Continuous 3-day exposure assessment of workplace manufacturing silver nanoparticles

In this study we present an overview of the research activities in nanotechnology for the period 2001?C2011 for six selected countries belonging to the Organization of Islamic cooperation (OIC). The selection has been made based on the research output of these countries. The countries are Iran, Turkey, Egypt, Malaysia, Saudi Arabia, and Pakistan. The factors considered are the number of publications, citations per paper, p-index, and collaborative research output. Iran with 7,795 publications and an annual growth rate of 41?% leads the group, followed by Turkey with 3,169 publications and an annual growth rate of 29?%. Turkey however, has a much better citation per paper (8.96), and p-index (63.34) as compared to Iran (4.59 and 54.36, respectively). We can classify the six countries into two categories. Those, that have a well coordinated national program in nanotechnology, namely, Iran, Malaysia, and Saudi Arabia and those that do not have any national program but are still showing a reasonable good activity in nanotechnology namely Turkey, Egypt, and Pakistan. A brief account of the initiatives taken by the six selected countries of OIC in the field of nanotechnology is also presented.     

Environmental exposure assessment framework for nanoparticles in solid waste

Information related to the potential environmental exposure of engineered nanomaterials (ENMs) in the solid waste management phase is extremely scarce. In this paper, we define nanowaste as separately collected or collectable waste materials which are or contain ENMs, and we present a five-step framework for the systematic assessment of ENM exposure during nanowaste management. The framework includes deriving EOL nanoproducts and evaluating the physicochemical properties of the nanostructure, matrix properties and nanowaste treatment processes as well as transformation processes and environment releases, eventually leading to a final assessment of potential ENM exposure. The proposed framework was applied to three selected nanoproducts: nanosilver polyester textile, nanoTiO₂ sunscreen lotion and carbon nanotube tennis racquets. We found that the potential global environmental exposure of ENMs associated with these three products was an estimated 0.5–143 Mg/year, which can also be characterised qualitatively as medium, medium, low, respectively. Specific challenges remain and should be subject to further research: (1) analytical techniques for the characterisation of nanowaste and its transformation during waste treatment processes, (2) mechanisms for the release of ENMs, (3) the quantification of nanowaste amounts at the regional scale, (4) a definition of acceptable limit values for exposure to ENMs from nanowaste and (5) the reporting of nanowaste generation data.     

The effect of different workplace nanoparticles on the immune systems of employees

Currently, nanoparticles are widely present in the environment and are being used in various industrial technologies. Nanoparticles affect immune functions, causing different immune responses. The aim of the current study was to evaluate several cytokines, interleukin (IL)-1b, IL-6, IL-8, tumour necrosis factor-a (TNF-α), interferon-γ, adhesive molecule sICAM-1, macrophage inhibitory protein 1a (MIP1a) and secretory immunoglobulin A, in nasal lavage fluid and in the peripheral blood of healthy subjects exposed to workplace nanoparticles. Thirty-six employees from three different environments were examined: 12 from a metalworking company, 12 from a woodworking company and 12 office workers. The nanoparticles in the different workplaces were detected in the air in the immediate vicinity of the employees. The particle number concentration and surface area values were significantly higher in the workplaces of the metal- and woodworking industries, but concentrations of mass were lower (the measurements were performed by an electrical low-pressure impactor ELPI+). Energy dispersive X-ray spectroscopy (EDS, an attachment to a high-resolution SEM) was used to provide elemental analysis or chemical characterization of the dust particles in a low-vacuum field-free mode operating at a potential of 15 kV spot 3.0. The technique used provided quantitative and spatial analyses of the distribution of elements through mapping (two to three parallel measurements) and point analysis (four to five parallel measurements). Samples from the metal industry contained more ultramicroscopic and nanometric particles, e.g. toxic metals such as Zn, Mn and Cr, and fewer microscopic dust particles. The nasal lavage and peripheral blood were taken at the beginning and the end of the working week, when immune indices were measured. Our data showed a statistically significant increased level of the pro-inflammatory cytokine TNF-α in serum in both exposed groups compared with office workers as well as a higher level of TNF-α in workers from the woodworking company compared with the metalworking employees. We found an elevated level of IL-6 in the exposed groups as well as an elevated level of IL-8 in the nasal lavage in woodworking employees after work.     

Reduction of nanoparticle exposure to welding aerosols by modification of the ventilation system in a workplace

Nanometer particle size distributions were measured in booths with two different ventilation patterns in an occupational environment with welding operations underway. The measurements were used to illustrate the impact of change of ventilation methods (existing – with ventilation ducts located at the top, modified – with ventilation ducts located below the weld bench) on the aerosol size distributions at different locations: close to the weld, in the vicinity of the welder’s face, and in the exhaust duct. Particle number concentrations measured in the vicinity of the welder’s face (mask) during a horizontal standard arc welding process in a booth with ventilation at the top was in the range of 7.78×10⁵ particles cm⁻³ with a geometric mean size of 181 nm and geometric standard deviation of 1.8. This reduced to 1.48×10⁴ particles cm⁻³ in the vicinity of the welder’s face with the modified ventilation system. The clearance of the welding aerosol was also faster in the modified booth (6 min compared to 11 min in a conventional booth). Particles were collected in the booth for the various test conditions, and analyzed to determine their composition and morphology. The particles were composed of hazardous heavy metals such as manganese, chromium and nickel, and had varying morphologies.     

Characterization of exposure to silver nanoparticles in a manufacturing facility

An assessment of the extent of exposure to nanomaterials in the workplace will be helpful in improving the occupational safety of workers. It is essential that the exposure data in the workplace are concerned with risk management to evaluate and reduce worker exposure. In a manufacturing facility dealing with nanomaterials, some exposure data for gas-phase reactions are available, but much less information is available regarding liquid-phase reactions. Although the potential for inhaling nanomaterials in a liquid-phase process is less than that for gas-phase, the risks of exposure during wet-chemistry processes are not negligible. In this study, we monitored and analyzed the exposure characteristics of silver nanoparticles during a liquid-phase process in a commercial production facility. Based on the measured exposure data, the source of Ag nanoparticles emitted during the production processes was indentified and a mechanism for the growth of Ag nanoparticle released is proposed. The data reported in this study could be used to establish occupational safety guidelines in the nanotechnology workplace, especially in a liquid-phase production facility.     

Estimation of surface area concentration of workplace incidental nanoparticles based on number and mass concentrations

Surface area was estimated by three different methods using number and/or mass concentrations obtained from either two or three instruments that are commonly used in the field. The estimated surface area concentrations were compared with reference surface area concentrations (SA_REF) calculated from the particle size distributions obtained from a scanning mobility particle sizer and an optical particle counter (OPC). The first estimation method (SA_PSD) used particle size distribution measured by a condensation particle counter (CPC) and an OPC. The second method (SA_INV1) used an inversion routine based on PM1.0, PM2.5, and number concentrations to reconstruct assumed lognormal size distributions by minimizing the difference between measurements and calculated values. The third method (SA_INV2) utilized a simpler inversion method that used PM1.0 and number concentrations to construct a lognormal size distribution with an assumed value of geometric standard deviation. All estimated surface area concentrations were calculated from the reconstructed size distributions. These methods were evaluated using particle measurements obtained in a restaurant, an aluminum die-casting factory, and a diesel engine laboratory. SA_PSD was 0.7–1.8 times higher and SA_INV1 and SA_INV2 were 2.2–8 times higher than SA_REF in the restaurant and diesel engine laboratory. In the die casting facility, all estimated surface area concentrations were lower than SA_REF. However, the estimated surface area concentration using all three methods had qualitatively similar exposure trends and rankings to those using SA_REF within a workplace. This study suggests that surface area concentration estimation based on particle size distribution (SA_PSD) is a more accurate and convenient method to estimate surface area concentrations than estimation methods using inversion routines and may be feasible to use for classifying exposure groups and identifying exposure trends.     

Simplified pregnant woman models for the fetus exposure assessment

In this paper, we introduce a study that we carried out in order to validate the use of a simplified pregnant woman model for the assessment of the fetus exposure to radio frequency waves. This simplified model, based on the use of a homogeneous tissue to replace most of the inner organs of the virtual mother, would allow us to deal with many issues that are raised because of the lack of pregnant woman models for numerical dosimetry. Using specific absorption rate comparisons, we show that this model could be used to estimate the fetus exposure to plane waves.     

Monitor for detecting and assessing exposure to airborne nanoparticles

An important safety aspect of the workplace environment concerns the severity of its air pollution with nanoparticles (NP; <100 nm) and ultrafine particles (UFP; <300 nm). Depending on their size and chemical nature, exposure to these particles through inhalation can be hazardous because of their intrinsic ability to deposit in the deep lung regions and the possibility to subsequently pass into the blood stream. Recommended safety measures in the nanomaterials industry are pragmatic, aiming at exposure minimization in general, and advocating continuous control by monitoring both the workplace air pollution level and the personal exposure to airborne NPs. This article describes the design and operation of the Aerasense NP monitor that enables intelligence gathering in particular with respect to airborne particles in the 10–300 nm size range. The NP monitor provides real time information about their number concentration, average size, and surface areas per unit volume of inhaled air that deposit in the various compartments of the respiratory tract. The monitor’s functionality relies on electrical charging of airborne particles and subsequent measurements of the total particle charge concentration under various conditions. Information obtained with the NP monitor in a typical workplace environment has been compared with simultaneously recorded data from a Scanning Mobility Particle Sizer (SMPS) capable of measuring the particle size distribution in the 11–1086 nm size range. When the toxicological properties of the engineered and/or released particles in the workplace are known, personal exposure monitoring allows a risk assessment to be made for a worker during each workday, when the workplace-produced particles can be distinguished from other (ambient) particles.     

Physicochemical properties and toxicological assessment of modified CdS nanoparticles

The synthesis procedure represents a key aspect in designing the physical and chemical properties of gold nanoparticles. The current study proposes a simple approach for gold nanoparticles synthesis using non-thermal plasma. The novelty of the setup consists in producing an in-liquid plasma discharge in argon bubbles that are externally generated in the solution exposed to treatment. Because plasma is the source of active species which are directly involved in gold reduction, no additional reducing agent was necessary. Collagen protein was used as capping agent. A plasma treatment of 10 min is sufficient for obtaining stable colloidal solutions with UV-Vis absorption maximum at 530 nm. Transmission electron microscopy images revealed preponderant spherical nanoparticles with dimensions in the range of 6–20 nm. The method of synthesis distinguishes by its good reproducibility, facility, efficiency, and ability to generate stable colloidal nanoparticles after several minutes of plasma exposure.     

Workplace exposure to nanoparticles and the application of provisional nanoreference values in times of uncertain risks

Nano reference values (NRVs) for occupational use of nanomaterials were tested as provisional substitute for Occupational Exposure Limits (OELs). NRVs can be used as provisional limit values until Health-Based OELs or derived no-effect levels (DNEL) become available. NRVs were defined for 8?h periods (time weighted average) and for short-term exposure periods (15?min-time weighted average). To assess the usefulness of these NRVs, airborne number concentrations of nanoparticles (NPs) in the workplace environment were measured during paint manufacturing, electroplating, light equipment manufacturing, non-reflective glass production, production of pigment concentrates and car refinishing. Activities monitored were handling of solid engineered NPs (ENP), abrasion, spraying and heating during occupational use of nanomaterials (containing ENPs) and machining nanosurfaces. The measured concentrations are often presumed to contain ENPs as well as process-generated NPs (PGNP). The PGNP are found to be a significant source for potential exposure and cannot be ignored in risk assessment. Levels of NPs identified in workplace air were up to several millions of nanoparticles/cm³. Conventional components in paint manufacturing like CaCO₃ and talc may contain a substantial amount of nanosized particulates giving rise to airborne nanoparticle concentrations. It is argued that risk assessments carried out for e.g. paint manufacturing processes using conventional non-nano components should take into account potential nanoparticle emissions as well. The concentrations measured were compared with particle-based NRVs and with mass-based values that have also been proposed for workers protection. It is concluded that NRVs can be used for risk management for handling or processing of nanomaterials at workplaces provided that the scope of NRVs is not limited to ENPs only, but extended to the exposure to process-generated NPs as well.     

Excitation of high energy levels under laser exposure of suspensions of nanoparticles in liquids

Laser exposure of suspensions of nanoparticles in liquids leads to excitation of high energy levels in both liquid and nanoparticle material. The emission spectrum of the colloidal solution under exposure of a suspension metallic nanoparticles in water to radiation of a Nd:YAG laser of a picosecond range of pulse duration is discussed. Excitation of nuclear energy levels and neutron release is experimentally studied on the model system of transmutation of Hg into Au that occurs under exposure of Hg nanodrops suspended in D₂O. The proposed mechanism involves: (i) emission of X-ray photons by Hg nanoparticles upon laser exposure, leading to neutron release from D₂O, (ii) initiation of Hg → Au transmutation by the capture of neutrons. The effect of transmutation is more pronounced using ¹⁹⁶Hg isotope instead of Hg of natural isotope composition. The influence of laser pulse duration on the degree of transmutation (from fs through ns range) is discussed.     

An examination of silver nanoparticles in socks using screening-level life cycle assessment

Screening-level life cycle assessment (LCA) can provide a quick tool to identify the life cycle hot spots and focus research efforts to help to minimize the burdens of a technology while maximizing its benefits. The use of nanoscale silver in consumer products has exploded in popularity. Although its use is considered beneficial because of antimicrobial effects, some attention must be given to the potential environmental impacts it could impart on the life cycle of these nanoproducts as production demands escalate. This work examines the environmental impact of including silver nanoparticles in commercially available socks using screening-level LCA. Initial results suggest washing during the use phase contributes substantially more than the manufacturing phase to the product life cycle impacts. Comparison of nanoparticles prepared by either chemical reduction, liquid flame spray (LFS), or plasma arc demonstrate how the type of manufacturing process used for the nanoscale silver can change the resulting life cycle impact of the sock product. The magnitude of this impact will depend on the type of process used to manufacture the nanoscale silver, with LFS having the most impact because of the need for large quantities of hydrogen and oxygen. Although the increased impacts for a single nanoproduct may be relatively small, the added environmental load can actually be a significant quantity when considered at the regional or global production level.     

Chronic exposure to zinc oxide nanoparticles increases ischemic-reperfusion injuries in isolated rat hearts

The use of zinc oxide nanoparticles (ZnO NPs) in numerous products is increasing, although possible negative implications of their long-term consumption are not known yet. Our aim was to evaluate the chronic, 6-week oral exposure to two different concentrations of ZnO NPs on isolated rat hearts exposed to ischemic-reperfusion injury and on small intestine morphology. Wistar rats of both sexes (n = 18) were randomly divided into three groups: (1) 4 mg/kg ZnO NPs, (2) 40 mg/kg ZnO NPs, and (3) control. After 6 weeks of treatment, the hearts were isolated, the left ventricular pressure (LVP), the coronary flow (CF), the duration of arrhythmias and the lactate dehydrogenase release rate (LDH) were measured. A histological investigation of the small intestine was performed. Chronic exposure to ZnO NPs acted cardiotoxic dose-dependently. ZnO NPs in dosage 40 mg/kg maximally decreased LVP (3.3-fold) and CF (2.5-fold) and increased the duration of ventricular tachycardia (all P < 0.01) compared to control, whereas ZnO NPs in dosage 4 mg/kg acted less cardiotoxic. Goblet cells in the small intestine epithelium of rats, treated with 40 mg ZnO NPs/kg, were enlarged, swollen and numerous, the intestinal epithelium width was increased. Unexpectedly, ZnO NPs in both dosages significantly decreased LDH. A 6-week oral exposure to ZnO NPs dose-dependently increased heart injuries and caused irritation of the intestinal mucosa. A prolonged exposure to ZnO NPs might cause functional damage to the heart even with exposures to the recommended daily doses, which should be tested in future studies.     

The time-dependent cellular response mechanism upon exposure to zinc oxide nanoparticles

Zinc oxide nanoparticle is one of the nanomaterials people engaged most in their life and its health effect has been taken into concern. In this work, A549 cell line was used as cell model, and the cytotoxicity of zinc oxide nanoparticles was revealed to be concentration-dependent. Through the measurement of cellular proteome, much more differentially expressed proteins were observed after the cells being treated for 9 h than 24 h. Also, most of these proteins expressed in the pattern which showed a significant decrease after exposure to zinc oxide nanoparticles and then an increase at 24 h. Intracellular reactive oxygen species and glutathione determination indicated that high level of oxidative stress was presented in cell after treatment with zinc oxide nanoparticles for 9 h. It can be observed from western blot analysis that the expression of NF-κB p65, PNPase, and HSP90 rose significantly after 9 h of exposure. Thus, a deduction was reached that toxicity of nanoparticles consists both of particle toxicity and ion toxicity, and a long-time treatment may conceal the toxicity induced by particles. The conclusion we made highlighted the importance of exposure time in the study of nanoparticle toxicity and would provide a new perspective for studying toxicity mechanism of nanoparticles.     

Relevance of aerosol dynamics and dustiness for personal exposure to manufactured nanoparticles

Production and handling of manufactured nanoparticles (MNP) may result in unwanted worker exposure. The size distribution and structure of MNP in the breathing zone of workers will differ from the primary MNP produced. Homogeneous coagulation, scavenging by background aerosols, and surface deposition losses are determinants of this change during transport from source to the breathing zone, and to a degree depending on the relative time scale of these processes. Modeling and experimental studies suggest that in MNP production scenarios, workers are most likely exposed to MNP agglomerates or MNP attached to other particles. Surfaces can become contaminated by MNP, which constitute potential secondary sources of airborne MNP-containing particles. Dustiness testing can provide insight into the state of agglomeration of particles released during handling of bulk MNP powder. Test results, supported by field data, suggest that the particles released from powder handling occur in distinct size modes and that the smallest mode can be expected to have a geometric mean diameter >100 nm. The dominating presence of MNP agglomerates or MNP attached to background particles in the air during production and use of MNP implies that size alone cannot, in general, be used to demonstrate presence or absence of MNP in the breathing zone of workers. The entire respirable size fraction should be assessed for risk from inhalation exposure to MNP.     

Emission measurement and safety assessment for the production process of silicon nanoparticles in a pilot-scale facility

Emission into the workplace was measured for the production process of silicon nanoparticles in a pilot-scale facility at the Institute of Energy and Environmental Technology e.V. (IUTA). The silicon nanoparticles were produced in a hot-wall reactor and consisted of primary particles around 60 nm in diameter. We employed real-time aerosol instruments to measure particle number and lung-deposited surface area concentrations and size distribution; airborne particles were also collected for off-line electron microscopic analysis. Emission of silicon nanoparticles was not detected during the processes of synthesis, collection, and bagging. This was attributed to the completely closed production system and other safety measures against particle release which will be discussed briefly. Emission of silicon nanoparticles significantly above the detection limit was only observed during the cleaning process when the production system was open and manually cleaned. The majority of the detected particles was in the size range of 100–400 nm and were silicon nanoparticle agglomerates first deposited in the tubing then re-suspended during the cleaning process. Appropriate personal protection equipment is recommended for safety protection of the workers during cleaning.     

Accelerated alpha decay under laser exposure of metallic nanoparticles in aqueous solutions of uranium salt

The recent experimental results on the acceleration of alpha decay under laser exposure of metallic nanoparticles in aqueous solutions (D₂O or H₂O) of uranium salt UO₂Cl₂ are reviewed. It is demonstrated that the rate of the alpha decay of uranium branching depends on the laser wavelength and laser peak power both under exposure of the solution of uranium salt in colloidal solutions of metallic nanoparticles and under laser ablation of a bulk target in an aqueous solution. Tuning the laser wavelength to the plasmon resonance allows observation of large deviations of the contents of radio-nuclides of ²³⁸U branching from their equilibrium values. The effect of laser exposure is characterized by high isotopic selectivity towards the decay of different nuclides. Possible mechanisms of the laser-induced alpha decay of uranium isotopes and their potential applications are discussed.     

Implications of exposure to dextran-coated and uncoated iron oxide nanoparticles to developmental toxicity in zebrafish

Iron oxide nanoparticles (IONPS) have been widely investigated as a platform for a new class of multifunctional theranostic agents. They are considered biocompatible, and some formulations are already available in the market for clinical use. However, contradictory results regarding toxicity of IONPs raise a concern about the potential harm of these nanoparticles. Changes in the nanoparticle (NP) physicochemical properties or exposure media can significantly alter their behavior and, as a consequence, their toxic effects. Here, behavior and two-step RT-qPCR were employed to access the potential toxicological effects of dextran-coated IONPs (CLIO-NH2) and uncoated IONPs (UCIO) in zebrafish larvae. Animals were exposed for 7 days to NP solutions ranging from 0.1–100 μg/mL directly mixed to the system water. UCIO showed high decantation and instability in solution, altering zebrafish mortality but showing no alterations in behavior and molecular expression analysis. CLIO-NH2 exposure did not cause significant mortality or changes in hatching rate of zebrafish larvae; however, behavior and expression profiles of the group exposed to lower concentration (1 μg/mL) presented a tendency to decrease the locomotor activity and apoptotic pathway activation.     

Exposure assessment of process by-product nanoparticles released during the preventive maintenance of semiconductor fabrication facilities

This study characterized the process by-product particles (mostly nanoparticles) released during the preventive maintenance of semiconductor fabrication facilities, such as chemical mechanical planarization (CMP), plasma-enhanced chemical vapor deposition (PECVD), and ion implantation. Manual sampling and real-time measurements with direct reading instruments were conducted to assess the exposure levels of nanoparticles and their physical and chemical properties. Significant amount of nanoparticles were observed in the breathing zone of the workers during the maintenance of the PECVD and ion implanters with the peak number concentrations as high as 6,470,000 and 65,444 #/cm³, respectively, indicating that the deposited residual chemicals in the reaction chambers were released as airborne nanoparticles by the maintenance activities. In contrast, nanoparticles released during the maintenance of the local scrubber, CMP, and replacing CMP slurry drums were insignificant. Causes of the particle release were discussed and suggestions were made to mitigate the nanoparticle release and reduce the exposure levels.