particles can occur from the soluble part of the element. Size distribution analysis measured by photon correlation spectroscopy (PCS) were frequently unvalid, particularly due to polydispersity and/or too low concentrations in the leachates. A low sensitivity device is required, and further improvement is desirable in that field. For some waste leachates, particles had a zeta potential strong enough to remain in suspension. Mn, As, Co, Pb, Sn, Zn had always a colloidal form (MF concentration/UF concentration>1.5) and total organic carbon (TOC), Fe, P, Ba, Cr, Cu, Ni are partly colloidal for more than half of the samples). Nearly all the micro-pollutants (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Sb, Sn, V and Zn) were found at least once in colloidal form greater than 100 µgl(-1). In particular, the colloidal forms of Zn were always by far more concentrated than its dissolved form. The TEM-EDS method showed various particles, including manufactured nanoparticles (organic polymer, TiO(2), particles with Sr, La, Ce, Nd). All the waste had at least one element detected as colloidal. The solid waste leachates contained significant amount of colloids different in elemental composition from natural ones. The majority of the elements were in colloidal form for wastes of packaging (3), a steel slag, a sludge from hydrometallurgy, composts (2), a dredged sediment (#18), an As contaminated soil and two active landfill leachates. These results showed that cascade filtration and ICP elemental analysis seems valid methods in this field, and that electronic microscopy with elemental detection allows to identify particles. Particles can be formed from dissolved elements during TEM sample preparation and cross-checking with MF and UF composition by ICP is useful. The colloidal fraction of leachate of waste seems to be a significant source term, and should be taken into account in studies of emission and transfer of contaminants in the environment. Standardized cross-filtration method could be amended for the presence of colloids in waste leachates.

Ecotoxicity of non-aged and aged CeO2 nanomaterials towards freshwater microalgae.

The ecotoxicity of artificially alterated cerium dioxide nanoparticles (nano-CeO2) suspensions was determined using the freshwater microalgae growth inhibition test. The agglomeration or aggregation state of the alterated suspensions was followed because it represents one of the obvious modifications when nanoparticles reached the environment. In addition, its influence on the ecotoxicity of nanoparticles is currently not well-addressed. Our results showed that the suspensions were stable within the first 24 h and then agglomerate up to 10 µm after 3 and 30 days. The inhibitory effect on the growth of exposed algae was however similar whatever the tested suspension. This supports the fact that the agglomeration state of nano-CeO2, in our conditions, has few influences on the ecotoxicity toward these organisms. The EC50 values were 5.6; 4.1 and 6.2 mg L(-1), after exposure to non aged, 3 and 30 days aged suspensions respectively. The interaction between algal cells and nano-CeO2 was also addressed.