Nanotechnology and Occupational Health

An overview of the special issue of the Journal of Nanoparticle Research on nanotechnology and occupational health is presented.

Past experience has shown that the successful introduction of a new technology requires careful attention to the interactions between the technology and society. These interactions are bi-directional: on the one hand, technology changes and challenges social patterns and, on the other hand, the governance structures and values of the society affect progress in developing the technology. Nanotechnology is likely to be particularly affected by these kinds of interactions because of its great promise and the unusually early public attention it has received. Moreover, it represents a new kind of experiment in packaging a rather wide range of fundamental research activities under a single “mission-like” umbrella. Although this gives it more impetus as a field, it sets a higher bar for showing successful applications early on and because it links disparate fields, regulatory regimes reasonable for one kind of nanotechnology development may be inappropriately extended to others. There are a number of lessons to be gleaned from experience with the introduction of other technologies, which offer guidance with respect to what pitfalls to avoid and what issues to be sensitive to as we move forward with the development of nanotechnology applications. The problems encountered by nuclear power point out the dangers of over-promising and the role the need for the technology plays in ameliorating fears of risk. The public reaction to biomedical engineering and biotechnology highlights, in addition, the cultural factors that come into play when technologies raise questions about what is “natural” and what is “foreign” and what conceptions are involved in defining “personhood”. In all cases, it has been clear that a main task for those introducing new technology is building public trust-in the safety of the technologies and the integrity of those introducing it. The advocates of nanotechnology have already shown that they are generally aware of the need to consider the public’s reaction, and they have taken the first steps to act on that awareness. We have to build on those beginnings, not limiting our considerations simply to issues of safety. If we do so well, we have the opportunity to develop a new paradigm for technology introduction, which will serve society well in the future.

Nanotechnology, the design and manipulation of materials at the atomic scale, may well revolutionize many of the ways our society manufactures products, produces energy, and treats diseases. New materials based on nanotechnology are already reaching the market in a wide variety of consumer products. Some of the observed properties of nanomaterials call into question the adequacy of current methods for determining hazard and exposure and for controlling resulting risks. Given the limitations of existing regulatory tools and policies, we believe two distinct kinds of initiatives are needed: first, a major increase in the federal investment in nanomaterial risk research; second, rapid development and implementation of voluntary standards of care pending development of adequate regulatory safeguards in the longer term. Several voluntary programs are currently at various stages of evolution, though the eventual outputs of each of these are still far from clear. Ultimately, effective regulatory safeguards are necessary to provide a level playing field for industry while adequately protecting human health and the environment. This paper reviews the existing toxicological literature on nanomaterials, outlines and analyzes the current regulatory framework, and provides our recommendations, as an environmental non-profit organization, for safe nanotechnology development.

Because of their small size, the specific surface areas of nanoparticulate materials (NP), described as particles having at least one dimension smaller than 100 nm, can be large compared with micrometer-sized respirable particles. This high specific surface area or nanostructural surface properties may affect NP toxicity in comparison with micrometer-sized respirable particles of the same overall composition. Respirable particles depositing on the deep lung surfaces of the respiratory bronchioles or alveoli will contact pulmonary surfactants in the surface hypophase. Diesel exhaust ultrafine particles and respirable silicate micrometer-sized insoluble particles can adsorb components of that surfactant onto the particle surfaces, conditioning the particles surfaces and affecting their in vitro expression of cytotoxicity or genotoxicity. Those effects can be particle surface composition-specific. Effects of particle surface conditioning by a primary component of phospholipid pulmonary surfactant, diacyl phosphatidyl choline, are reviewed for in vitro expression of genotoxicity by diesel exhaust particles and of cytotoxicity by respirable quartz and aluminosilicate kaolin clay particles. Those effects suggest methods and cautions for assaying and interpreting NP properties and biological activities.

Functional nanocrystals are widely considered as novel building blocks for nanostructured materials and devices. Numerous synthesis approaches have been proposed in the solid, liquid and gas phase. Among the gas phase approaches, low pressure nonthermal plasmas offer some unique and beneficial features. Particles acquire a unipolar charge which reduces or eliminates agglomeration; particles can be electrostatically confined in a reactor based on their charge; strongly exothermic reactions at the particle surface heat particles to temperatures that significantly exceed the gas temperature and facilitate the formation of high quality crystals. This paper discusses two examples for the use of low pressure nonthermal plasmas. The first example is that of a constricted capacitive plasma for the formation of highly monodisperse, cubic-shaped silicon nanocrystals with an average size of 35 nm. The growth process of the particles is discussed. The silicon nanocubes have successfully been used as building blocks for nanoparticle-based transistors. The second example focuses on the synthesis of photoluminescent silicon crystals in the 3–6 nm size range. The synthesis approach described has enabled the synthesis of macroscopic quantities of quantum dots, with mass yields of several mg/hour. Quantum yields for photoluminescence as high as 67% have been achieved.

The risk of nanoparticles by inhalation for human health is still being debated but some evidences of risk on specific properties of particles <100 nm diameter exist. One of the nanoparticle parameters discussed by toxicologists is their surface area concentration as a relevant property for e.g. causing inflammation. Concentrations of these small particles (⊃ <100 nm) are currently not measured, since the mass concentrations of these small particles are normally low despite large surface area concentrations. Airborne particles will always be polydisperse and show a size distribution. Size is normally described by an equivalent diameter to include deviations in properties from ideal spherical particles. Here only nanoparticles below a certain size to be defined are of interest. Total concentration measures are determined by integration over the size range of interest. The ideal instrument should measure the particles according to the size weighting of the wanted quantity. Besides for the geometric surface area the wanted response function can be derived for the lung deposited surface area in the alveolar region. This can be obtained by weighting the geometric surface area as a function of particle size with the deposition efficiency for the alveolar region for e.g. a reference worker for work place exposure determination. The investigation of the performance of an Electrical Aerosol Detector (EAD) for nearly spherical particles showed that its response function is close to the lung deposited surface areas in different regions of the human respiratory system. By changing the ion trap voltage an even better agreement has been achieved. By determining the size dependent response of the instrument as a function of ion trap voltage the operating parameters can be optimized to give the smallest error possible. Since the concept of the instrument is based on spherical particles and idealized lung deposition curves have been used, in all other cases errors will occur, which still have to be defined. A method is now available which allows in principle the determination of the total deposited surface area in different regions of the lung in real time. It can easily be changed from one deposited region to another by varying the ion trap voltage. It has the potential to become a routine measurement technique for area measurements and personal control in e.g. work place environments.

TSI Nanoparticle Surface Area Monitor (NSAM) Model 3550 has been developed to measure the nanoparticle surface area deposited in different regions of the human lung. It makes use of an adjustable ion trap voltage to match the total surface area of particles, which are below 100 nm, deposited in tracheobronchial (TB) or alveolar (A) regions of the human lung. In this paper, calibration factors of NSAM were experimentally determined for particles of different materials. Tests were performed using monodisperse (Ag agglomerates and NaCl, 7–100 nm) and polydisperse particles (Ag agglomerates, number count mean diameter below 50 nm). Experimental data show that the currents in NSAM have a linear relation with a function of the total deposited nanoparticle surface area for the different compartments of the lung. No significant dependency of the calibration factors on particle materials and morphology was observed. Monodisperse nanoparticles in the size range where the response function is in the desirable range can be used for calibration. Calibration factors of monodisperse and polydisperse Ag particle agglomerates are in good agreement with each other, which indicates that polydisperse nanoparticles can be used to determine calibration factors. Using a CFD computer code (Fluent) numerical simulations of fluid flow and particle trajectories inside NSAM were performed to estimate response function of NSAM for different ion trap voltages. The numerical simulation results agreed well with experimental results.

In this study, the axial flow cyclone used in Tsai et al. (2004) was further tested for the collection efficiency of both solid (NaCl) and liquid (OA, oleic acid) nanoparticles. The results showed that the smallest cutoff aerodynamic diameters achieved for OA and NaCl nanoparticles were 21.7 nm (cyclone inlet pressure: 4.3 Torr, flow rate: 0.351 slpm) and 21.2 nm (5.4 Torr, 0.454 slpm), respectively. The collection efficiencies for NaCl and OA particles were close to each other for the aerodynamic diameter ranging from 25 to 180 nm indicating there was almost no solid particle bounce in the cyclone. The 3-D numerical simulation was conducted to calculate the flow field in the cyclone and the flow was found to be nearly paraboloid. Numerical simulation of the particle collection efficiency based on the paraboloid flow assumption showed that the collection efficiency was in good agreement with the experimental data with less than 15% of error. A semi-empirical equation for predicting the cutoff aerodynamic diameter at different inlet pressures and flow rates was also obtained. The semi-empirical equation is able to predict the cutoff aerodynamic diameter accurately within 9% of error. From the empirical cutoff aerodynamic diameter, a semi-empirical square root of the cutoff Stokes number, √St ₅₀ ^* , was calculated and found to be a constant value of 0.241. This value is useful to the design of the cyclone operating in vacuum to remove nanoparticles.

As-produced single-walled carbon nanotube (SWCNT) material is a complex matrix of carbon nanotubes, bundles of nanotubes (nanoropes), non-tubular carbon and metal catalyst nanoparticles. The pulmonary toxicity of material released during manufacture and handling will depend on the partitioning and arrangement of these components within airborne particles. To probe the physicochemical structure of airborne SWCNT aggregates, a new technique was developed and applied to aerosolized as-produced material. Differential Mobility Analysis-classified aggregates were analyzed using an Aerosol Particle Mass Monitor, and a structural parameter Γ (proportional to the square of particle mobility diameter, divided by APM voltage) derived. Using information on the constituent components of the SWCNT, modal values of Γ were estimated for specific particle compositions and structures, and compared against measured values. Measured modal values of Γ for 150 nm mobility diameter aggregates suggested they were primarily composed of non-tubular carbon from one batch of material, and thin nanoropes from a second batch of material — these findings were confirmed using Transmission Electron Microscopy. Measured modal values of Γ for 31 nm mobility diameter aggregates indicated that they were comprised predominantly of thin carbon nanoropes with associated nanometer-diameter metal catalyst particles; there was no indication that either catalyst particles or non-tubular carbon particles were being preferentially released into the air. These results indicate that the physicochemistry of aerosol particles released while handling as-produced SWCNT may vary significantly by particle size and production batch, and that evaluations of potential health hazards need to account for this.

Two different air filter test methodologies are discussed and compared for challenges in the nano-sized particle range of 10–400 nm. Included in the discussion are test procedure development, factors affecting variability and comparisons between results from the tests. One test system which gives a discrete penetration for a given particle size is the TSI 8160 Automated Filter tester (updated and commercially available now as the TSI 3160) manufactured by the TSI, Inc., Shoreview, MN. Another filter test system was developed utilizing a Scanning Mobility Particle Sizer (SMPS) to sample the particle size distributions downstream and upstream of an air filter to obtain a continuous percent filter penetration versus particle size curve. Filtration test results are shown for fiberglass filter paper of intermediate filtration efficiency. Test variables affecting the results of the TSI 8160 for NaCl and dioctyl phthalate (DOP) particles are discussed, including condensation particle counter stability and the sizing of the selected particle challenges. Filter testing using a TSI 3936 SMPS sampling upstream and downstream of a filter is also shown with a discussion of test variables and the need for proper SMPS volume purging and filter penetration correction procedure. For both tests, the penetration versus particle size curves for the filter media studied follow the theoretical Brownian capture model of decreasing penetration with decreasing particle diameter down to 10 nm with no deviation. From these findings, the authors can say with reasonable confidence that there is no evidence of particle thermal rebound in the size range.

The goal of this study is to model the data from the experiments of nanoparticle filtration performed at the Particle Technology Lab, University of Minnesota and at the 3M Company. Comparison shows that the experimental data for filter efficiency are bounded by the values computed from theoretical expressions which do not consider thermal rebound. Therefore thermal rebound in the tested filter media is not detected down to 3 nm particles in the present analysis. The efficiency measured experimentally is in good agreement with the theoretical expression by Stechkina (1966, Dokl. Acad. Nauk SSSR 167, 1327) when the Pectlet number Pe is larger than 100; it agrees well with the theoretical expression by Kirsch and Stechkina (1978, Fundamentals of Aerosol Science. Wiley, New York) when Pe is of the order of unit. We develop an empirical power law model for the efficiency depending on the Peclet number, which leads to satisfactory agreement with experimental results.

In this study, nanoparticle penetration was measured with a wide range of filter media using silver nanoparticles from 3 nm to 20 nm at three different face velocities in order to define nanoparticle filtration characteristics of commercial fibrous filter media. The silver particles were generated by heating a pure silver powder source via an electric furnace with a temperature of 870°C, which was found to be the optimal temperature for generating an adequate amount of silver nanoparticles for the size range specified above. After size classification using a nano-DMA, the particle counts were measured by an Ultrafine Condensation Particle Counter (UCPC) both upstream and downstream of the test filter to determine the nanoparticle penetration for each specific particle size. Particle sampling time continued long enough to detect more than 10⁵ counts at the upstream and 10 counts at the downstream sampling point so that 99.99% efficiency can be detected with the high efficiency filter. The results show a very high uniformity with small error bars for all filter media tested in this study. The particle penetration decreases continuously down to 3 nm as expected from the classical filtration theory, and together with a companion modeling paper by Wang et al. in this same issue, we found no significant evidence of nanoparticle thermal rebound down to 3 nm.

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.

Uncertainties in conventional quantitative risk assessment typically relate to values of parameters in risk models. For many environmental contaminants, there is a lack of sufficient information about multiple components of the risk assessment framework. In such cases, the use of default assumptions and extrapolations to fill in the data gaps is a common practice. Nanoparticle risks, however, pose a new form of risk assessment challenge. Besides a lack of data, there is deep scientific uncertainty regarding every aspect of the risk assessment framework: (a) particle characteristics that may affect toxicity; (b) their fate and transport through the environment; (c) the routes of exposure and the metrics by which exposure ought to be measured; (d) the mechanisms of translocation to different parts of the body; and (e) the mechanisms of toxicity and disease. In each of these areas, there are multiple and competing models and hypotheses. These are not merely parametric uncertainties but uncertainties about the choice of the causal mechanisms themselves and the proper model variables to be used, i.e., structural uncertainties. While these uncertainties exist for PM2.5 as well, risk assessment for PM2.5 has avoided dealing with these issues because of a plethora of epidemiological studies. However, such studies don’t exist for the case of nanoparticles. Even if such studies are done in the future, they will be very specific to a particular type of engineered nanoparticle and not generalizable to other nanoparticles. Therefore, risk assessment for nanoparticles will have to deal with the various uncertainties that were avoided in the case of PM2.5. Consequently, uncertainties in estimating risks due to nanoparticle exposures may be characterized as ‘extreme’. This paper proposes a methodology by which risk analysts can cope with such extreme uncertainty. One way to make these problems analytically tractable is to use expert judgment approaches to study the degree of consensus and/or disagreement between experts on different parts of the exposure-response paradigm. This can be done by eliciting judgments from a wide range of experts on different parts of the risk causal chain. We also use examples to illustrate how studying expert consensus/disagreement helps in research prioritization and budget allocation exercises. The expert elicitation can be repeated over the course of several years, over which time, the state of scientific knowledge will also improve and uncertainties may possibly reduce. Results from expert the elicitation exercise can be used by risk managers or managers of funding agencies as a tool for research prioritization.

In this study, nanoparticle emission of TiO₂ nanopowder coated on different substrates including wood, polymer, and tile, was evaluated in a simulation box and measured with a Scanning Mobility Particle Sizer (SMPS) for the first time. The coating process for the substrate followed the instructions given by the supply company. In the simulation box, UV light, a fan, and a rubber knife were used to simulate the sun light, wind, and human contacting conditions. Among the three selected substrates, tile coated with TiO₂ nanopowder was found to have the highest particle emission (22 #/cm³ at 55 nm) due to nanopowder separation during the simulation process. The UV light was shown to increase the release of particle below 200 nm from TiO₂ nanopowder coating materials. The results show that, under the conditions of UV lamps, a fan and scraping motion, particle number concentration or average emission rate decreases significantly after 60 and 90 min for TiO₂/polymer and TiO₂/wood, respectively. However, the emission rate continued to increase after 2 h of testing for TiO₂/tile. It is suggested that nanoparticle emission evaluation is necessary for products with nanopowder coating.

Challenges and opportunities for appropriate oversight of nanotechnology applied to or derived from biological systems (nano-bio interface) were discussed in a public workshop and dialog hosted by the Center for Science, Technology, and Public Policy of the University of Minnesota on September 15, 2005. This paper discusses the themes that emerged from the workshop, including the importance of analyzing potential gaps in current regulatory systems; deciding upon the general approach taken toward regulation; employing non-regulatory mechanisms for governance; making risk and other studies transparent and available to the public; bolstering mechanisms for public participation in risk analysis; creating more opportunities for meaningful discussion of the social and ethical dimensions of the nano-bio interface; increasing funds for implications and problem-solving research in this area; and having independent and reliable sources for communication. The workshop was successful in identifying ways of moving forward responsibly so that ultimately nanotechnology and its products can succeed in developers’, researchers’, regulators’, and the public’s eyes.