Nano-objects And Their Agglomerates And Aggregates Research Articles

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

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). 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. 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.

The Influence of Air Humidity on the Output Signal from an Ionization Smoke Detector in the Presence of Soot Nanoparticles

In 2019, the European Committee for Standardization (CEN) initiated work on the preparation of a strategy for air quality monitoring at workplaces. The aim was to determine the concentrations of nano-objects and their aggregates and agglomerates (NOAA) by means of direct measurements using low-cost sensors. There is a growing need for low-cost devices that can continuously monitor the concentrations of nanoparticles, and that can be installed where nanoparticles are used or created spontaneously. In search of such a device, in this study, a smoke detector with an ionization sensor was tested. The aim of the research was to investigate the response of the analog output signal with respect to changes in environmental parameters such as the relative humidity of air. The research was conducted in controlled laboratory conditions, and the results confirmed that an ionization detector could be used to measure the concentrations of nanoaerosols. The modified smoke detector detected soot particles smaller than 100 nm. The linear regression line was calculated for the relative humidity dataset and had a slope coefficient of −1.214 × 10−4; thus, the value of the output signal was constant during the experiment. The dependence on air temperature was approximated by a second-degree curve, with a slope coefficient of −8.113 × 10−2. Air humidity affected aerosol concentrations, which may be related to surface modification of nanoparticles.

Safe-by-design strategies applied to scaffold hybrid manufacturing

The EU-project FAST (GA 685825) has developed a 3D printer machine prototype for the manufacture of bone implants (scaffolds), by merging masterbatches of biodegradable polymer poly(ethylene oxide)terephthalate/poly(butylene terephthalate) [PEOT/PBT] doped with nanofillers [reduced graphene oxide (rGO), hydroxyapatite (HA) and magnesium aluminium hydroxide ciprofloxacin hydrotalcite (LDH-CFX)], and atmospheric plasma technology. This paper focus on the safe design strategies identified by FAST to address the risk to health resulting from the potential airborne emission of nano-objects and their aggregates and agglomerates (NOAAs) by the 3D printer prototype, which might result in occupational exposures by inhalation. The work also includes measurements of airborne emissions and occupational exposures carried out during the verification stage of the prototype design. Nanofillers particles (rGO, n-HA, LDH-CFX) were not observed, neither at source nor in the working area, suggesting no release of free nanofillers to the air one they have been embedded in the polymer masterbatch. Additionally, the exposure in the workplace was far below the selected Occupational Exposure Levels (OELs), for total particle number concentration (PNC), dust, elemental carbon (EC) and volatile organic compounds (VOCs). The results showed that, when working with the current prototype in normal operation (for its intended use) and with controls enabled [enclosure with the doors closed and Local Exhaust Ventilation (LEV) activated], the emission from the machine and the worker’s exposure to NOAAs are well controlled.

Workers' Exposure to Nano-Objects with Different Dimensionalities in R&D Laboratories: Measurement Strategy and Field Studies.

With the increasing interest in the potential benefits of nanotechnologies, concern is still growing that they may present emerging risks for workers. Various strategies have been developed to assess the exposure to nano-objects and their agglomerates and aggregates (NOAA) in the workplace, integrating different aerosol measurement instruments and taking into account multiple parameters that may influence NOAA toxicity. The present study proposes a multi-metric approach for measuring and sampling NOAA in the workplace, applied to three case studies in laboratories each dedicated to materials with different shapes and dimensionalities: graphene, nanowires, and nanoparticles. The study is part of a larger project with the aim of improving risk management tools in nanomaterials research laboratories. The harmonized methodology proposed by the Organization for Economic Cooperation and Development (OECD) has been applied, including information gathering about materials and processes, measurements with easy-to-use and hand-held real-time devices, air sampling with personal samplers, and off-line analysis using scanning electron microscopy. Significant values beyond which an emission can be attributed to the NOAA production process were identified by comparison of the particle number concentration (PNC) time series and the corresponding background levels in the three laboratories. We explored the relations between background PNC and microclimatic parameters. Morphological and elemental analysis of sampled filters was done to identify possible emission sources of NOAA during the production processes: rare particles, spherical, with average diameter similar to the produced NOAA were identified in the nanoparticles laboratory, so further investigation is recommended to confirm the potential for worker exposure. In conclusion, the information obtained should provide a valuable basis for improving risk management strategies in the laboratory at work.

Measurement techniques of exposure to nanomaterials in the workplace for low- and medium-income countries: A systematic review.

Nanotechnology offers many opportunities but there is still considerable uncertainty about the health risks and how to assess these.In the field of risk analysis for workers potentially exposed to nano-objects and their agglomerates and aggregates (NOAA) different methodological approaches to measure airborne NOAA have been proposed.This study proposes a systematic review of scientific literature on occupational exposure to NOAA in the workplace with the aim to identify techniques of exposure measurement to be recommended in low- and medium-income countries.We gathered scientific papers reporting techniques of NOAA exposure measurements in the workplace, we summarized the data for each eligible technique according to PRISMA guidelines, and we rated the quality of evidence following an adapted GRADE approach.We found 69 eligible studies to be included in qualitative synthesis: the majority of studies reported a moderate quality and only two studies demonstrated the use of a high quality exposure measurement technique.The review demonstrates that a basic exposure measurement, i.e. evidence for the presence or absence of NOAA in the workplace air, can be achieved with moderate (40 techniques) to high (2 techniques) quality; comprehensive exposure measurement, that allow the quantification of NOAA in the workplace, can be achieved with moderate (11 techniques) to high (2 techniques) quality.The findings of the study also allowed to finalize a list of requirements that must be fulfilled by an effective measurement technique (either basic or comprehensive) and to highlight the main weaknesses that need to be tackled for an effective affordability evaluation of measurement techniques to be recommended in low- and medium-income countries.

Development of International Standard on Nano Aerosol Generation for Inhalation Toxicology Study

Development ISO TR 19601 : Aerosol generation for NOAA (nano-objects and their aggregates and agglomerates) air exposure studies is completed recently. The technical report (TR) reviews methods for generating aerosols of NOAA for in vivo and in vitro inhalation studies. The goals of this technical report is to aid in selecting appropriates NOAA aerosol generator to perform a planned toxicology design. The TR describes how to approach air exposure study design after considering workplace exposure scenario with providing a flow chart to select a proper NOAA generator for aimed study. The TR presents variety of NOAA generator currently used, and describes the principles of operation, advantage at limitation of the NOAA generators. This TR will assist investigators on NOAA inhalation toxicity testing how to design inhalation exposure study with selection of proper generators. This mini-review summarizes contents of the technical report and provides the current status of science in NOAA aerosol generation.

Assessment of Determinants of Emission Potentially Affecting the Concentration of Airborne Nano-Objects and Their Agglomerates and Aggregates.

Nano-specific inhalation exposure models could potentially be effective tools to assess and control worker exposure to nano-objects, and their aggregates and agglomerates (NOAA). However, due to the lack of reliable and consistent collected NOAA exposure data, the scientific basis for validation of the existing NOAA exposure models is missing or limited. The main objective of this study was to gain more insight into the effect of various determinants underlying the potential on the concentration of airborne NOAA close to the source with the purpose of providing a scientific basis for existing and future exposure inhalation models. Four experimental studies were conducted to investigate the effect of 11 determinants of emission on the concentration airborne NOAA close to the source during dumping of ~100% nanopowders. Determinants under study were: nanomaterial, particle size, dump mass, height, rate, ventilation rate, mixing speed, containment, particle surface coating, moisture content of the powder, and receiving surface. The experiments were conducted in an experimental room (19.5 m3) with well-controlled environmental and ventilation conditions. Particle number concentration and size distribution were measured using real-time measurement devices. Dumping of nanopowders resulted in a higher number concentration and larger particles than dumping their reference microsized powder (P < 0.05). Statistically significant more and larger particles were also found during dumping of SiO2 nanopowder compared to TiO2/Al2O3 nanopowders. Particle surface coating did not affect the number concentration but on average larger particles were found during dumping of coated nanopowders. An increase of the powder's moisture content resulted in less and smaller particles in the air. Furthermore, the results indicate that particle number concentration increases with increasing dump height, rate, and mass and decreases when ventilation is turned on. These results give an indication of the direction and magnitude of the effect of the studied determinants on concentrations close to the source and provide a scientific basis for (further) development of existing and future NOAA inhalation exposure models.

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.

The Validity and Applicability of Using a Generic Exposure Assessment Model for Occupational Exposure to Nano-Objects and Their Aggregates and Agglomerates.

Control banding can be used as a first-tier assessment to control worker exposure to nano-objects and their aggregates and agglomerates (NOAA). In a second tier, more advanced modelling approaches are needed to produce quantitative exposure estimates. As currently no general quantitative nano-specific exposure models are available, this study evaluated the validity and applicability of using a generic exposure assessment model (the Advanced REACH Tool-ART) for occupational exposure to NOAA. The predictive capability of ART for occupational exposure to NOAA was tested by calculating the relative bias and correlations (Pearson) between the model estimates and measured concentrations using a dataset of 102 NOAA exposure measurements collected during experimental and workplace exposure studies. Moderate to (very) strong correlations between the ART estimates and measured concentrations were found. Estimates correlated better to measured concentration levels of dust (r = 0.76, P < 0.01) than liquid aerosols (r = 0.51, P = 0.19). However, ART overestimated the measured NOAA concentrations for both the experimental and field measurements (factor 2-127). Overestimation was highest at low concentrations and decreased with increasing concentration. Correlations seemed to be better when looking at the nanomaterials individually compared to combined scenarios, indicating that nanomaterial-specific characteristics are not well captured within the mechanistic model of the ART. Although ART in its current state is not capable to estimate occupational exposure to NOAA, the strong correlations for the individual nanomaterials indicate that the ART (and potentially other generic exposure models) have the potential to be extended or adapted for exposure to NOAA. In the future, studies investigating the potential to estimate exposure to NOAA should incorporate more explicitly nanomaterial-specific characteristics in their models.

Occupational Exposure to Nano-Objects and Their Agglomerates and Aggregates Across Various Life Cycle Stages; A Broad-Scale Exposure Study.

Occupational exposure to manufactured nano-objects and their agglomerates, and aggregates (NOAA) has been described in several workplace air monitoring studies. However, data pooling for general conclusions and exposure estimates are hampered by limited exposure data across the occupational life cycle of NOAA and a lack in comparability between the methods of collecting and analysing the data. By applying a consistent method of collecting and analysing the workplace exposure data, this study aimed to provide information about the occupational NOAA exposure levels across various life cycle stages of NOAA in the Netherlands which can also be used for multi-purpose use. Personal/near field task-based exposure data was collected using a multi-source exposure assessment method collecting real time particle number concentration, particle size distribution (PSD), filter-based samples for morphological, and elemental analysis and detailed contextual information. A decision logic was followed allowing a consistent and objective way of analysing the exposure data. In total, 46 measurement surveys were conducted at 15 companies covering 18 different exposure situations across various occupational life cycle stages of NOAA. Highest activity-effect levels were found during replacement of big bags (<1000-76000 # cm(-3)), mixing/dumping of powders manually (<1000-52000 # cm(-3)) and mechanically (<1000-100000 # cm(-3)), and spraying of liquid (2000-800000 # cm(-3)) showing a high variability between and within the various exposure situations. In general, a limited change in PSD was found during the activity compared to the background. This broad-scale exposure study gives a comprehensive overview of the NOAA exposure situations in the Netherlands and an indication of the levels of occupational exposure to NOAA across various life cycle of NOAA. The collected workplace exposure data and contextual information will serve as basis for future pooling of data and modelling of worker exposure.

Migration of Ag- and TiO2-(Nano)particles from Textiles into Artificial Sweat under Physical Stress: Experiments and Exposure Modeling

Engineered nanoparticles (ENP) are increasingly used to functionalize textiles taking advantage, e.g., of the antimicrobial activity of silver (Ag)-ENP or the UV-absorption of titania (TiO2)-ENP. Mobilization and migration of ENPs from the textile into human sweat can result in dermal exposure to these nanoobjects and their aggregates and agglomerates (NOAA). In this study we assessed exposure to NOAA migrating from commercially available textiles to artificial sweat by an experimental setup that simulates wear-and-tear during physical activity. By combining physical stress with incubation in alkaline and acidic artificial sweat solutions we experimentally realized a worst case scenario for wearing functionalized textiles during sports activities. This experimental approach is not limited to NOAA, but can be used for any other textile additive. Out of four investigated textiles, one T-shirt and one pair of trousers with claimed antimicrobial properties were found to release Ag <450 nm in detectable amounts (23-74 μg/g/L). Textiles containing TiO2 for UV protection did not release significant amounts of TiO2 <450 nm, but the antimicrobial T-shirt released both TiO2 and Ag <450 nm. The silver was present in dissolved and particulate form, whereas TiO2 was mainly found as particulate. On the basis of our experimental results we calculated external dermal exposure to Ag and TiO2 for male and female adults per use. For silver, maximal amounts of 17.1 and 8.2 μg/kg body weight were calculated for total and particulate Ag <450 nm, respectively. For TiO2, the exposure levels amount to maximal 11.6 μg/kg body weight for total (mainly particulate) TiO2. In comparison with other human exposure pathways, dermal exposure to NOAA from textiles can be considered comparably minor for TiO2-NOAA, but not for Ag-NOAA.