Use of Nanoparticles in Swiss Industry: A Targeted Survey

This targeted phone survey shows the patterns of nanoparticle usage in Swiss ... A large number of applications using manufactured nanoparticles of le...
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Policy Analysis Use of Nanoparticles in Swiss Industry: A Targeted Survey KASPAR SCHMID AND MICHAEL RIEDIKER* Institute for Work and Health, Universities of Lausanne and Geneva Lausanne, Switzerland

Received July 23, 2007. Revised manuscript received January 3, 2008. Accepted January 7, 2008.

A large number of applications using manufactured nanoparticles of less than 100 nm are currently being introduced into industrial processes. There is an urgent need to evaluate the risks of these novel particles to ensure their safe production, handling, use, and disposal. However, today we lack even rudimentary knowledge about type and quantity of industrially used manufactured nanoparticles and the level of exposure in Swiss industry. The goal of this study was to evaluate the use of nanoparticles, the currently implemented safety measures, and the number of potentially exposed workers in all types of industry. To evaluate this, a targeted telephone survey was conducted among health and safety representatives from 197 Swiss companies. The survey showed that nanoparticles are already used in many industrial sectors; not only in companies in the new field of nanotechnology, but also in more traditional sectors, such as paints. Forty-three companies declared to use or produce nanoparticles, and 11 imported and traded with prepackaged goods that contain nanoparticles. The following nanoparticles were found to be used in considerable quantities (>1000 kg/year per company): Ag, Al-Ox, Fe-Ox, SiO2, TiO2, and ZnO. The median reported quantity of handled nanoparticles was 100 kg/year. The production of cosmetics, food, paints, powders, and the treatment of surfaces used the largest quantities of these nanoparticles. Generally, the safety measures were found to be higher in powder-based than in liquid-based applications. However, the respondents had many open questions about best practices, which points to the need for rapid development of guidelines and protection strategies.

Introduction Nanoparticles are generally defined as particles smaller than 100 nm in at least two dimensions (1–4). These materials are increasingly being used for commercial purposes such as fillers, opacifiers, catalysts, semiconductors, cosmetics, microelectronics, drug carriers, etc (5). The chemical, physical, and biological properties of materials in nanoscale are often different from the properties of the same materials in larger scale (2). The same properties that make nanoparticles (NPs) so attractive for development in nanomedicine and for specific industrial processes could also prove deleterious when NPs interact with cells (6). Nanosized particles are suspected to enter the human cells more easily than microsized particles (7), and ambient * Corresponding author phone: +41-21-3147453; fax: +41-213147430; e-mail: [email protected]. 10.1021/es071818o CCC: $40.75

Published on Web 02/26/2008

 2008 American Chemical Society

air-pollution particles smaller than 2.5 µm (PM2.5) have already been shown to be harmful to human health (8–10). The surface-to-volume ratio of nanoparticles is large, which may explain their high biological activity. Several types of nanoparticles have been shown to have toxic effects (11, 12). The development of mass-production of products and materials containing nanoparticles has begun despite limited knowledge of the risks associated with exposure to and release into the environment of nanoparticles (13, 14). The potential long-term impact on workers’ health and the environment needs to be studied (15–17). Even at relatively low mass, nanoparticles represent important numbers and surface concentrations, which might pose a hazard if released in the air. Therefore, attention will have to be paid especially to up-scaled productions. Thus, evaluating the safety of NPs should be of highest priority given their expected worldwide distribution for industrial applications and the likelihood of human exposure, either directly or through release into the environment (air, water, soil) (6, 18). The potential for effects on ecosystems will depend not only on nanoparticle characteristics but also on the amount of nanoparticles emitted by industry. A better knowledge of mass flows, storage quantities, application types, and protective measures will provide valuable information for the development of dispersion models and worst-case scenarios. Occupational exposure to nanoparticles is not a new phenomenon. In the past, heat-associated processes such as fuel-combustion or welding produced nanosized particles (ultrafine particles (1)); the new nanoparticles, however, are produced intentionally, and some producers even develop nanoparticles with low tendency to agglomerate. Currently, there are no standardized safety guidelines describing safe and responsible handling and application of nanoparticles. The International Organization for Standardization (ISO) started with the creation of nanotechnology standard in 2005 (TC 229, Nanotechnologies). The EU Commission asked member states to make inventories of use and exposures of nanosciences and nanotechnologies applications, in particular, manufactured nanoscale entities (15). There are currently no specific reporting requirements for nanoparticles in Switzerland, nor in other countries. As a consequence, we have limited knowledge of where what types of nanoparticles are being used the production sector. Industry, ISO, governmental, and nongovernmental organizations call for guidelines for the safe and responsible production, handling, and disposal of nanoparticles. Currently, the scientific basis for recommendations about the safe handling of nanoparticles is insufficient, and recommendations are mostly based on analogy with other particles. More information about exposure resulting from the various handling methods and the effectiveness of different protection measures is needed to develop evidence-based guidelines for the industrial use of nanoparticles. However, very few studies so far have evaluated the industrial use of nanoparticles. These studies were literature reviews (3) or collected data selectively from nanoparticle producing companies (14, 19). Objectives. The principal objective of this study was to evaluate the prevalence and level of nanoparticle use in the Swiss industry as well as the potential for exposure of the Swiss working population to engineered nanoparticles. Occupational cohorts are likely to have earlier and higher exposures than the general population, which makes them a particularly suitable population for risk-assessments. Studies on toxicological effects need to be combined with VOL. 42, NO. 7, 2008 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

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TABLE 1. Types of Nanoparticles, Quantity of Used Nanomaterials, and Total Number of Employees in the Companies Identified by the Targeted Telephone Interviewa No. by company size (number of employees) total No. of companies

micro (1 µm. Protection Measures. Table 3 shows the protection measures used by the interviewed companies. Most of the companies working with nanopowder used several types of protection-measures and many of those working with nanoliquids used only personal protective equipment. The following protection types were found: separation (the application of closed environments like closed machines or separated rooms); airflow (the use of a fume cupboard or a suction device); filter (the use of some form of air filtering system); and personal protective equipment (the use of masks, gloves, eyeglasses, etc.). Few other protection types were indicated. All companies with nanoparticle-powders used protection measures, most of them used several types of protection. Seven of the 22 companies with liquid-only applications provided only respiratory personal protective equipment (not detailed in Table 3). Two companies with a liquid and a solid application type did not use any protection at all. The sum of the lines does not equal the number of the identified companies because several companies applied more than one protection type. The application of nanoparticles in a liquid or powder form was equally distributed between the different sizes of companies. Solid applications of nanoparticles were found in two companies, both with more than 250 employees. Only 34 companies provided the information about protection means. The number of companies per size-group (Table 4) was sometimes very small, but there was a tendency for most increased number of protection measures in the small to middle sized companies. Chart 2 shows how often the persons in charge inform themselves about risks of nanoparticles. “Rarely” and “often” were the predominant answers. Chart 2 also shows the highest level of management being involved in the topic of nanoparticles. In many cases the respondents were unsure about VOL. 42, NO. 7, 2008 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

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CHART 2. (A) Self-information frequency of the respondents about the topic “nanoparticles and EHS” (n=43), (B) level of the highest-ranked management taking care of this topic (n=43)

this point, and one company had no designated person in charge of the topic. The top management of very small and very big companies tended to be more implicated in the topic nanoparticles and EHS than the one of medium sized companies.

Discussion This is the first survey to investigate the occurrence and handling of nanoparticles in Swiss industry. It investigated a wide range of industrial branches, not only companies in the field of nanotechnology. The study gives a good impression of types and quantities of nanoparticles used in the investigated Swiss industrial sectors. In this targeted survey, 43 of the 197 contacted companies reported an application with manipulation or production of nanoparticles, and 11 reported to import and trade with prepackaged goods that contain nanoparticles. Additional information was obtained about who was using the nanoparticles (in terms of company-size), how they were used (in terms of protection measures), and in what type of application they were used (in terms of physical condition: powder/liquid or solid). The reported quantities of used nanoparticles ranged from a few grams to up-scaled productions with hundreds of tons. The majority of nanoparticle applications were on a small production scale of less than 100 kg/year. An up-scaled production with more than a few tons per year was only found for nanoparticles of Ag, Al-Ox, Fe-Ox, SiO2, TiO2, ZnO, and carbon black. The reported amount of nanoparticles is associated with some uncertainties, as it was sometimes very difficult for the responding person to estimate the quantities they used, and the reported information was not verified by a third party. Another limitation of this study is that the reported proportion of companies with and without nanoparticles is likely to be not representative; some sectors may be missing (this is a survey targeted on nanoparticle applications described in literature), and some sectors may be under- or overestimated due to the selection of only 10–15 companies per sector. Nanoparticle applications were identified in the fields of cleaning products, cosmetics, food and food- packaging, milling machines, paints, paper, pharmaceutical products, plastics, powder-production, printing and packaging, sensors/ microelectronics, surfaces, coating, textiles, watches/optics. According to literature, the primary use of carbon black is in rubber products, mainly tires and other automotive products, but also in many other rubber products such as hoses, gaskets, and coated fabrics. Much smaller amounts of carbon black are used in inks and paints, in plastics, and in the manufacture of dry-cell batteries (23). The carbon black row in Table 2 is probably incomplete; only late in the 2258

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telephone survey it became clear that most of the security managers, because it has been used for years, did not consider carbon black as nanoparticles. Most companies were middle-sized with 50-250 employees. The top management of small and large companies tended to be more involved in the topic of nanoparticles and EHS than those of middle-sized companies. Although a flatter hierarchy could explain this fact in small companies, it remains unclear for big companies. Most of the protection measures seemed to have been conceived to be adapted to the perceived risk of the application type. For liquid or solid applications, most persons in charge assumed that nanoparticles would not become airborne. Consequently, they did not apply airways protection measures. Almost all contacted safety managers answered our questions about nanoparticle applications and protection measures. Many of them gave detailed information about their EHS approach even though the predominant message was “I am very interested in the topic of nanoparticles and EHS, but I don’t know enough”. The European Commission recently called for the development of detailed inventories about industrial applications and exposure to nanoparticles (15). The present study provides information that will be helpful for this task. The uncertainties manifested in the responses of the interviewed safety managers points to the need of evaluating existing protection strategies and to develop guidelines about health and safety practices in occupational settings relevant to nanotechnologies. Recently, several research programs and projects started in Europe to assess the occupational and environmental risk of nanotechnology-based products and materials (e.g., Nanosafe, Impart, Nanotox, Nanoderm, Nanohealth, Nanocare, etc.). However, they did not yet publish data about emission and exposure, which could be used for evidence based risk assessment. There are only few studies about ecotoxicology, mainly C60 on fish models (e.g., refs (28) and (29)), very few studies about the mobility and behavior of nanoparticles in the environment (e.g., ref (18)), but none about an unintended or accidental release of nanoparticles into the environment (search in database of pubmed and sciencedirect: (industrial AND nanoparticl* AND (release OR accident)). The here presented data can help estimate the amounts of nanoparticles that can be released into the environment in a worst-case scenario. The ICON Review of Current Practices in the Nanotechnology Industry (32) was another attempt to evaluate current safety practices by a survey within the nanomaterials industry of mostly Asian and North American companies. The ICON survey was based on small enterprises (half of the companies

had less than 50 employees) and also a few big companies (with more than 1000 employees). The review followed a nonsystematic procedure for selecting the companies (mostly referrals). The amount of nanoparticles used by these companies was not given as weight-units, but in terms of “small”, “pilot”, and “full or commercial” scale; the interviewed company did that classification. From our experience, this can lead to a misclassification when comparing companies of different sizes: for example, whereas the one big company using carbon black in the amount of hundreds of tons per year described this process as a “small” production, it would be classified as a very large production in comparison with other Swiss industries. However, similar to our study, the ICON report described small-scale production to be predominant. In contradiction to the ICON report, this survey describes the most diverse protection types in the middle and small but not in the big companies. The difference might be one of different company culture in the concerning countries but also one of the methods of how to chose the companies. In the past, the Swiss government had a passive attitude with regards to this question and tended to be awaiting scientific results before taking any regulatory actions (30). However, at the present time the Swiss government shows more proactive interest in the field, by publishing a basis report (31), which was used for the definition of an Action Plan “Risk Assessment and Risk Management for Synthetic Nanomaterials 2006–2009”, and by supporting research projects such as this work. We show with this study that nanoparticles are already a reality in many industrial sectors in Switzerland and that some companies use already high quantities of a few types of nanoparticles. This study contributes to the development of evidence-based risk assessments and guidelines toward the responsible and safe development of nanotechnology based products and materials. The consequences of accidental release of such quantities need to be evaluated, and the continuous release from such production plants needs to be further investigated.

Acknowledgments We would like to acknowledge the contributions and the financial support of the Swiss Federal Offices for Public Health and the Environment (FOPH, FOEN), the State Secretariat for Economic Affairs (SECO), the Swiss National Accident Insurance Fund (SUVA), the French Agency for Occupational and Environmental Health Safety (AFSSET), and all the persons in charge in the interviewed companies for their kind responses.

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