Issue Date: May 1, 2006
Chance Of A Lifetime
On March 31, aerosol household sprays that may or may not have contained nanoparticles were pulled off the market in Germany. That unprecedented action was brought about after nearly 100 reports of respiratory problems among people using the Magic Nano sprays. In addition to a propellant, the sprays contain a silicate sol-gel to make glass and ceramic surfaces water- and dirt-repellant, according to the product's distributor, Kleinmann GmbH.
The cause of the respiratory problems—even whether any nanomaterials were in the aerosol spray to reach the lungs of those affected—remains unclear. The products have been "tested extensively over prolonged periods and by various agencies," and no associated contraindications have been found, Kleinmann International Sales Manager Bernd Zimmermann told C&EN. The company immediately recalled the product and cooperated with authorities to understand and rectify the problem. "We have taken all possible steps to inform the public about any possible problems," he added.
Nanoethics Group, which calls itself a nonpartisan think tank, described the recall as a "wake-up call to regulators, industry, and the public that nanotechnology's risks are not just theoretical, but all too real." Environmental activist ETC Group renewed its call for a ban on nanotech research and products. Likewise, Greenpeace also thinks a moratorium on the environmental release of nanoparticles is warranted until they are found to be safe.
The incident embodies all the challenges that companies, regulators, consumers, and others are facing as products based on engineered nanomaterials emerge. Kleinmann, which takes pride in its health and safety record, trusted its nanomaterial and aerosol suppliers to provide test data that, as of mid-April, it did not have to give to authorities. At the same time, regulatory and health authorities essentially had their hands tied with too little data or sway to allow them to act.
Nanoscale particles are nothing new. Not only do they occur naturally, but they are also formed in combustion processes and have been manufactured for decades. What's changed is the capability to control production and make engineered particles of very specific sizes and shapes. These nanomaterials are now appearing in marketed applications. The Woodrow Wilson Center's Project on Emerging Nanotechnologies lists more than 200 nanolabeled consumer products in its database.
Nevertheless, engineered nanoparticles are an embryonic commercial endeavor. The science and technology base, including toxicological studies, is still emerging. Manufacturing methods are just being scaled up. Regulators have not figured out how to oversee production and use. Consumer perceptions are being formed as they see products labeled as "nano" that may not even contain nanomaterials.
Input from nongovernmental organizations (NGOs) is joining that from regulators, trade associations, and research consortia in discussions about the risks and benefits of nanomaterials (C&EN, Dec. 5, 2005, page 46). Lawyers who used to speak about patent issues now offer advice on regulatory compliance, worker protection, and product liability. Major insurers, such as Swiss Re and Allianz, have published analyses of the economic opportunities, potential risks, and insurability of nanotechnology.
Despite the range of views, there's actually some agreement on a few issues: namely, that nanotechnology may offer gains in the energy, medical, and environmental fields; its impact will be large; and nanoparticles present a large exposure risk. Also, because there's little data with which to identify, assess, and manage environmental, health, and safety (EHS) risks, most experts agree that more resources need to be applied to these issues and that industry and government must be proactive in addressing them.
"There has been a lot of engagement and a lot of dialogue from a very broad cross section of stakeholders, and that is very positive," says Terry Medley, global director of corporate regulatory affairs at DuPont. "And it is happening early and globally as well." In June 2005, DuPont Chairman Charles O. Holliday Jr. and Environmental Defense President Fred Krupp coauthored an opinion piece in the Wall Street Journal expressing their commitment to research, action, and engagement and calling on others to do the same.
Since then, DuPont and Environmental Defense have been developing a framework, or systematic process, to evaluate all key factors for the responsible development, production, use, and disposal of nanomaterials. "We are trying to take a life-cycle view of the materials and applications," explains Scott Walsh, Environmental Defense's project manager for corporate partnerships.
"We are about to go out publicly to get feedback on the overall architecture of this framework," he continues. "We want to see how well it makes sense for others' particular materials and applications, how they might be able to incorporate this overall approach, and what their thoughts are to help guide our work on filling in the details."
Environmental Defense's interest in nanotechnology was sparked by the possible environmental benefits. "But once we started learning more, we started seeing the potential for environmental and health risks," he says. "And before we start pushing the technology, we want to make sure we get a handle on how to manage it safely."
It's an opportunity to "get it right the first time," Walsh adds, and find the best approaches to achieve the promised benefits and avoid the downside. "There is a long list of examples where we, as a society, developed and adopted on a wide scale a technology without really identifying and understanding the potential risks," he says. This, he believes, has been very costly in terms of human health, environmental damage, cleanup, litigation, and even policy-making.
Environmental Defense and DuPont also participate in the International Council on Nanotechnology (ICON), which is housed within the Center for Biological & Environmental Nanotechnology (CBEN) at Rice University. ICON was created in late 2004 as a neutral, technically based group that works on assessing, communicating, and reducing EHS risks of nanotechnology while maximizing the technology's value. Its participants represent corporate, government, academic, and NGO interests.
"There were very few models for doing this in an emerging technology," points out Kristen Kulinowski, CBEN's executive director for education and public policy. Although most of ICON's funding is from industry, she says a balance among participants on the group's executive committee is "scrupulously maintained."
When CBEN was set up in 2001, the idea that there might be EHS issues needing attention was not popular in either academic or corporate circles, she notes. "That time is long past and now the focus has shifted to what should we do." The task, she says, is ensuring that the best scientific knowledge is injected into the decision-making process, finding out how to get that knowledge, filling research gaps, and then proceeding with good regulatory policy.
In the same vein, a coalition of companies, NGOs, and the NanoBusiness Alliance trade group have urged Congress to increase funding for nanotech EHS research. In 2006, $38.5 million, or just 3.7% of the National Nanotechnology Initiative's (NNI) more than $1 billion annual budget, targets such efforts. Another 4.0%, or $42.6 million, is to be spent on research on ethical, legal, and societal issues and education-related activities.
Within NNI, the federal multiagency nanotech R&D program, the chemical industry provides input via the Chemical Industry Consultative Board for Advancing Nanotechnology (ChI CBAN). Its working groups look at EHS issues and focus areas for research. CBAN stems from a partnership of NNI, the Council for Chemical Research, and the Chemical Industry Vision2020 Technology Partnership, which prepared a 2004 R&D road map for nanomaterials at the behest of NNI.
In late 2005, the Environmental Protection Agency produced a white paper that has recently undergone external peer review. It includes the agency's view of nanotech research needs and risk assessment issues. While views were mixed, William Kovacs, vice president for environment, technology, and regulatory affairs at the U.S. Chamber of Commerce, wrote that "failure to get regulatory policy correct could result in the loss of billions of dollars in profits and wasted R&D resources and undercut our ability to remain a technological leader."
Early this year, J. Clarence Davies, a senior adviser to the Project on Emerging Nanotechnologies, released a report commenting on the regulatory situation (C&EN, Jan. 30, page 34). He concluded that overseeing the development of nanotechnology and managing any potential negative effects would be difficult under current regulations, and he proposed that there should be new ones. Meanwhile, other parties, such as the American Chemistry Council (ACC), believe that creating new regulations or regulatory authorities isn't practical or necessary.
"The regulatory authorities are in place to broadly address any of the risks that might be identified," DuPont's Medley remarks, "but DuPont is committed to the regulations being assessed and amended as necessary."
Last year, Environmental Defense and ACC's nanotechnology panel crafted a joint statement of principles that could serve as the basis of a government program trying to assess the potential risks of nanomaterials. According to ACC, these principles helped shape discussions by EPA's National Pollution Prevention Technical Advisory Committee on a voluntary reporting program.
Walsh believes government should move quickly because products are already on the market. "But we are realists, and that's why we're also trying to work with industry to come up with voluntary standards before there is clear policy," he comments. A proposed nanomaterials stewardship program would involve collecting data on material characterization, hazards, use, exposure, and risk management, followed by a review.
"We're more likely to get voluntary consensus guidelines that make sense based on the best available data in place quickly as we continue to explore the prospects for new regulations," Kulinowski remarks. "It's a start to get EPA thinking about how to handle these issues, because they are grappling with some pretty difficult technical and legal questions."
In the long-term, Walsh sees any voluntary program as an interim step. "Government's not providing the guidance right now, so industry has got to step up and provide its own," he says. Voluntary standards only work when there are proactive companies. And these same companies could be at a disadvantage if others try to cut corners, he explains, whereas mandatory regulations would create a level playing field.
"There's also a broader business, or even societal, risk in that the public doesn't understand nanotechnology very well," he continues, in arguing for eventual mandatory regulations. "If a company doesn't follow the voluntary standards and irresponsibly puts something on the market that isn't safe, a market backlash could hamper our ability to capture some of the benefits that nanotechnology promises."
Complicating matters is that dozens of organizations and regulatory agencies worldwide are getting involved in discussions about regulations, and it's uncertain which ones should or will apply, when it might happen, and how much reporting will be required. It's also unclear if, or even how, nanomaterials might be classified or prioritized for regulation.
The best thing governments can do is remove regulatory ambiguity, says Matthew M. Nordan, president of the nanotech advisory firm Lux Research. "EHS concerns are impacting nanotech commercialization," he explains. "I would need more than two hands to count the companies that have really interesting technology that has led to a product candidate but are not going forward because the regulation is a moving target."
Large corporations have long-term shareholders who will take them to task for any product-related repercussions—"once bitten, twice shy," Nordan remarks about their caution—but investors in start-ups are motivated to get in and out quickly. "We have not really seen EHS concerns come up in due diligence for a start-up," he adds, possibly because most venture capitalists don't have experience in the chemicals or materials areas.
"The hole largely lies with start-up companies that either don't have the resources or aren't asking the right questions," he continues. These firms generally haven't created product stewardship or EHS structures like those in large companies built on environmental or product liability lessons and designed to prevent future incidents.
Nevertheless, he thinks it's unlikely any small firm will be producing significant volumes of nanomaterials without a major corporate partner helping it. Nordan has encouraged government actions, such as linking public funding to EHS research, even making small-business grants conditional on the submission of materials for testing.
Despite the rapid advances under way, Nordan says, overall there's a "massive disconnect" between EHS efforts and R&D or business development. "EHS offices tend to operate in a reactionary mode and mobilize when there is a perceived threat from an NGO creating concern or a real health and safety risk that has been demonstrated through scientific experiments," he explains.
"Neither one of those [situations] has really reached critical mass in the field of nanotechnology," he asserts. To bring the EHS, R&D, and business sides together, Lux Research has partnered with a toxicology consultancy to provide an auditing service. Through site visits and interviews, the team will issue a "bill of health" regarding the company's practices involving nanomaterials. The first such audit is under way at an aerospace and defense company.
"One thing companies can do is band together to educate each other and share ideas," says Roger Ackerson, EHS manager at FEI, an ion- and electron-beam technology company focused on nanoscale analysis and instrumentation. Resources are becoming available, he says, "and companies do have the tools to work in nanotechnology safely."
Although advances in enabling tools are supporting nanotech R&D, what doesn't yet exist is a simple monitoring instrument that an industrial hygienist might use to measure exposure limits, Ackerson points out. Nevertheless, he indicates that one need not know everything about a hazard to control it, and thus many companies operate under stringent safety precautions.
But with few EHS professionals around, many companies don't fully understand how to apply the controls that are available, he adds. To address these needs, FEI, Kennedy/Jenks Consultants, and Oregon Nanoscience & Microtechnologies Institute sponsored the Safer Nano Conference in March to share information on EHS best practices and on relevant laws and regulations.
After attending meetings in Washington, D.C., Ackerson says there clearly are strong feelings that more resources are needed to find answers about nanomaterials, but he emphasizes the importance of targeting nanoparticles of the highest concern. "Otherwise, we may squander the money trying to investigate everything about every particle while the real hazards go without the depth of research that's required." He hopes for "good, credible research we can hang onto."
To this end, nanomaterial producers and others are working alone and through collaborations to expand the breadth of toxicology data and measurement methods. ICON manages an EHS literature database that NNI-ChI CBAN commissioned Oak Ridge National Laboratory to compile. Similarly, the Wilson Center maintains an EHS research project inventory, and the National Institute for Occupational Safety & Health (NIOSH) has a nanoparticle information library.
BASF, Arkema, and Oxonica are among the two dozen members of NanoSafe II, a European Union initiative on the safe production, use, and disposal of nanoparticles. BASF, Bayer, and Degussa participate in NanoCare, a nanomaterials safety project run by the German government. And Arkema, Bayer, and Nanocyl just launched a consortium under the European Chemical Industry Council (CEFIC) that will collect and disseminate EHS information about carbon nanotubes.
"BASF is highly engaged in these discussions, and at the moment the debate is still based on scientific questions," says Martin Kayser, senior vice president and head of the department of product safety at BASF. The firm works in many nanotechnology areas; for example, it supplies nanoscale titanium dioxide and zinc oxide as UV protectants in sunscreens.
BASF conducts its own testing and also is part of Washington, D.C.-based ILSI Health & Environmental Sciences Institute's nanomaterial safety subcommittee. It has found that the sunscreen particles do not penetrate skin. BASF is also developing a method for inhalation studies. In many instances, Kayser points out, what's new is not the substance but the questions around the size of the particles.
Fundamental properties of nanoscale and bulk materials differ, and the effect of particle size on toxicology is still under investigation (C&EN, Dec. 19, 2005, page 52). Existing regulations don't recognize differences in a substance's toxicology based on particle size. Kayser also emphasizes the importance of research centering on free nanoparticles and the related issue of exposure, because without exposure to a hazard, there's no risk.
Another problem is defining "nano," adds Oxonica Chief Executive Officer Kevin Matthews. "How do we make sure we are capturing the right thing? Is it the primary particle size or the size of an agglomeration of smaller particles?" Many conventional materials have a spread of particle size, so he asks, what percentage needs to be "nano" for a material to be treated differently? Not surprisingly, standards organizations, such as ASTM and ISO, are attempting to define consistent standards, nomenclature, and terminology.
Oxonica, a spin-off from Oxford University, has two products: Optisol, a UV absorber for use in cosmetics, and Envirox, a fuel-borne cerium oxide catalyst that reduces fuel consumption and particulate emissions. "We have a duty to ensure that our materials are safe, and so we've actually carried out testing that goes well beyond the requirements of the current regulatory procedures in many parts of the world," Matthews says.
"We've not seen any adverse health effects and believe the benefits of Optisol in UV protection mean that the product should go forward," he says. "And as the product gets used, we continue to scale up our toxicology studies." The company posts some information on its website and intends to publish data in peer-reviewed journals.
Envirox has undergone a similar assessment. "We have looked at the absolute toxicology of cerium oxide in nanoparticle form in conventional toxicology tests, and it's nontoxic," Matthews says, describing some of the steps. Tests exposing synthetic lungs to neat cerium oxide aerosols and those with diesel particulates showed no difference. An environmental impact and life-cycle assessment taking into account fuel efficiency savings was positive as well.
Even before they move products into the marketplace, nanomaterials producers say most of their EHS attention goes to the workplace as the first line of defense. Although the jobsite offers the greatest chance for exposure, it may also be the easiest situation to control.
ICON has just contracted with researchers at the University of California, Santa Barbara, to survey how companies are handling nanomaterials in the workplace and protecting workers. Similarly, DuPont and others have created the Nanoparticle Occupational Safety & Health Consortium. The group's deliverables include assessments of available instrumentation and protection measures and development of a portable air-sampling method.
Since inhalation is often the biggest risk, Oxonica, for example, moves its materials in a liquid or slurry; BASF uses many measures, including closed systems. Ceramic nanomaterials made at Altair Nanotechnologies are handled as 1- to 3-??m aggregates, which are five to 10 times the size of commonly produced white pigments, according to Alan Gotcher, the firm's president and CEO. "Thus, we are reasonably safe in the assumption that standard procedures for handling pigments are probably adequate," he says.
Altair has been working on a voluntary project with NIOSH and the University of Nevada, Reno. They are looking at Altair's operating procedures; monitoring workplace environments, including lab and production areas; and analyzing data against current regulations. They are also trying a range of test methods that vary in cost and sophistication to see what will do the job of testing.
"As we bring these materials out of the lab through the scale-up process, work to understand the impact on the workers needs to be done in lockstep, since anything other than that runs risks that are unwarranted," Gotcher asserts. The results will be made public, he emphasizes.
Arkema has taken an even more precautionary approach by designing a completely automated carbon nanotube pilot plant. It's estimated to be among the largest plants in Europe making multiwalled nanotubes. "We have the capacity to produce around 10 to 12 metric tons per year and the possibility to increase capacity to 50 metric tons with a very small investment," says Daniel Bernard, senior science and technology adviser in Arkema's R&D department.
"We are obligated to have knowledge about the risk of our chemicals," Bernard explains. "With the gap in knowledge about nanoparticles, we decided to make our development of carbon nanotubes as safe as possible." The reactor is housed in a closed building that can be washed internally with water; the residue is incinerated to avoid any environmental release.
To ensure that its customers have no contact with free nanomaterials, Arkema presently does not sell carbon nanotubes directly. Instead, the output of the nanotube reactor goes directly to a compounding plant that produces precomposites that can be incorporated into polymers by plastics producers.
Beyond worker and customer safety, nanomaterial producers must consider environmental and product end-of-life implications. Carbon nanotubes can simply be incinerated to yield carbon dioxide, Bernard says. "The problem, which is not solved at the present time, is how to recover all the goods using nanomaterials so that industry can treat the waste."
Alternative green routes to producing nanomaterials are being investigated (C&EN, April 17, page 37). The idea is to create economically viable processes using fewer reagents, less solvent, and less energy, while being safer, generating less waste, and having a milder environmental impact than current technologies have. Both EPA and the Wilson Center have so-called GreenNano initiatives.
Other emerging areas include understanding the long-term health and environmental effects of nanomaterials and communicating with the public about risk and benefits, observers say. Many government efforts are backing education and communication programs. In the U.S., NNI and the National Science Foundation have such programs, while the EU has Nanologue. Communication and outreach are also part of NanoSafe, NanoCare, ICON, and ACC programs.
Transparency is a key principle of the DuPont and Environmental Defense framework. "You want to be able to have a very open, robust discussion about identifying issues and concerns and then assess and address those, so that going forward, products have been developed accordingly," Medley says. "It's very consistent with our core values in terms of safety and product stewardship, but addressing these questions early also makes good business sense."
Last year, Oxonica's Matthews was on the advisory panel of the NanoJury U.K. project, which is sponsored by Greenpeace, the University of Cambridge, the University of Newcastle, and the Guardian newspaper, to assess public understanding and reactions toward nanotechnology. Around the same time, the Wilson Center released a study by Jane Macoubrie of North Carolina State University on public perceptions of nanotechnology.
Despite initial low levels of awareness, these analyses found, the public reacted positively to nanotechnology's potential benefits upon learning more about it, although they still want more action on EHS, public information, and regulatory issues. "The public can make a decision here, just like they did with genetically modified organisms, that they don't want any of this stuff," Matthews warns. "But if we do this properly, and are open and explain what we are doing, then I don't see that as the natural outcome of this debate."
"It is critical that people understand the opportunities and also the risks, so that you can have an informed and balanced debate," BASF's Kayser adds. "These are complicated issues with regard to unique properties of nanosized materials, so there needs to be quite an effort from industry and government to inform people."
But just as the level of activity on EHS issues varies among companies and organizations, so too does the willingness to make information available and to engage publicly. Many involved are optimistic about the already close engagement among different groups. But others worry that technology development is rapidly outpacing regulatory or public communication efforts.
"Opinions haven't been formed yet, so the game from a public perception perspective is there to be lost by folks who are commercializing nanotechnology but not really acting on it," Lux Research's Nordan says. One reason may be the desire to avoid issues where there aren't any yet. "They recognize the long-term problem but are unwilling to take a short-term risk, and that's a big concern.
"There is a window here that's very clearly open," Nordan continues. And it represents a fairly unique opportunity to engage regulators, the public, and critics in identifying concerns early and working to satisfy them while the technology is emerging. Better that than having companies and governments moving forward with multi-billion-dollar investments and then finding out that the products or technology proves to be either hazardous or simply unacceptable.
- Chemical & Engineering News
- ISSN 0009-2347
- Copyright © American Chemical Society