Environmental t News PBDEs in electronics-recycling workers in China can impact thyroid hormones and alter brain development. Some of the newest research, presented at the Brominated Flame Retardants conference in April, shows that laboratory rats can metabolize BDE–209 to produce hydroxylated compounds that “may have Basel Action Ne t work
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lectronics-dismantling laborers in China are taking up very high concentrations of heavy polybrominated diphenyl ether (PBDE) flame retardants, according to new research published in ES&T (pp 5647–5653). The median levels of the heaviest PBDE, BDE–209, in the Chinese workers’ blood sera were 50–200 times higher than previously reported for occupationally exposed populations, and one worker had by far the highest concentration (3100 parts per billion) ever reported. The research suggests that air pollution from electronics recycling may be spreading the toxic compounds to other Chinese cities. The dismantlers participating in the study worked in Guiyu, “the largest center for e-waste dismantling in China,” says coauthor Xin hui (Cindy) Bi of the Guangzhou Institute of Geochemistry. “Every day a large amount of electrical and electronic waste likely to contain BDE–209, such as computers, printers, mobile phones, television sets, and so on, is processed in Guiyu,” she explains. “We do not know where the waste being recycled in China originates from, but much of it is believed to come from developed countries in the West,” says Gareth Thomas of Lancaster University (U.K.), the study’s other coauthor. BDE–209 is the main constituent of the Deca BDE formulation, which is used as a flame retardant in the plastic components of electronics products, particularly highimpact polystyrene. Deca BDE is now the only PBDE flame retardant used in North America and Europe. It has always been the primary formulation used in China. Toxicology studies conducted with animals show that BDE–209
Much of the electronics recycling in Guiyu, China, is done in the open air by workers not wearing masks.
very long half-lives and be very accumulative,” says Juliette Legler, a toxicologist at the Vrije Universiteit Amsterdam. The record level of BDE–209 found in the most contaminated Chinese worker “approaches the toxic doses administered to animals in the two most sensitive neurotoxicity studies, leaving no margin of safety,” points out Sonya Lunder, a senior analyst with the Environmental Working Group, an environmental group. Heather Stapleton at Duke University’s Nicholas School of the Environment says that the workers may be metabolically debrominating BDE–209, because the amount of two other heavy PBDE compounds, BDE–207 and BDE–
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197, in their blood was higher than what is found in the Deca formulation. This finding is consistent with “what we’ve observed in fish when we know that they’re debrominating PBDEs,” she adds. However, Thomas points out that more research is needed to confirm this possibility. He and his colleagues did not look for hydroxylated PBDE metabolites. One of the reasons that the Chinese laborers are likely to take up such high levels of PBDEs is because “we believe that masks and gloves are rarely or never used by most of the workers involved in this industry at present,” Bi says. The European Brominated Flame Retardant Industry Panel noted in a written statement that the ES&T research “just emphasizes the need for industrial hygiene.” Bi says that the Chinese government now recognizes “the severe environmental pollution and potential health effects resulting from e-waste dismantling.” Although China does not yet regulate the recycling of electronics produced outside of the country, Bi says that both the National Development and Reform Commission and the Ministry of Information Industry have developed regulations that “are in the process of being issued.” In the meantime, Bi and her colleagues are planning to investigate the source of the relatively high levels of PBDEs they found in the blood of residents of Haojiang, a city 50 kilometers east of Guiyu where fishing is the main industry. Bi suspects that atmospheric transport is the culprit because “most of the e-waste was processed in enclosed yards with no roofs,” and unsalvageable materials are burned in the open air. —KELLYN BETTS © 2007 American Chemical Society
When computers, televisions, music systems, and other electronic products reach the ends of their lives, they often end up in China or other developing countries as ewaste. Such waste is a serious environmental threat in these parts of the world because of the poorly regulated conditions under which the waste is dismantled and recycled. A new study published in ES&T (pp 5641–5646) shows that Guiyu, a major e-waste recycling center in China, has the highest documented levels of atmospheric polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs) in the world. In e-waste recycling centers in China, discarded products are dipped into open pits of acid and heated over grills fueled with coal blocks to extract precious metals, such as gold. These processes often release toxic metals, such as lead, and organic compounds, such as dioxins. The emissions are not regulated, and occupational exposure is high because of the poor working conditions for e-waste recycling laborers. In March 2007, researchers at Hong Kong Baptist University showed that soil at e-waste recycling sites in China has high levels of dioxins and polybrominated diphenyl ether (PBDE) flame retardants. In the current study, Ping’an Peng of the Guangzhou Institute of Geochemistry and his colleagues sampled the air from Guiyu for a week in the summer and the winter and analyzed the samples for 2,3,7,8-PCDD/Fs. The levels varied between 64.9 and 2765 picograms per cubic meter (pg/m3). The toxic equivalent (TEQ)—a value used to account for the different levels of toxicity of the individual dioxins— was 0.909–48.9 pg TEQ/m3. Given
the absence of other major dioxin sources in Guiyu, the authors attribute their results to e-waste recycling. The team also found that the dioxin concentrations in the air around Guiyu were 12–18 times higher than those in Chendian, a town 9 kilometers (km) from Guiyu, and 37–133 times higher than those in Guangzhou, which is 450 km from the e-waste site, suggesting that dioxin pollution from e-waste recycling is spreading to nearby areas. The calculated exposure of adults to dioxins through inhalation (68.9 and 126 pg TEQ/kg/day in the summer and winter, respectively) was significantly higher than the World Health Organization recommended maximum of 1–4 pg TEQ/kg/day. “The significance of the paper is to provide us with the first estimate of what [levels] to expect,” says Oladele Ogunseitan of the University of California Irvine. “As a next step, what needs to be done is as an epidemiological study looking for actual symptoms.” The results emphasize the need to “implement the kind of restrictions we have” in the developed world, says Gareth Thomas of Lancaster University (U.K.). M. H. Wong of Hong Kong Baptist University agrees. We need to “switch to proper recycling facilities” with cleaner technologies, he says. “The U.S. must now take very seriously the Basel Convention that prohibits the shipment of hazardous wastes to other countries,” says Ogunseitan. Some state laws prevent shipping e-waste to developing countries. Yet, the nonprofit Basel Action Network calculates that 50–80% of U.S. e-waste is sent to China. —RHITU CHATTERJEE
News Briefs Investing in renewable energy
At one time the renewable-energy market depended on the ups and downs of oil prices. Not any more. According to a new report by the UN Environment Programme, Global Trends in Sustainable Energy Investment 2007, investment in sustainable energy sources is growing steadily, with no signs of slowing down in the near future. Venture capital and private equity going into this sector have jumped from $2.7 million in 2005 to $7.1 million in 2006 and continue to grow in 2007, enabled by various policies that have provided incentives for such investments. Although the U.S., EU, and other developed countries still lead the market, developing countries are rapidly catching up, according to the report. India, China, and Brazil are now major producers of and markets for greener energy sources.
Mixed reports on EU industrial pollutants
Emissions of two-thirds of the EU’s industrial pollutants decreased between 2001 and 2004, according to the second European Pollutant Emission Register (EPER). Data were collected on 50 air and water pollutants from industrial facilities. Nitrogen compounds released into the water were down 14.5%, and dioxins and furans emitted into the atmosphere were down 22.5%, for example. However, CO2 increased by 5.7%. The report, published in June, is the first to cover the expanded EU—now 27 member states—and Norway. A new registry will replace EPER in 2009, starting with data from 2007 and covering more than 90 substances, plus sources such as road traffic, domestic heating, and agriculture.
August 15, 2007 / Environmental Science & Technology n 5577
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E-waste recycling spews dioxins into the air
Environmentalt News The muddy waters of wetland protection decision, creating two separate tests for determining the Corps’s jurisdiction over water bodies. The plurality opinion, written by Justice Antonin Scalia, said that the CWA can protect only traditionally navigable waters, their tributaries, and adjacent wetlands. Jupiterimages
The protection of the nation’s smaller streams and wetlands is unlikely to improve despite guidance issued in June by the U.S. EPA and the U.S. Army Corps of Engineers. The guidance was formulated in response to what most agree is a confusing Supreme Court decision issued last year. It sets forth a new test to determine whether certain wetlands are protected and requires that the Corps make its decisions on a case-by-case basis. This new test, patterned after language in the court decision, would allow the protection of small wetlands only if the Corps demonstrates that they significantly affect larger water bodies downstream. According to section 404 of the Clean Water Act (CWA), landowners and developers must obtain permits from the Corps before they can perform any activity—such as discharging pollutants or dumping dredged materials—that would harm a wetland. In the past, the Corps has protected wetlands, including small ones without obvious surface connections to larger water bodies, by relying on provisions in the CWA that refer to “navigable waters”. Landowners and developers disagree strongly that most wetlands should be protected, and several lawsuits filed over the past two decades have made their way to the Supreme Court. The most recent legal case, Rapanos v. U.S., resulted in a court decision that significantly changed the way the government can protect wetlands. The lawsuit involved John Rapanos, a landowner in Midland, Mich., who dredged and filled wetlands on his land without first obtaining a permit from the Corps. In his lawsuit, Rapanos argued that the Corps had no jurisdiction over the wetlands on his property because they were separated from larger waters by 32 kilometers and connected to them by ditches only. The court gave a split
New EPA and Corps joint guidelines of fer little help in protecting isolated wet lands under the CWA.
A second test, put forward by Justice Anthony Kennedy, stated that smaller streams and wetlands with no surface connection to larger waters also can be protected, provided the Corps can demonstrate what he called a “significant nexus”—meaning that the wetlands significantly influence the chemical, biological, and physical properties of larger water bodies. By combining both the Scalia and the Kennedy tests, the new guidelines note that the traditionally navigable waters and their tributaries will continue to be protected. The guidance adopts Kennedy’s significant nexus and applies it to smaller, often isolated, wetlands and streams. These can
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be protected under the CWA only if the Corps has shown such a nexus by considering hydrologic and ecological factors. However, those wetlands whose effects on the quality of downstream waters are “speculative or insubstantial” will not be protected. “We don’t think that the guidance itself provides clarification” for landowners or their lawyers, says Parker Moore, an attorney with Beveridge & Diamond, a law firm that represents landowners. “It establishes a situation where confusion is piled on top of confusion.” “In my view, the Corps and EPA have not clarified that ruling in any significant fashion,” says John Devine, an attorney at the advocacy group Natural Resources Defense Council. But part of the problem is “the nature of the beast,” says wetland expert Joy Zedler of the University of Wisconsin Madison. “We’re trying to draw a line where there is a gradient.” Wetlands perform extremely important functions, such as removing nutrients and trapping pollutants from water. But a range of functions exist, and not all wetlands behave the same way, says Richard Ambrose, a wetlands scientist at the University of California Los Angeles. This makes it inherently difficult to classify wetlands and to provide strict benchmarks by which the Corps can evaluate individual wetlands, he says. The guidance will involve more money, resources, and time in the decision-making process, he adds. “Well, I do think that there remains a level of uncertainty that will take some time to resolve,” says David Evans, director of EPA’s wetlands program. Evans admits that some wetlands that were protected before the Rapanos decision was issued will be more difficult to protect. But that’s an outcome less of the guidance than of the nature of the Supreme Court decision, he says. —RHITU CHATTERJEE
News Briefs
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Improvements in technology coupled with the rising costs and decreasing reliability of traditional water supplies are leading watershort cities to look to the oceans for drinking water. Despite its popularity, the process of removing salt from seawater to make
Drought, encouraged by climate change, could worsen with the worldwide trend to convert seawater into clean drinking water.
drinking water is so energy intensive, however, that the resulting greenhouse-gas emissions could contribute to regional water scarcity, according to a global survey of desalination plants by the environmental group WWF. “An awful lot of electricity is chewed up to desalinate this water, and that electricity, if generated from fossil fuels, will exacerbate the greenhouse effect,” says Jamie Pittock, who is a director of WWF’s global freshwater program and is a report author. Climate change may also be responsible for erratic weather patterns such as drought, which creates even more water scarcity. Recent industry statistics estimate that worldwide desalination capacity will increase 61% between 2006 and 2010 and a total of 140% by 2015 to 97.5 million cubic meters of water per day. Most of the
growth in capacity will occur in the Middle East and northern Africa, but capacity will also increase in China, India, Australia, Spain, the U.S., and even the U.K. The trend toward more and larger desalination plants raises issues about climate change, “although it’s not clear what the relative importance of desalination is versus every other greenhousegas-emitting activity,” points out Heather Cooley, a senior research associate at the Pacific Institute, an environmental think tank. She also listed increasing greenhouse gases as a possible negative environmental effect from desalination in a report she wrote on California’s market. A larger concern, Cooley points out, are the as-yet unknown longterm effects of several ecological impacts. For example, numerous tiny marine organisms are killed as they get sucked up into a desalination plant. And the plants produce a brine byproduct laced with chemicals, such as coagulants, antiscalants, biocides, and detergents, used in the treatment process, for example, to prevent membrane fouling. The brine waste is typically discharged directly into the ocean. The WWF report stresses that in most cases, other options—including conservation, more efficient water use, and recycling wastewater—would provide the same benefits as desalination, at lower economic, social, and environmental costs. Wade Miller, executive director of the WateReuse Association, an industry group, agrees that desalination isn’t a panacea. “Every major water utility needs to look at the whole portfolio of water supply options and see where desalination fits in,” Miller says. He adds that his organization is working in conjunction with others to fill research gaps raised by the WWF report. —KRIS CHRISTEN
Battling climate change the American way
Americans are ready for action on climate change, recent surveys say, but what steps are they willing to take? A new poll finds that the most popular policy option among pocketbook-conscious Americans is low-carbon standards, in which companies are given limits and told how to curb their emissions. Nearly 1500 adults rated the appeal of standards, emissions taxes, and cap-andtrade policies that allow companies to trade emission credits. Of the respondents, 73% supported standards that would raise electricity bills by $10 per month, but only 47% supported cap-and-trade schemes at the same price point. No vehicle fuel policies won majority support. Economists say standards are more expensive than the other options. The poll was commissioned by New Scientist magazine, Stanford University, and the nonprofit think tank Resources for the Future.
Nuclear energy: not a climate cure
Nuclear power would have to expand worldwide at its highest historical rate for the next 50 years to be a significant part of a greenhouse-gas mitigation plan, according to a new report on the future of this energy source. Building 14 new plants and replacing 7.4 retired ones every year would reduce carbon emissions by about 1 billion tons per year by 2050, enough to form one of seven or more “stabilization wedges” needed to prevent CO2 concentrations from rising above 500 parts per million. However, the report’s 27 authors from various groups had trouble agreeing on how much, or even whether, nuclear capacity will actually expand in coming years. The nonprofit Keystone Center spearheaded the yearlong assessment, Nuclear Power Joint Fact-Finding.
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Environmental costs of desalination
Environmentalt News
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A trip to the seashore inspired one of this year’s winners of the Presidential Green Chemistry Challenge. Kaichang Li, a wood chemist at Oregon State University, recalled seeing the strong tendrils of a mussel gripping seashore rocks and wood flotsam. His curiosity was piqued, and Li later made a wood adhesive that is based on the same proteins that mussels use to create
A technique to make mussel proteins into wood glue is one of five Presiden tial Green Challenge winners.
their anchoring fibers. That biobased glue is one of the five winners honored at the 11th Annual Green Chemistry and Engineering Conference in June. After determining how mussels create the protein chitosan, Li and his colleagues manufactured a similar polymer by creating a reaction that would add the proper amino acids to soy flour, which lacks the proteins that mussels make. The result was an adhesive that cross-linked with wood fibers in a “gigantic network, like putting a key in a lock and turning it,” Li said in his presentation at the meeting. Li’s team’s work, begun in earnest in 2000, has borne enough fruit to garner the interest of two wood-and-paper products companies, Columbia Forest Products and Hercules, Inc. The musselbound woods have lower volatile organic compound emissions
than typical compressed woods and meet the U.S. Green Building Council’s Leadership in Energy and Environmental Design standards (LEED). The products also have similar strength characteristics—even after multiple “drownings” to test the dissolvability of the glue. The green chemistry awards, established and sponsored by companies and organizations (including the American Chemical Society) in partnership with the U.S. EPA, highlight research from academia and industry that focuses on more efficient techniques using less water or feedstocks, among other criteria, to create better products. This year’s other awardees included Cargill’s BiOH Polyols, a vegetable-oil-based compound that is used as a major component of polyurethane foams. NovaSterilis, Inc., a small company based in Ithaca, N.Y., found a way to use supercritical CO2 to sterilize medical materials, including skin grafts and vaccines, without the usual methods that require ethylene oxide or g radiation. In the pursuit of “greener” reactions, Headwaters Technology Innovation developed a synthesis method for hydrogen peroxide (H2O2) that uses a 4-nanometer palladium–platinum catalyst. The process makes H2O2 directly from hydrogen and oxygen, with no need for vacuum purification and none of the quinine byproducts associated with more widely used methods. Michael J. Krische at the University of Texas Austin and colleagues won for developing a new class of basic, widely used hydrogenation reactions that use metals to catalyze more efficient, cleaner reactions. The new hydrogenation process forms carbon–carbon bonds (instead of carbon–hydrogen bonds) to make pharmaceuticals, pesticides, and other products used every day. —NAOMI LUBICK
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News Briefs Shift urged for chemical toxicity testing
It’s time for a fundamental change in the way chemicals are assessed for potential toxicity, the National Academies’ National Research Council says in a report, Toxicity Testing in the Twenty-First Century: A Vision and a Strategy. The June report, requested by the U.S. EPA, urges a rapid shift away from the entrenched reliance on animal testing. Instead, the committee says, much of the needed baseline information can be gleaned with high-throughput assays of human cells. The committee says this information, combined with multidisciplinary research on human populations and the fate of chemicals in the environment, could lead to better models for predicting chemical effects on critical pathways in the human body. The recommended changes are expected to allow faster, more relevant evaluations of chemicals at lower cost.
Sustainable coal use
U.S. reliance on domestic coal reserves is expected to remain strong and may increase over the next several decades. More-accurate assessments of these deposits and research to counteract potential environmental impacts from rising demand for coal are sorely needed, according to the U.S. National Research Council (NRC). NRC’s new report, Coal: Research and Development to Support National Energy Policy, points out that although U.S. coal reserves are vast, current technologies can only recover a small portion of the total. Mining deeper, less accessible seams could disturb hydrologic systems, cause ground collapse, and exacerbate waste-management issues at mines and processing plants. The NRC panel recommends more than quadrupling federal funding for coal research to $190 million annually.
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Green chemistry gets the prize
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