Pure Chemistry

On a drizzly afternoon in early March, Adam Andrewjeski, an 18-year-old college freshman from Las Vegas, walks out of his dormitory room and, in his slippers, pads down a flight of stairs to a common laundry room on the University of California, Berkeley campus. But he’s not looking to do his laundry. He just wants to score some lint.

Andrewjeski leans into a dryer and pulls out a dark clump of fuzz. Thinking he may need a little more, he opens the next dryer and sweeps its lint catcher clean too. As he balls the two together in his pocket, he explains that he’s hunting for traces of PBDEs, chemical flame retardants. PBDEs were designed to be persistent; even after many washes, fabrics treated with the chemicals may still be shedding them. With that, he turns and heads up the stairs. He’ll collect the rest of his samples -- dust, bits of foam from dorm room furniture -- another day.

Andrewjeski is one of a growing number of students learning to think differently about the safety and sustainability of the molecules that make up our lives. Over the past decade, colleges and universities across the country have begun to offer courses in green chemistry, some even awarding Ph.D.’s in the field. But whereas other schools focus on teaching the principles of green chemistry exclusively to chemists, Berkeley intends to do something more. The idea here is that the best way to make chemistry sustainable is to bring together the chemists who will invent new molecules with the biologists who will unravel their toxicological effects, the future business leaders who will sell the products made from those molecules, and the policy makers who will regulate them. And because all this is happening in what is generally regarded as the nation’s most prestigious school of chemistry, where more than a thousand Ph.D. and undergraduate students grind away in classrooms and laboratories every day, there’s reason to be cautiously optimistic that green chemistry is on track to become the field of chemistry itself.

Chemistry is you and everything around you. Trillions of chemical reactions take place in your body at any given moment, allowing you to read the words on this page, to know you’re thirsty and get up for a glass of water, to sense that the room is a bit stuffy and open a window. And of all the goods bought and sold in the United States, some 97 percent incorporate manufactured chemicals of one kind or another. Many of them make life better: they are used to purify water, fight cancerous tumors, and keep the lights on. The problem is that of the 82,000 synthetic chemicals that have come into production to date, nobody is quite sure which ones simply make life better and which ones are harmful. That is because for the past 200 years, since the advent of modern chemistry, nobody ever asked chemists to consider that question.

John Warner is an industrial chemist-turned-entrepreneur who now runs a research and development center called the Warner Babcock Institute for Green Chemistry in Wilmington, Massachusetts. Over the course of his career, Warner has filed more than 200 molecular patents and founded the first Ph.D. program in green chemistry, at the University of Massachusetts at Boston, in 2001. His childhood friend Paul Anastas, who grew up with him in blue-collar Quincy, south of Boston, is now head of the office of research and development at the Environmental Protection Agency (EPA), where he oversees the latest science on chemicals assessment, including which methods toxicologists use to determine whether a substance is toxic. Together, Warner and Anastas pioneered the field of green chemistry in the 1990s, writing the first book for chemists seeking to design compounds sustainably, Green Chemistry: Theory and Practice.

At last year’s Bioneers conference, an annual gathering of thousands of business leaders, environmental advocates, and academics with a common interest in sustainability, Warner told the story of his father, an electrician, who "couldn’t come into your house and change a lightbulb without a document that said he could do it safely." Teachers, architects, doctors -- all need to prove that they have met a set of requirements for practicing their profession responsibly. But chemists, he lamented -- the people who design products we eat, breathe, and absorb through our skin -- have no such responsibility. "Imagine you want to be a chemist," he said. "Think of any university you can imagine. Go online and find the courses you have to take to get a job as an industrial chemist. You will find that not one university will have you take a course in toxicology."

Figuring out the effects on human health and the environment of the reagents, solvents, and final products used and produced by chemists simply hasn’t been the chemist’s job. In the lab, goggles, gloves, and gale-force fume hoods protected chemists from whatever dangers lurked, so it didn’t much matter what they mixed up as long as the end result was something new and wonderful that worked as it was meant to. But over the years we began to learn that molecules that were supposed to be locked away forever inside our TV sets and plastic toys found ways of escaping. By the close of the twentieth century, scientists were discovering that some of these molecules were making their way not only into the air, soil, and water, but also into fish and mammals -- including us. Today the Centers for Disease Control routinely tests Americans’ blood for the presence of 219 classes of chemicals as part of its annual National Health and Nutrition Examination Survey. Other studies have detected as many as 493 in our blood. The effect of that chemical cocktail on the human body remains largely unknown, though a growing body of research is revealing that many of its components can wreak havoc on the delicate balance of hormones, proteins, and other molecules that make us tick.

Public health experts agree that the law that was meant to protect us from potentially dangerous chemicals -- the Toxic Substances Control Act (TSCA) -- is broken. The burden of proving that a substance is toxic falls to the government; industry has no obligation to prove that a chemical it has synthesized is safe. The law, passed in 1976, stipulates that when a company invents a new compound, it is required to give the Environmental Protection Agency (EPA) just 90 days’ notice before the product is introduced into the marketplace. If the agency doesn’t raise any safety concerns within this period, no further barriers stand in the way of full-scale manufacturing. Although the law says that a company should submit any available safety data, it’s also okay not to if no data exist. To date, about 85 percent of all new chemical notices have been submitted without any safety data at all.

When the law went into effect, some 60,000 chemicals were already in production, and they got a free pass -- no safety data required. Among these were some nasty chemicals that in a few cases are now being voluntarily phased out or restricted. These include some members of the PBDE family of flame retardants as well as BPA, which was removed from some baby products and other plastics (though only in some states) after concerns about its role as an endocrine disruptor emerged in the 1990s. But the vast majority of chemicals have been subject to no restriction. The law places an enormous burden on the government to prove not only that a chemical is causing irrefutable harm but that any regulations imposed will lead to no increase in costs over doing business as usual. Translated, that means that only five chemicals have ever been regulated under TSCA: PCBs, CFCs, dioxins, hexavalent chromium, and asbestos.

This article was made possible by the Jonathan And Maxine Marshall Fund for Environmental Journalism.

Two years ago, the Obama administration pledged to change that. EPA administrator Lisa Jackson testified before Congress that TSCA should be strengthened, arguing that "in the rare cases where EPA has adequate data on a chemical and wants to protect the public against well-known, unreasonable risks to human health and the environment, there are too many legal hurdles to take quick and effective regulatory action." Last year, Senator Frank Lautenberg of New Jersey introduced legislation that would enable such action, but it failed to come to a vote. Lautenberg’s bill was reintroduced in April of this year, but it’s not yet clear how far it will advance.

Either way, the Berkeley Center for Green Chemistry aims to help fill the gap. The center’s mission is threefold: to educate the next generation of chemists; to share the best available science on chemistry and toxicology with policy makers and the public; and to conduct interdisciplinary research at the intersection of health, chemistry, policy, and business. These are lofty goals, all of which will take time, says John Arnold, the head of the center and a professor of chemistry at the school.

"In the same way that it took a generation to change how people think about putting on a seatbelt or not smoking," he says, "we’re not going to change things overnight. Legislation can’t do that, though it will certainly help push things in the right direction. You have to change hearts and minds, and that’s what we’re trying to do."

On a Monday afternoon in early March, forty or so students -- mostly graduate students in chemistry and engineering with a handful of public health and law students mixed in -- file into a classroom in Etcheverry Hall. They’re enrolled in Green Chemistry: An Interdisciplinary Approach to Sustainability, a graduate-level course taught by a team of experts from the schools of chemistry, natural resources, public health, and engineering, as well as Berkeley’s Haas School of Business. It’s the first course offered by the new center, and there’s a slight sense that everyone in the room is going someplace where no one has gone before. In the back row, the professors themselves sit, pens and notebooks ready, as Mike Wilson walks up to the podium.

Wilson’s job is to help connect the various disciplines that fall under the center’s umbrella. One of the driving forces behind its creation, he’s also a widely respected expert in public and occupational health and is often called on by the California legislature to write reports on the intersection of chemistry, public health, and environmental science and to testify before lawmakers. Today he is talking about the properties of various compounds and how people are exposed to them.

He recounts a startling firsthand experience that led him to champion the emerging field of green chemistry. While working toward his Ph.D. in occupational health, Wilson, a firefighter and paramedic-turned-scientist, studied the workplace exposures of auto mechanics in the San Francisco area. Healthy young men suddenly found themselves suffering from severe peripheral nerve damage, to the point where some ended up in wheelchairs. The common link: they all worked in auto repair shops.

The culprit proved to be a commonly used brake-cleaning solvent that combined acetone and hexane, which react inside the human body to form altogether different molecules that destroy nerve fibers. The mechanics were going through several cans a day, Wilson discovered, and though they often worked in garages that would be considered well ventilated, the properties of the toxic vapors caused them to hover under the cars where the mechanics were working for long enough to cause significant exposure.

To make matters worse, this combination of solvents had been introduced as an alternative to the carcinogenic chlorinated solvents that had been used before. But the manufacturer’s failure to consider fully how workers might typically be exposed to its product -- and the lack of any rules that would force it to do so -- led to disastrous consequences.

From the back of the room, John Arnold pipes up with a question. Was the switch from the earlier solvents beneficial? Were fewer workers falling ill overall? Students swivel in their chairs. How could it be beneficial if humans were losing the ability to walk? But Arnold’s question reflects the reality of where chemistry, health, public policy, and business overlap today. The trade-offs that must be made often amount to settling for the best among a set of bad alternatives.

"Part of what we need to do is ask those big questions," Arnold tells me later, "and we can’t do that if the chemists aren’t talking to the toxicologists and the economists and the people in public health." Purely as a chemist, he says, he would have regarded hexane as a perfectly logical solvent. However, shouldn’t a chemist "at least be in the position when making a new compound or a better polymer to ask: What’s that going to do to people? How long is it going to be around? Is it going to end up in breast milk in Sweden? We don’t think about that."

on Wednesday, class meets again. With her red curls pulled back and tucked behind her ears, Meg Schwarzman leans over the podium that holds her laptop and flashes her first slide. Schwarzman is a research scientist at the school of public health and a practicing physician. Along with Wilson, she was instrumental in the creation of the Center for Green Chemistry. Her topic today is how toxicologists identify the biological pathways that, when altered, raise the risk of disease.

"How do we know what hazards these things pose?" she asks. "That’s toxicity testing." She goes on to explain such fundamental concepts as the difference between morbidity (illness) and mortality (death). "Like, 'I have cancer,'" she says, drawing a stick figure with a slumping head. The class laughs. "Or, 'I am dead,'" she adds, drawing a stick figure lying prone.

Eight years ago, while Schwarzman was completing her residency training at the University of California, San Francisco, she was assigned to work in a clinic that served an area of the city that included one Superfund site and more than 100 brownfield sites. The rate of hospitalization from asthma there was five times higher than in surrounding neighborhoods. Handing out inhalers, she says, was like "trying to catch a tidal wave in a teacup." Band-Aid medicine could not fix problems that were rooted in environmental exposures.

Schwarzman eventually gave up her job as a full-time clinician and went back to school to earn a master’s degree in environmental health. She still sees patients once a week, but her focus has shifted dramatically, with most of her time now spent on research. In collaboration with Sarah Janssen, a physician and scientist with the Natural Resources Defense Council, Schwarzman has identified toxicity tests that could be used to determine whether a given chemical will alter a biological pathway relevant to breast cancer and so raise the risk of the disease.

Today she is talking to her class about phthalates, a class of chemicals found in a wide variety of substances -- in fragrances, for example, and in certain plastics, such as rubber duckies, IV tubing, and credit cards, where they are used to strike the right balance between rigidity and flexibility. "Does everyone know what phthalates are?" she asks. The group nods. In humans, she says, phthalates have been associated with higher rates of feminization of newborn boys. Cryptorchidism, or undescended testicles, is one of the most common birth defects in the United States, though it is typically corrected soon after birth. Even so, the fix requires invasive surgery, and the condition has been linked to increased rates of testicular cancer and infertility. But how exactly do we point a finger at phthalates as the cause rather than mere coincidence? That’s where understanding the mode of action comes in.

In the case of phthalates, Schwarzman explains, the chemicals decrease the production of testosterone and insulin-like growth factor 3. The role of testosterone in male sexual development begins in the womb, where it is essential to forming the testicles and positioning them outside the body. Without enough testosterone, the developmental road map is altered, and feminization can occur.

While Wilson and Schwarzman’s lectures have raised some of the basic intellectual and ethical challenges that chemists must face, sitting in a seminar won’t give them the tools they need to design smarter, healthier products. They need basic lab skills and a functional understanding of the science of toxicology, translated into a language with which chemists are familiar -- that of molecular structures.

Take oxidation, for example, says Marty Mulvihill, who is the executive director of the Center for Green Chemistry and responsible for developing its curriculum. Oxidation is one of the most common reactions that take place once a chemical enters the body. "Is it going to create a bad chemical?" Mulvihill asks. As chemists come to understand how particular molecular structures determine particular outcomes, he believes, they will begin to develop an intuitive sense for which new molecules may be toxic and which are likely to be more benign.

Mulvihill’s strategy starts with the lab experiments that freshmen like Adam Andrewjeski are conducting in introductory chemistry. In early 2010, Mulvihill began to work with Michelle Douskey, a chemistry lecturer, to rethink undergraduate lesson plans. To teach students about mixing precise concentrations, they wanted to devise a task with some relevance to an 18-year-old. They decided to create biofuel. Now they’re further refining the experiment, asking students to use the waste products from the biofuel to make bioplastic.

In Mulvihill’s laboratory-cum-office, small yellow trays containing shards of plastic bear labels that reveal their chemical makeup. Different concentrations of glycerin and gelatin, for example, impart different physical properties, from hard and clear to foggy and rubbery. Nearby, there’s a small flask containing an orange liquid with bits of marinating pulp inside. "Carrots," Mulvihill says. "We’re teaching students about dyes, so we want them to extract natural beta-carotene." Why not consider where the dyes come from in the first place? Budding chemists need that basic awareness: they may work in isolation under fume hoods, but their products do not remain in that vacuum.

Mulvihill is also working with Chris Vulpe in the toxicology department of Berkeley’s College of Natural Resources to devise the school’s first graduate toxicology course specifically geared to chemists, which they intend to offer next spring. John Warner hopes that Berkeley will not only offer such a course but require it. He believes it will lead to more benign chemicals and products and also land students good jobs. Some 120 students went through Warner’s Ph.D. program in Boston, and all of them learned about the role that molecular structures play in determining potential toxicity. They also learned about designing molecules at room temperature using nontoxic solvents -- saving energy and money on waste disposal costs. Those are just a couple of the basic principles of green chemistry that make students trained in the discipline appealing to employers, he believes. According to Warner, his students got jobs, on average, just three days after graduation.

Benign and efficient design is not the goal only of do-gooder idealists. Many major corporations are moving swiftly to apply the principles of green chemistry to research and development initiatives.

"I can’t name a brand-name company that doesn’t have an internal green chemistry program," Warner says. Pfizer, Merck, DuPont, Dow: all the big guys have them, he says, but "they don’t beat their chests about it. One reason is that it’s a catch-22. If they say, 'We’re going to make safe materials,' well…that kind of acknowledges they weren’t making them before. So many companies have decided to do it because it’s the right thing to do, not as a marketing tool but to make them more competitive."

Dow, through its charitable foundation, has established a $10 million program in sustainable product design at the Haas School. Though not affiliated with the Center for Green Chemistry, the initiative funded the university's first graduate-level seminar series on green chemistry, which is credited with sparking interest in the topic within the College of Chemistry. Tony Kingsbury, a Dow chemical engineer and executive on loan from the company, currently oversees the sustainable products program at the Haas School. His post is temporary but, while here, he teaches classes and works with other researchers on campus to bring industry’s perspective to bear on identifying which big questions to pursue. "Dow has sinned in the past and we don’t deny that," Kingsbury says. But the need for scientists who can think about safety in the first place is clear to company executives, he says, citing a case in which not doing so was harmful to the bottom line. Several years ago, Dow chemists developed a "superplastic" -- perfectly clear and ultrastrong -- only to discover that 1 percent of the population was allergic to the stuff. That’s millions of people and, in turn, millions of dollars of Dow’s research money down the drain. That may be pocket change to a behemoth like Dow, but the ability to dramatically reduce the risk of such losses simply by hiring savvier chemists has clear appeal. Kingsbury says Dow is eager to hire students who are trained to think in a more holistic, benign-by-design way.

The basic logic of training chemists to anticipate problems is hard for any company to argue with. "Nobody sets out to hurt people," John Arnold says. "But inadvertently, they may do that through not knowing about toxicology or the bioaccumulation of a material." Chemists, of course, are not the same as chemical companies, which may have financial motives for disregarding warning signs. But ignorance is a huge part of the problem, and avoiding those mistakes saves time, money, and reputation -- something that is increasingly important as more consumers demand to know what’s in the products they buy.

Even in the absence of strong national policy and stricter regulation of new and old chemicals, this consumer pressure is mounting. Newer, entrepreneurial companies such as Method and Seventh Generation are building their brands on safe, eco-friendly cleaning and personal care products -- products that are proliferating on grocery store shelves. The biggest changes, however, are unfolding less visibly at some of the largest brand-name retailers and manufacturers.

At Staples, the world’s largest office-supply chain and parent company to Staples Advantage, a separate $9 billion business-to-business janitorial supply operation, change is well under way. "Customers are demanding this information," says Roger McFadden, a chemist and vice president at Staples. As a pass-through retailer, which sells products made by other companies -- printers manufactured by HP, pens made by Bic -- Staples believes it has a responsibility to find out what’s in the products it sells. As expected, when the company requests ingredient disclosures and safety information from suppliers, hazard data are thin or lacking altogether. McFadden is quick to point out that some companies, including HP, do have that information and are eager to share it, making their products more appealing to informed customers.

Staples has developed its own line of safer cleaning products for its business-to-business operation, which serves 65 percent of all Fortune 100 companies. That label, Sustainable Earth by Staples, has seen considerable growth in recent years. At the same time, more companies doing business with Staples are asking for office and janitorial supplies that avoid specific substances of concern. These include chemicals that consumers already know about, like phthalates and BPA, but others are compounds that have largely flown under the public radar.

Staples is not alone. For other large, well-established brands -- such as Clorox, SC Johnson, and Procter & Gamble -- consumer pressure is leading to greater transparency in the disclosure of ingredients. In 2008 the American Cleaning Institute, a trade association for manufacturers of cleaning products, announced that its members would begin voluntarily disclosing ingredients. Clorox has now posted all ingredients used in its products on the company’s Web site, and SC Johnson has launched a dedicated site where consumers can search the company’s offerings by brand, product type, or chemical ingredient.

Dow’s Kingsbury is among those who believe the market will continue to shift in this direction. "Those with brands to protect care more," he says. Unlike smaller companies that sell widgets to other businesses, those that sell things like personal care products have more to lose by ignoring the mounting pressure to come clean about all their ingredients, even if -- or perhaps especially if -- there are questions about safety.

Consumer services like GoodGuide, which rates products based on their health, environmental, and social responsibility bona fides, have played an integral role in pushing industry toward greater transparency. GoodGuide, which was founded by Berkeley associate professor Dara O’Rourke, has compiled a database of publicly available toxicological data on many thousands of chemicals. Some 700,000 people visit its Web site every month. Savvy consumers can search by brand or product type to find out how their preferred products -- cleaning sprays, baby wipes, lipstick, even smartphones -- stack up. For every searched product, the site displays a shortlist of higher-scoring alternatives. Even supposedly "green" manufacturers receive demerits in their rankings, O’Rourke says, for using vague and unregulated terms such as "naturally derived surfactant." This summer, GoodGuide’s product rankings will begin to appear alongside products for sale through selected online retailers.

Ultimately, consumer advocates like O’Rourke and the folks at the Center for Green Chemistry are striving for more than just transparency. It’s the obvious next step: the use of safer alternatives. Two chemicals from the class of PBDEs, the flame retardants that Adam Andrewjeski was hunting down in the laundry room, have been voluntarily phased out. Once a suite of alternatives is on the table, it will be easier to let go of bad chemicals like these, even if they serve an essential purpose. Right now, however, there are no truly safe flame retardants on the market; there are only less-bad choices. The case of PBDEs highlights the need to design safer chemicals from the ground up.

John Warner has a back-of-the-envelope estimate for how this may all shake out. About 10 percent of the chemicals on the market are probably safe, he says. Perhaps another 25 percent can be phased out and replaced with safer alternatives that already exist. And for the remaining 65 percent? Well, he believes there are no alternatives yet that are safe enough. For that, we’ll need to head back to the lab and tap green chemists to invent benign molecules that will meet our needs.

"You can look at this and despair, or you can look at it and say, 'What better time in history to be a chemist?'" he says. "Why doesn’t every kid want to be a chemist and have such important work to do? Not only having a good job, but also doing the most intellectually challenging thing you can imagine doing and saving the world at the same time."