Determinants of workplace exposure and release of ultrafine particles during atmospheric plasma spraying in the ceramic industry

Atmospheric plasma spraying (APS) is a frequently used technique to produce enhanced-property coatings for different materials in the ceramic industry. This work aimed to characterise and quantify the impact of APS on workplace exposure to airborne particles, with a focus on ultrafine particles (UFPs, <100 nm) and nanoparticles (<50 nm). Particle number, mass concentrations, alveolar lung deposited surface area concentration, and size distributions, in the range 10 nm – 20 μm were simultaneously monitored at the emission source, in the worker breathing zone, and in outdoor air. Different input materials (known as feedstock) were tested: (a) micro-sized powders, and (b) suspensions containing submicron- or nano-sized particles. Results evidenced significant UFP emissions (up to 3.3x106/cm3) inside the projection chamber, which impacted exposure in the breathing zone outside the projection chamber (up to 8.3x105/cm3). Environmental release of UFPs was also detected and quantified (3.9x105/cm330 ). Engineered nanoparticle (ENP) release to workplace air was also evidenced by TEM microscopy. UFP emissions were detected during the application of both micro-sized powder and suspensions containing submicron- or nano-sized particles, thus suggesting that emissions were process- (and not material-) dependent. An effective risk prevention protocol was implemented, which resulted in a reduction of worker UFP exposure in the breathing zone. These findings evidence the potential risk of occupational exposure to UFPs during atmospheric plasma spraying, and raise the need for further research on UFP formation mechanisms in high-energy industrial processes

Modeling of High Nanoparticle Exposure in an Indoor Industrial Scenario with a One-Box Model

Mass balance models have proved to be effective tools for exposure prediction in occupational settings. However, they are still not extensively tested in real-world scenarios, or for particle number concentrations. An industrial scenario characterized by high emissions of unintentionally-generated nanoparticles (NP) was selected to assess the performance of a one-box model. Worker exposure to NPs due to thermal spraying was monitored, and two methods were used to calculate emission rates: the convolution theorem, and the cyclic steady state equation. Monitored concentrations ranged between 4.2 × 104–2.5 × 105 cm−3. Estimated emission rates were comparable with both methods: 1.4 × 1011–1.2 × 1013 min−1 (convolution) and 1.3 × 1012–1.4 × 1013 min−1 (cyclic steady state). Modeled concentrations were 1.4-6 × 104 cm−3 (convolution) and 1.7–7.1 × 104 cm−3 (cyclic steady state). Results indicated a clear underestimation of measured particle concentrations, with ratios modeled/measured between 0.2–0.7. While both model parametrizations provided similar results on average, using convolution emission rates improved performance on a case-by-case basis. Thus, using cyclic steady state emission rates would be advisable for preliminary risk assessment, while for more precise results, the convolution theorem would be a better option. Results show that one-box models may be useful tools for preliminary risk assessment in occupational settings when room air is well mixed

Contribution of Volcanic and Fumarolic Emission to the Aerosol in Marine Atmosphere in the Central Mediterranean Sea: Results from Med-Oceanor 2017 Cruise Campaign

This work studied the contribution of the geogenic sources volcanoes and fumaroles to the aerosol in marine atmosphere in the central Mediterranean basin. For this purpose, in the framework of the Med-Oceanor measurement program, we carried out a cruise campaign in the summer of 2017 to investigate the impact to the aerosol of the most important Mediterranean volcanoes (Mount Etna, Stromboli Island, and Marsili Seamount) and solfatara areas (Phlegraean Fields complex, Volcano Islands, Ischia Island, and Panarea submarine fumarole). We collected PM10 and PM2.5 samples in 12 sites and performed chemical characterization to gather information about the concentration of major and trace elements, elemental carbon (EC), organic carbon (OC), and ionic species. The use of triangular plots and the calculation of enrichment factors confirmed the interception of volcanic plume. We integrated the outcomes from chemical characterization with the use of factor analysis and SEM/EDX analysis for the source apportionment. Anthropogenic and natural sources including shipping emissions, volcanic and fumarolic load, as well as sea spray were identified as the main factors affecting aerosol levels in the study area. Furthermore, we performed pattern recognition analysis by stepwise linear discriminant analysis to seek differences in the composition of PM10 and PM2.5 samples according to their volcanic or solfatara origin.This research was funded by the European Commission—H2020, the ERA-PLANET programme (www.era-planet.eu; contract no. 689443) within the IGOSP project (www.igosp.eu).Peer reviewe

Unveiling the Toxicity of Fine and Nano-Sized Airborne Particles Generated from Industrial Thermal Spraying Processes in Human Alveolar Epithelial Cells

High-energy industrial processes have been associated with particle release into workplace air that can adversely affect workers' health. The present study assessed the toxicity of incidental fine (PGFP) and nanoparticles (PGNP) emitted from atmospheric plasma (APS) and high-velocity oxy-fuel (HVOF) thermal spraying. Lactate dehydrogenase (LDH) release, 2-(4-nitrophenyl)-2H-5-tetrazolio]-1,3-benzene disulfonate (WST-1) metabolisation, intracellular reactive oxygen species (ROS) levels, cell cycle changes, histone H2AX phosphorylation (γ-H2AX) and DNA damage were evaluated in human alveolar epithelial cells at 24 h after exposure. Overall, HVOF particles were the most cytotoxic to human alveolar cells, with cell viability half-maximal inhibitory concentration (IC50) values of 20.18 μg/cm2 and 1.79 μg/cm2 for PGFP and PGNP, respectively. Only the highest tested concentration of APS-PGFP caused a slight decrease in cell viability. Particle uptake, cell cycle arrest at S + G2/M and γ-H2AX augmentation were observed after exposure to all tested particles. However, higher levels of γ-H2AX were found in cells exposed to APS-derived particles (~16%), while cells exposed to HVOF particles exhibited increased levels of oxidative damage (~17% tail intensity) and ROS (~184%). Accordingly, APS and HVOF particles seem to exert their genotoxic effects by different mechanisms, highlighting that the health risks of these process-generated particles at industrial settings should not be underestimated. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.Funding text 1: transitória (Ref. DL-57/INSA-06/2018). Thanks are also due to FCT/MCTES for the financial support to EPIUnit and ITR (UIDB/04750/2020 and LA/P/0064/2020). Informed Consent Statement: Not applicable. Institutional Review Board Statement: Not applicable.; Funding text 2: Funding: This research was funded by the project CERASAFE with the support of ERA-NET SIINN (project id:16) and the Portuguese Foundation for Science and Technology (FCT; SIINN/0004/2014). This work was also supported by the project NanoBioBarriers (PTDC/MED-TOX/31162/2017), cofinanced by the Operational Program for Competitiveness and Internationalization (POCI) through European Regional Development Funds (FEDER/FNR) and FCT and the Spanish Ministry of Sci- ence and Innovation (projects PCIN-2015-173-C02-01 and CEX2018-000794-S-Severo Ochoa). M.J. Bessa (SFRH/BD/120646/2016) and F. Brandão (SFRH/BD/101060/2014) are recipients of FCT PhD scholarships under the framework of the Human Capital Operating Program (POCH) and European Union funding. The Doctoral Program in Biomedical Sciences of the ICBAS—University of Porto Int.J.Mol. Sci. 2022,of23fer, x FOR PEER REVIEWed additional funds. S. Fraga thanks FCT for funding through program DL 57/2016—Norm

In Vitro Toxicity of Industrially Relevant Engineered Nanoparticles in Human Alveolar Epithelial Cells: Air-Liquid Interface versus Submerged Cultures

Diverse industries have already incorporated within their production processes engineered nanoparticles (ENP), increasing the potential risk of worker inhalation exposure. In vitro models have been widely used to investigate ENP toxicity. Air–liquid interface (ALI) cell cultures have been emerging as a valuable alternative to submerged cultures as they are more representative of the inhalation exposure to airborne nano-sized particles. We compared the in vitro toxicity of four ENP used as raw materials in the advanced ceramics sector in human alveolar epithelial-like cells cultured under submerged or ALI conditions. Submerged cultures were exposed to ENP liquid suspensions or to aerosolised ENP at ALI. Toxicity was assessed by determining LDH release, WST-1 metabolisation and DNA damage. Overall, cells were more sensitive to ENP cytotoxic effects when cultured and exposed under ALI. No significant cytotoxicity was observed after 24 h exposure to ENP liquid suspensions, although aerosolised ENP clearly affected cell viability and LDH release. In general, all ENP increased primary DNA damage regardless of the exposure mode, where an increase in DNA strand-breaks was only detected under submerged conditions. Our data show that at relevant occupational concentrations, the selected ENP exert mild toxicity to alveolar epithelial cells and exposure at ALI might be the most suitable choice when assessing ENP toxicity in respiratory models under realistic exposure conditions.This research was funded by CERASAFE (www.cerasafe.eu; accessed on 26 October 2021), with the support of ERA-NET SIINN (project id:16) and the Portuguese Foundation for Science and Technology (FCT; SIINN/0004/2014). This work was also supported by the NanoBioBarriers project (PTDC/MED-TOX/31162/2017), co-financed by the Operational Program for Competitiveness and Internationalization (POCI) through European Regional Development Funds (FEDER/FNR) and FCT; Spanish Ministry of Science and Innovation (projects PCIN-2015-173-C02-01 and CEX2018-000794-S-Severo Ochoa), and by the Romanian National Authority for Scientific Research and Innovation (CCCDI-UEFISCDI, project number 29/2016 within PNCDI III). M.J. Bessa (SFRH/BD/120646/2016) and F. Brandão (SFRH/BD/101060/2014) are recipients of FCT PhD scholarships under the framework of Human Capital Operating Program (POCH) and European Union funding. The Doctoral Program in Biomedical Sciences, of the ICBAS—University of Porto, offered additional funds. S. Fraga thanks FCT for funding through program DL 57/2016–Norma transitória (Ref. DL-57/INSA-06/2018). Thanks are also due to FCT/MCTES for the financial support to EPIUnit (info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB/04750/2020/PT)

Characterizing the Chemical Profile of Incidental Ultrafine Particles for Toxicity Assessment Using an Aerosol Concentrator

Incidental ultrafine particles (UFPs) constitute a key pollutant in industrial workplaces. However, characterizing their chemical properties for exposure and toxicity assessments still remains a challenge. In this work, the performance of an aerosol concentrator (Versatile Aerosol Concentration Enrichment System, VACES) was assessed to simultaneously sample UFPs on filter substrates (for chemical analysis) and as liquid suspensions (for toxicity assessment), in a high UFP concentration scenario. An industrial case study was selected where metal-containing UFPs were emitted during thermal spraying of ceramic coatings. Results evidenced the comparability of the VACES system with online monitors in terms of UFP particle mass (for concentrations up to 95 µg UFP/m3 ) and between filters and liquid suspensions, in terms of particle composition (for concentrations up to 1000 µg/ m3). This supports the applicability of this tool for UFP collection in view of chemical and toxicological characterization for incidental UFPs. In the industrial setting evaluated, results showed that the spraying temperature was a driver of fractionation of metals between UF (<0.2 µm) and fine (0.2– 2.5 µm) particles. Potentially health hazardous metals (Ni, Cr) were enriched in UFPs and depleted in the fine particle fraction. Metals vaporized at high temperatures and concentrated in the UF fraction through nucleation processes. Results evidenced the need to understand incidental particle formation mechanisms due to their direct implications on particle composition and, thus, exposure. It is advisable that personal exposure and subsequent risk assessments in occupational settings should include dedicated metrics to monitor UFPs (especially, incidental).What’s important about this paper: Our work addresses the challenge of characterizing the bulk chemical composition of ultrafine particles in occupational settings, for exposure and toxicity assessments. We tested the performance of an aerosol concentrator (VACES) to simultaneously sample ultrafine particles (UFPs) on filter substrates and as liquid suspensions, in a high UFP concentration scenario. An industrial case study was selected where metal-bearing UFPs were emitted. We report the chemical exposures characterized in the industrial facility, and evidence the comparability of the VACES system with online monitors for UFP particle mass (up to 95 µg UFP/m3) as well as between UFP chemical composition on filters and in suspension. This supports the applicability of this tool for UFP collection in view of chemical and toxicological characterization of exposures to incidental UFPs in workplace settings.Highlights: - The VACES system is a useful tool for UFP sampling in high-concentration settings; - UFP collected simultaneously on filters and in suspension showed good comparability; - UFP chemical profiles were characterized; - Health-hazardous metals Ni and Cr accumulated in UFPs; - Understanding emission mechanisms is key to identifying exposure sources.This work was funded by SIINN ERA-NET (project id: 16), the Spanish MINECO (PCIN-2015-173-C02-01) and the French agency (Region Hauts de France). The Spanish Ministry of Science and Innovation (Project CEX2018-000794-S; Severo Ochoa) and the Generalitat de Catalunya (project number: AGAUR 2017 SGR41) provided support for the indirect costs for the Institute of Environmental Assessment and Water Research (IDAEA-CSIC). We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).info:eu-repo/semantics/publishedVersio

In vitro cell-transforming capacity of micro- and nanoplastics derived from 3D-printing waste

The increasing use of plastic polymers in 3D printing applications may lead to human exposure to micro- and nanoplastics (MNPLs), raising concerns regarding adverse health consequences such as cancer induction. Little attention has been given to MNPLs originated at the end of the life cycle of 3D-printed objects because of the mechanical and environmental degradation of plastic waste. This study assessed the carcinogenic potential of secondary MNPLs generated through cryomilling of 3D objects using the validated in vitro Bhas 42 cell transformation assay (CTA). Three-dimensional objects were printed using four types of polycarbonate (PC)- and polypropylene (PP)-modified thermoplastic filaments, undoped and doped with single-walled carbon nanotubes (PC-CNT) and silver nanoparticles (PP-Ag), respectively. MNPLs (< 5 µm) generated following a three-step top-down process were thoroughly characterized. Bhas 42 cells were treated once (initiation assay) or repeatedly (promotion assay) with several concentrations of MNPLs (3.125–100 µg/mL) mimicking realistic exposure conditions, and transformed foci formation was evaluated after 21 days. Furthermore, cellular internalization and the mRNA expression of seven genes previously recognized as part of a predictive early cell transformation signature were also evaluated. Despite being internalized, none of the particles was able to initiate or promote in vitro cell transformation, regardless of doping with nanomaterials. Alternatively, all the particles significantly increased and decreased the mRNA expression of Prl2c3 and Timp4, respectively, under promotion conditions, indicating early changes that occur before the formation of transformed foci. These findings suggest that the test MNPLs could have a tumorigenic potential despite not showing morphological changes in Bhas 42 cells

In vitro toxicity of industrially relevant engineered nanoparticles in human alveolar epithelial cells: air–liquid interface versus submerged cultures

Diverse industries have already incorporated within their production processes engineered nanoparticles (ENP), increasing the potential risk of worker inhalation exposure. In vitro models have been widely used to investigate ENP toxicity. Air–liquid interface (ALI) cell cultures have been emerging as a valuable alternative to submerged cultures as they are more representative of the inhalation exposure to airborne nano-sized particles. We compared the in vitro toxicity of four ENP used as raw materials in the advanced ceramics sector in human alveolar epithelial-like cells cultured under submerged or ALI conditions. Submerged cultures were exposed to ENP liquid suspensions or to aerosolised ENP at ALI. Toxicity was assessed by determining LDH release, WST-1 metabolisation and DNA damage. Overall, cells were more sensitive to ENP cytotoxic effects when cultured and exposed under ALI. No significant cytotoxicity was observed after 24 h exposure to ENP liquid suspensions, although aerosolised ENP clearly affected cell viability and LDH release. In general, all ENP increased primary DNA damage regardless of the exposure mode, where an increase in DNA strand-breaks was only detected under submerged conditions. Our data show that at relevant occupational concentrations, the selected ENP exert mild toxicity to alveolar epithelial cells and exposure at ALI might be the most suitable choice when assessing ENP toxicity in respiratory models under realistic exposure conditions

In Vitro Toxicity of Industrially Relevant Engineered Nanoparticles in Human Alveolar Epithelial Cells: Air-Liquid Interface versus Submerged Cultures

This article belongs to the Special Issue Engineered Nanomaterials Exposure and Risk Assessment: Occupational Health and SafetyDiverse industries have already incorporated within their production processes engineered nanoparticles (ENP), increasing the potential risk of worker inhalation exposure. In vitro models have been widely used to investigate ENP toxicity. Air-liquid interface (ALI) cell cultures have been emerging as a valuable alternative to submerged cultures as they are more representative of the inhalation exposure to airborne nano-sized particles. We compared the in vitro toxicity of four ENP used as raw materials in the advanced ceramics sector in human alveolar epithelial-like cells cultured under submerged or ALI conditions. Submerged cultures were exposed to ENP liquid suspensions or to aerosolised ENP at ALI. Toxicity was assessed by determining LDH release, WST-1 metabolisation and DNA damage. Overall, cells were more sensitive to ENP cytotoxic effects when cultured and exposed under ALI. No significant cytotoxicity was observed after 24 h exposure to ENP liquid suspensions, although aerosolised ENP clearly affected cell viability and LDH release. In general, all ENP increased primary DNA damage regardless of the exposure mode, where an increase in DNA strand-breaks was only detected under submerged conditions. Our data show that at relevant occupational concentrations, the selected ENP exert mild toxicity to alveolar epithelial cells and exposure at ALI might be the most suitable choice when assessing ENP toxicity in respiratory models under realistic exposure conditions.This research was funded by CERASAFE (www.cerasafe.eu; accessed on 26 October 2021), with the support of ERA-NET SIINN (project id:16) and the Portuguese Foundation for Science and Technology (FCT; SIINN/0004/2014). This work was also supported by the NanoBioBarriers project (PTDC/MED-TOX/31162/2017), co-financed by the Operational Program for Competitiveness and Internationalization (POCI) through European Regional Development Funds (FEDER/FNR) and FCT; Spanish Ministry of Science and Innovation (projects PCIN-2015-173-C02-01 and CEX2018-000794- S-Severo Ochoa), and by the Romanian National Authority for Scientific Research and Innovation (CCCDI-UEFISCDI, project number 29/2016 within PNCDI III). M.J. Bessa (SFRH/BD/120646/2016) and F. Brandão (SFRH/BD/101060/2014) are recipients of FCT PhD scholarships under the framework of Human Capital Operating Program (POCH) and European Union funding. The Doctoral Program in Biomedical Sciences, of the ICBAS—University of Porto, offered additional funds. S. Fraga thanks FCT for funding through program DL 57/2016–Norma transitória (Ref. DL-57/INSA-06/2018). Thanks are also due to FCT/MCTES for the financial support to EPIUnit (UIDB/04750/2020).info:eu-repo/semantics/publishedVersio

Safe(r)-by-design principles in the thermoplastics industry: guidance on release assessment during manufacture of nano-enabled products

Background: The application of nanomaterials (NMs) and nano-enabled products (NEPs) across many industries has been extensive and is still expanding decades after first being identified as an emerging technology. Additive manufacturing has been greatly impacted and has seen the benefits of integrating NMs within products. With the expansion of nanotechnology, there has been a need to develop more adaptive and responsive methods to ascertain risks and ensure technology is developed safely. The Safe(r)-by-Design (SbD) concept can be used to establish safe parameters and minimise risks during the materials’ lifecycle, including the early stages of the supply chain. Exposure monitoring has advanced in recent years with the creation of standardised protocols for occupational exposure assessment of nano-objects and their aggregates and agglomerates (NOAA).Methods: To aid in the development of an online SbD-supporting platform by the EU-funded project SAbyNA, we adopt a Europe Standard for monitoring release of NOAA to identify if a greater release of NOAA is associated with incorporation of NMs within NEPs compared to a polymer matrix alone. Case studies included filaments of polypropylene (PP) with nano-Ag or polycarbonate (PC) with single-walled carbon nanotubes (SWCNTs). NMs were received in masterbatch, and therefore previously modified to align with SbD interventions. Results were collected in line with European Standard recommendations: monitoring particle concentrations using direct reading instruments (DRI), sampling for offline chemical and morphological analysis, and collecting contextual information.Results and discussion: Based on the criteria described in the European standard (BS EN 17058), data from both case studies identified that inhalation exposure relating to NM was “unlikely”. Despite this, during the production of the SWCNT-PC filaments, some noteworthy observations were made, including several DRI activity measurements shown to be higher than background levels, and material morphologically similar to the reference SWCNT/polymeric masterbatch observed in offline analysis. The data collected during this campaign were used to discuss choices available for data interpretation and decision-making in the European Standard for monitoring release of NOAA and also to facilitate the development of SAbyNA’s user-friendly industry platform for the SbD of NMs and NEPs