Warm Water Causes Extra-cold Winters in Northeastern North America and Northeastern Asia

PASADENA, Calif.—If you're sitting on a bench in New York City's Central Park in winter, you're probably freezing. After all, the average temperature in January is 32 degrees Fahrenheit. But if you were just across the pond in Porto, Portugal, which shares New York's latitude, you'd be much warmer—the average temperature is a balmy 48 degrees Fahrenheit.

Throughout northern Europe, average winter temperatures are at least 10 degrees Fahrenheit warmer than similar latitudes on the northeastern coast of the United States and the eastern coast of Canada. The same phenomenon happens over the Pacific, where winters on the northeastern coast of Asia are colder than in the Pacific Northwest.

Researchers at the California Institute of Technology (Caltech) have now found a mechanism that helps explain these chillier winters—and the culprit is warm water off the eastern coasts of these continents.

"These warm ocean waters off the eastern coast actually make it cold in winter—it's counterintuitive," says Tapio Schneider, the Frank J. Gilloon Professor of Environmental Science and Engineering.

Schneider and Yohai Kaspi, a postdoctoral fellow at Caltech, describe their work in a paper published in the March 31 issue of the journal Nature.

Using computer simulations of the atmosphere, the researchers found that the warm water off an eastern coast will heat the air above it and lead to the formation of atmospheric waves, drawing cold air from the northern polar region. The cold air forms a plume just to the west of the warm water. In the case of the Atlantic Ocean, this means the frigid air ends up right over the northeastern United States and eastern Canada.

For decades, the conventional explanation for the cross-oceanic temperature difference was that the Gulf Stream delivers warm water from the Gulf of Mexico to northern Europe. But in 2002, research showed that ocean currents aren't capable of transporting that much heat, instead contributing only up to 10 percent of the warming.

This image, taken by NASA's Terra satellite in March 2003, shows a much colder North America than Europe--even at equal latitudes. White represents areas with more than 50 percent snow cover. NASA's Aqua satellite also measured water temperatures. Water between 0 and -15 degrees Celsius is in pink, while water between -15 and -28 degrees Celsius is in purple.
Credit: NASA/Goddard Space Flight Center Scientific Visualization Studio; George Riggs (NASA/SSAI)

Kaspi's and Schneider's work reveals a mechanism that helps create a temperature contrast not by warming Europe, but by cooling the eastern United States. Surprisingly, it's the Gulf Stream that causes this cooling.

In the northern hemisphere, the subtropical ocean currents circulate in a clockwise direction, bringing an influx of warm water from low latitudes into the western part of the ocean. These warm waters heat the air above it.

"It's not that the warm Gulf Stream waters substantially heat up Europe," Kaspi says. "But the existence of the Gulf Stream near the U.S. coast is causing the cooling of the northeastern United States."

The researchers' computer model simulates a simplified, ocean-covered Earth with a warm region to mimic the coastal reservoir of warm water in the Gulf Stream. The simulations show that such a warm spot produces so-called Rossby waves.

Generally speaking, Rossby waves are large atmospheric waves—with wavelengths that stretch for more than 1,000 miles. They form when the path of moving air is deflected due to Earth's rotation, a phenomenon known as the Coriolis effect. In a way similar to how gravity is the force that produces water waves on the surface of a pond, the Coriolis force is responsible for Rossby waves.

In the simulations, the warm water produces stationary Rossby waves, in which the peaks and valleys of the waves don't move, but the waves still transfer energy. In the northern hemisphere, the stationary Rossby waves cause air to circulate in a clockwise direction just to the west of the warm region. To the east of the warm region, the air swirls in the counterclockwise direction. These motions draw in cold air from the north, balancing the heating over the warm ocean waters.

To gain insight into the mechanisms that control the atmospheric dynamics, the researchers speed up Earth's rotation in the simulations. In those cases, the plume of cold air gets bigger—which is consistent with it being a stationary Rossby-wave plume. Most other atmospheric features would get smaller if the planet were to spin faster.

Although it's long been known that a heat source could produce Rossby waves, which can then form plumes, this is the first time anyone has shown how the mechanism causes cooling that extends west of the heat source. According to the researchers, the cooling effect could account for 30 to 50 percent of the temperature difference across oceans.

This process also explains why the cold region is just as big for both North America and Asia, despite the continents being so different in topography and size. The Rossby-wave induced cooling depends on heating air over warm ocean water. Since the warm currents along western ocean boundaries in both the Pacific and Atlantic are similar, the resulting cold region to their west would be similar as well.

The next step, Schneider says, is to build simulations that more realistically reflect what happens on Earth. Future simulations would incorporate more complex features like continents and cloud feedbacks.

The research described in the Nature paper, "Winter cold of eastern continental boundaries induced by warm ocean waters," was funded by the NOAA Climate and Global Change Postdoctoral Fellowship, administrated by the University Corporation for Atmospheric Research; a David and Lucille Packard Fellowship; and the National Science Foundation.

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Marcus Woo
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Greening Caltech's Bottom Line

You can see signs of Caltech's commitment to sustainability everywhere you look on campus: there are recycling centers, LEED-certified buildings, and arrays of solar panels, not to mention landscaping that uses drought-tolerant plants, and dining rooms that feature compostable utensils.

But some of the campus's most impressive efforts are also its least visible ones. Caltech's efforts to finance urgently needed energy-efficiency upgrades—and to do so in ways that give back to the Institute—have been recognized by the Sustainable Endowments Institute in its recently released report, Greening the Bottom Line: The Trend toward Green Revolving Funds on Campus.

Green revolving funds are monies set aside to finance needed upgrades that will increase the efficiency of energy use; these projects are funded based on their likelihood to return the capital spent on them—plus some—once the reductions in energy use or operating expenses are realized. And it's that return on capital that allows the funds to revolve—to be used for yet another energy-saving project.

Caltech's own green revolving fund—the Caltech Energy Conservation Investment Program (CECIP)—was initiated in 2009, and it manages $8 million within an existing endowment created to finance capital projects.

"CECIP allows Caltech to effectively deploy capital to realize energy and cost savings from energy-conservation measures that would otherwise be unfunded," says John Onderdonk, Caltech's manager for sustainability programs. "It's a perfect example of Caltech's sustainability vision in that it reduces the campus's environmental footprint while enhancing the Institute's core mission."

The projects' impact has been nothing if not impressive. According to the Sustainability Research Institute, the efficiency measures funded by Caltech's CECIP has allowed an average return on investment of 33 percent, and had—by August 2010—reduced the Institute's energy bills by $1.5 million.

What's perhaps more impressive is that these projects aren't the high-visibility, easy-to-get funded initiatives like rooftop solar panels. "A lot of the work done through CECIP is behind the scenes," Onderdonk says.

Among the projects that CECIP has funded in the past two years are heating, ventilation, and air-conditioning upgrades at the Broad Center; the installation of auto-closing flume hoods in the Schlinger Laboratory; an LED lighting upgrade in the South Wilson Parking Structure; and lighting upgrades at South Mudd, North Mudd, the Beckman Institute, and the Keck Laboratories.

Any member of the Caltech community is welcome to submit a project proposal, says Onderdonk; projects will be approved if they have a 15 percent return on investment or a simple payback period of less than six years.

For more information on the efforts being made to reduce Caltech's environmental impact and promote stewardship within the Caltech community, visit Sustainability at Caltech.

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Lori Oliwenstein
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Solar Decathlon Back on the Mall

Thanks to a campaign led by a joint team of students from Caltech and the Southern California Institute of Architecture (SCI-Arc), the 2011 Solar Decathlon is back on the National Mall in Washington, D.C. The announcement made last week reverses an earlier decision by the U.S. Department of the Interior (DOI) to relocate the event.

The two-week competition, taking place in the fall, will now be held in West Potomac Park, on a swath of land between the Lincoln and Jefferson Memorials. "Everyone's relieved and happy that we're back on the Mall," says Caltech's Fei Yang, a senior majoring in mechanical engineering, and one of the leaders of the SCI-Arc/Caltech team.

The biennial competition, sponsored by the U.S. Department of Energy (DOE), invites 20 teams from around the world and challenges them to build the most energy-efficient, affordable, and attractive house they can. All four previous competitions have taken place on the National Mall—between the Capitol and the Washington Monument—providing a high-profile venue to inspire policymakers, industry leaders, and the public to pursue a sustainable future with state-of-the-art design and technology.

But in January, the DOI, with the approval of the DOE, decided that the event could no longer be held on the Mall, citing the need to protect and preserve the grounds. "It came as a shock," Yang says.

A statement posted January 11 on the DOE Solar Decathlon website noted that the decision to change locations was made "in support of the historic effort underway to protect, improve, and restore the National Mall." The DOI is embarking on a $600 million plan to renovate the grounds and areas around the monuments. But this justification didn't make sense, says Elisabeth Neigert, a recent SCI-Arc graduate and one of the project managers for the SCI-Arc/Caltech team; a clause in each team's contract already makes them financially responsible for any damage.

Furthermore, Neigert says, this sudden change in venue was made three-quarters of the way through the competition, after design, engineering, and logistical decisions had been made based on the expectation that the house would be built on the Mall. And the promise of high-profile exposure was crucial in securing sponsors. "This late in the game, it left us in a really difficult position," she says.

"They tore the heart out of the Solar Decathlon," says Cole Hershkowitz, also a Caltech senior in mechanical engineering and another leader of the team. "One of the reasons why the competition is so prestigious is because the government supported it and it's in arguably the most prominent place in our country, right there between the Capitol and the Washington Monument." There's no monetary prize for the winner, so the prestige and the opportunity to showcase their innovations are the teams' rewards. "If we had known that it would not be on the National Mall, I think only half of us would've applied," Hershkowitz says.  

What followed was a concerted effort led by Neigert and the SCI-Arc/Caltech team to appeal the DOI's decision. Working with the other 19 Solar Decathlon teams, the group of architecture and engineering students suddenly found themselves in the middle of a political campaign. After much lobbying, they received support from organizations such as the National Coalition to Save Our Mall. They also got official backing from more than a dozen senators and other congressional leaders, including California senator Barbara Boxer and Massachusetts representative Edward Markey, ranking member of the Natural Resources Committee.

Then, the Washington Post stepped in to cover the debate, and Neigert and Eric Owen Moss, director of SCI-Arc, penned opinion columns for the Huffington Post. Two days after the op-eds appeared—and after six weeks of relentless campaigning—the DOI reversed its ruling. "I was filled with disbelief, but I was also absolutely elated," Neigert says. "I was pretty speechless, which doesn't happen very often." Even though the event would no longer be right in front of the Capitol steps, the team is satisfied. "It was probably the best outcome we could've gotten, given the circumstances," she says.

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The full-sized model of the SCI-Arc/Caltech house with its soft, insulating exterior.

Now, the team can refocus on building their house, which is computerized to control and monitor energy usage to maximize efficiency. Every house in the competition is required to be net-zero—that is, to use only as much energy as its solar panels can generate. But perhaps what's most striking about the SCI-Arc/Caltech design is its soft, insulating exterior, which gives the building the appearance of a giant pillow. The house is also the only two-story structure in the competition.

With the Solar Decathlon back on the Mall, the team hopes their design will attract plenty of eyes. After all, from historic moments like Martin Luther King's "I Have a Dream" speech to the numerous festivals that attract hundreds of thousands of visitors, the National Mall is a place where things happen and are noticed, Hershkowitz says. "What makes the National Mall so iconic is not how green the grass is, but the quality of events."

The SCI-Arc/Caltech team will hold a groundbreaking event on April 2 at the SCI-Arc campus in Los Angeles.

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Marcus Woo
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Sustaining the Next Generation of Energy Scientists

Training the next generation of scientists capable of creating startling and transformational advances in sustainable energy research is a critical component of the mission of Caltech's Resnick Institute.

And although the institute is not yet two years old—it was created in June of 2009 by a gift from Stewart and Lynda Resnick and began operating the following April—it has already begun to fulfill that mission, thanks to the newly developed Resnick Fellowship program.

The first two Resnick Fellows began their work in the fall of 2010. Last week, the institute put out a call for applications for the next set of two-year awards, which provide tuition plus a $30,000-per-year stipend for graduate students from any discipline who are seeking to explore unusual and creative sustainable-energy research projects on campus.

"The Resnick Fellowships are unique because they provide an opportunity for Caltech students to think outside the box and take a chance on potentially groundbreaking new work in areas that might not otherwise get explored," says Neil Fromer, the institute's executive director. "Caltech has always been a place where creative individuals can have a big impact. With these fellowships, we are similarly enabling students to chart new paths."

As part of his Resnick Fellowship, Matt Smith, a graduate student in bioengineering working in the laboratory of Frances Arnold, is looking for better ways to create second-generation biofuels—biofuels made from cellulose, hemicellulose, or lignin, all of which are components of plant cell walls. Specifically, he's using new protein recombination techniques to try to create active, stable forms of the enzyme beta glucosidase, which is used to cut small-length cellulose chains into individual glucose molecules.

"It's a more unusual, riskier project," Smith says. "When I started talking about it, Frances suggested I apply for a Resnick Fellowship. She felt it was in the spirit of the institute—a project on energy and sustainability that's a bit 'out there.'"

Smith's fellow Fellow, David Abrecht, is working with both Brent Fultz and Theo Agapie on a stationary hydrogen-storage project using ionic liquids. "Hydrogen gas is uneconomical to store," Abrecht explains. But in order to develop hydrogen as a fuel, hydrogen needs to be stored cheaply, at room temperature and pressure, and it needs to be able to release quickly.

The answer, Abrecht says, may lie in liquid storage. "I'd been thinking about liquid-state storage systems for a while," he explains. "Liquid-state storage might allow you to use hydrogen as a buffer to prevent supply spikes in the electrical-generation grid, to fill in the gaps."

Abrecht is looking at what are known as ionic liquids—which are salts in a liquid state—that would be able to bind with hydrogen at more-or-less normal temperatures and pressures. "Trying to find funding for this kind of project from typical sources would have been very difficult," he says. "I would not have been able to do this project without this fellowship."

Smith and Abrecht are looking forward to the next generation of Resnick Fellows. "The more Fellows there are, the more opportunity we'll have for interaction," Smith says. "I'm looking forward to that, to creating a small community of students working toward similar goals."

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Caltech Geobiologists Uncover Links between Ancient Climate Change and Mass Extinction

PASADENA, Calif.—About 450 million years ago, Earth suffered the second-largest mass extinction in its history—the Late Ordovician mass extinction, during which more than 75 percent of marine species died. Exactly what caused this tremendous loss in biodiversity remains a mystery, but now a team led by researchers at the California Institute of Technology (Caltech) has discovered new details supporting the idea that the mass extinction was linked to a cooling climate.

"While it’s been known for a long time that the mass extinction is intimately tied to climate change, the precise mechanism is unclear," says Seth Finnegan, a postdoctoral researcher at Caltech and the first author of the paper published online in Science on January 27. The mass extinction coincided with a glacial period, during which global temperatures cooled and the planet saw a marked increase in glaciers. At this time, North America was on the equator, while most of the other continents formed a supercontinent known as Gondwana that stretched from the equator to the South Pole.

By using a new method to measure ancient temperatures, the researchers have uncovered clues about the timing and magnitude of the glaciation and how it affected ocean temperatures near the equator. "Our observations imply a climate system distinct from anything we know about over the last 100 million years," says Woodward Fischer, assistant professor of geobiology at Caltech and a coauthor.

The fact that the extinction struck during a glacial period, when huge ice sheets covered much of what's now Africa and South America, makes it especially difficult to evaluate the role of climate. "One of the biggest sources of uncertainty in studying the paleoclimate record is that it’s very hard to differentiate between changes in temperature and changes in the size of continental ice sheets," Finnegan says. Both factors could have played a role in causing the mass extinction: with more water frozen in ice sheets, the world’s sea levels would have been lower, reducing the availability of shallow water as a marine habitat. But differentiating between the two effects is a challenge because until now, the best method for measuring ancient temperatures has also been affected by the size of ice sheets.

The conventional method for determining ancient temperature requires measuring the ratios of oxygen isotopes in minerals precipitated from seawater. The ratios depend on both temperature and the concentration of isotopes in the ocean, so the ratios reveal the temperature only if the isotopic concentration of seawater is known. But ice sheets preferentially lock up one isotope, which reduces its concentration in the ocean. Since no one knows how big the ice sheets were, and these ancient oceans are no longer available for scientists to analyze, it's hard to determine this isotopic concentration. As a result of this "ice-volume effect," there hasn’t been a reliable way to know exactly how warm or cold it was during these glacial periods.

Rock strata on Anticosti Island, Quebec, Canada, one of the sites from which the researchers collected fossils.

But by using a new type of paleothermometer developed in the laboratory of John Eiler, Sharp Professor of Geology and professor of geochemistry at Caltech, the researchers have determined the average temperatures during the Late Ordovician—marking the first time scientists have been able to overcome the ice-volume effect for a glacial episode that happened hundreds of millions of years ago. To make their measurements, the researchers analyzed the chemistry of fossilized marine animal shells collected from Quebec, Canada, and from the midwestern United States.

The Eiler lab’s method, which does not rely on the isotopic concentration of the oceans, measures temperature by looking at the "clumpiness" of heavy isotopes found in fossils. Higher temperatures cause the isotopes to bond in a more random fashion, while low temperatures lead to more clumping.

"By providing independent information on ocean temperature, this new method allows us to know the isotopic composition of 450-million-year-old seawater," Finnegan says. "Using that information, we can estimate the size of continental ice sheets through this glaciation." And with a clearer idea of how much ice there was, the researchers can learn more about what Ordovician climate was like—and how it might have stressed marine ecosystems and led to the extinction.

"We have found that elevated rates of climate change coincided with the mass extinction," says Aradhna Tripati, a coauthor from UCLA and visiting researcher in geochemistry at Caltech.

The team discovered that even though tropical ocean temperatures were higher than they are now, moderately sized glaciers still existed near the poles before and after the mass extinction. But during the extinction intervals, glaciation peaked. Tropical surface waters cooled by five degrees, and the ice sheets on Gondwana grew to be as large as 150 million cubic kilometers—bigger than the glaciers that covered Antarctica and most of the Northern Hemisphere during the modern era’s last ice age 20,000 years ago.

"Our study strengthens the case for a direct link between climate change and extinction," Finnegan says. "Although polar glaciers existed for several million years, they only caused cooling of the tropical oceans during the short interval that coincides with the main pulse of mass extinction."

In addition to Finnegan, Eiler, Tripati, and Fischer, the other authors on the Science paper, "The magnitude and duration of Late Ordovician-Early Silurian glaciation magnitude," are Kristin Bergmann, a graduate student at Caltech; David Jones of Amherst College; David Fike of Washington University in St. Louis; Ian Eisenman, a postdoctoral scholar at Caltech and the University of Washington; and Nigel Hughes of the University of California, Riverside.

This research was funded by the Agouron Institute and the National Science Foundation.
 

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Marcus Woo
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Obama Touts Caltech Research

In last night's State of the Union Address, President Obama said, "We're issuing a challenge. We're telling America's scientists and engineers that if they assemble teams of the best minds in their fields, and focus on the hardest problems in clean energy, we'll fund the Apollo projects of our time. At the California Institute of Technology, they're developing a way to turn sunlight and water into fuel for our cars. At Oak Ridge National Laboratory, they're using supercomputers to get a lot more power out of our nuclear facilities. With more research and incentives, we can break our dependence on oil with biofuels, and become the first country to have a million electric vehicles on the road by 2015." Watch video of the speech.

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Allison Benter
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New Reactor Paves the Way for Efficiently Producing Fuel from Sunlight

PASADENA, Calif.—Using a common metal most famously found in self-cleaning ovens, Sossina Haile hopes to change our energy future. The metal is cerium oxide—or ceria—and it is the centerpiece of a promising new technology developed by Haile and her colleagues that concentrates solar energy and uses it to efficiently convert carbon dioxide and water into fuels.

Solar energy has long been touted as the solution to our energy woes, but while it is plentiful and free, it can't be bottled up and transported from sunny locations to the drearier—but more energy-hungry—parts of the world. The process developed by Haile—a professor of materials science and chemical engineering at the California Institute of Technology (Caltech)—and her colleagues could make that possible. 

The researchers designed and built a two-foot-tall prototype reactor that has a quartz window and a cavity that absorbs concentrated sunlight. The concentrator works "like the magnifying glass you used as a kid" to focus the sun's rays, says Haile.

At the heart of the reactor is a cylindrical lining of ceria. Ceria—a metal oxide that is commonly embedded in the walls of self-cleaning ovens, where it catalyzes reactions that decompose food and other stuck-on gunk—propels the solar-driven reactions. The reactor takes advantage of ceria's ability to "exhale" oxygen from its crystalline framework at very high temperatures and then "inhale" oxygen back in at lower temperatures.

"What is special about the material is that it doesn't release all of the oxygen. That helps to leave the framework of the material intact as oxygen leaves," Haile explains. "When we cool it back down, the material's thermodynamically preferred state is to pull oxygen back into the structure."

The ETH-Caltech solar reactor for producing H2 and CO from H2O and CO2 via the two-step thermochemical cycle with ceria redox reactions.

Specifically, the inhaled oxygen is stripped off of carbon dioxide (CO2) and/or water (H2O) gas molecules that are pumped into the reactor, producing carbon monoxide (CO) and/or hydrogen gas (H2). H2 can be used to fuel hydrogen fuel cells; CO, combined with H2, can be used to create synthetic gas, or "syngas," which is the precursor to liquid hydrocarbon fuels. Adding other catalysts to the gas mixture, meanwhile, produces methane. And once the ceria is oxygenated to full capacity, it can be heated back up again, and the cycle can begin anew.

For all of this to work, the temperatures in the reactor have to be very high—nearly 3,000 degrees Fahrenheit. At Caltech, Haile and her students achieved such temperatures using electrical furnaces. But for a real-world test, she says, "we needed to use photons, so we went to Switzerland." At the Paul Scherrer Institute's High-Flux Solar Simulator, the researchers and their collaborators—led by Aldo Steinfeld of the institute's Solar Technology Laboratory—installed the reactor on a large solar simulator capable of delivering the heat of 1,500 suns.

In experiments conducted last spring, Haile and her colleagues achieved the best rates for CO2 dissociation ever achieved, "by orders of magnitude," she says. The efficiency of the reactor was uncommonly high for CO2 splitting, in part, she says, "because we're using the whole solar spectrum, and not just particular wavelengths." And unlike in electrolysis, the rate is not limited by the low solubility of CO2 in water. Furthermore, Haile says, the high operating temperatures of the reactor mean that fast catalysis is possible, without the need for expensive and rare metal catalysts (cerium, in fact, is the most common of the rare earth metals—about as abundant as copper).

In the short term, Haile and her colleagues plan to tinker with the ceria formulation so that the reaction temperature can be lowered, and to re-engineer the reactor, to improve its efficiency. Currently, the system harnesses less than 1% of the solar energy it receives, with most of the energy lost as heat through the reactor's walls or by re-radiation through the quartz window. "When we designed the reactor, we didn't do much to control these losses," says Haile. Thermodynamic modeling by lead author and former Caltech graduate student William Chueh suggests that efficiencies of 15% or higher are possible.

Ultimately, Haile says, the process could be adopted in large-scale energy plants, allowing solar-derived power to be reliably available during the day and night. The CO2 emitted by vehicles could be collected and converted to fuel, "but that is difficult," she says. A more realistic scenario might be to take the CO2 emissions from coal-powered electric plants and convert them to transportation fuels. "You'd effectively be using the carbon twice," Haile explains. Alternatively, she says, the reactor could be used in a "zero CO2 emissions" cycle: H2O and CO2 would be converted to methane, would fuel electricity-producing power plants that generate more CO2 and H2O, to keep the process going.

A paper about the work, "High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria," was published in the December 23 issue of Science. The work was funded by the National Science Foundation, the State of Minnesota Initiative for Renewable Energy and the Environment, and the Swiss National Science Foundation.

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Kathy Svitil
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Caltech and the Clean-Energy "Sputnik Moment"

The quest for clean energy, and our country's competitiveness both now and in the future is, according to Secretary of Energy Steven Chu (seen here in a photo from Caltech's 2009 Commencement ceremonies), our "Sputnik Moment."

"From wind power to nuclear reactors to high-speed rail," Chu noted in a speech to the National Press Club on Monday, November 29, "China and other countries are moving aggressively to capture the lead. Given that challenge, and given the enormous economic opportunities in clean energy, it's time for America to do what we do best: innovate."

Where to find that innovation? At Caltech, of course. More specifically—as Chu pointed out in his descriptions of some of the top technological innovators in the United States—at the Joint Center for Artificial Photosynthesis. JCAP, a DOE Energy Innovation Hub headed by Caltech's Nate Lewis and his Lawrence Berkeley National Lab counterpart, Peidong Yang, is focused on producing a fully artificial version of photosynthesis with no living components or wires.

In his speech, Chu spoke of JCAP as "a program that will produce abundant domestic fuel directly from sunlight."

Look at the way a plant makes chemical energy. It takes sunlight, it takes water, and it uses sunlight and energy to split the water into hydrogen and oxygen. And it takes carbon dioxide, and reduces the carbon dioxide and builds a carbohydrate that we can then turn into a sugar that can turn into a fuel.
And so the question is, can we design, using nanotechnology, something that begins to replicate what a plant does? But we have an advantage. We have access to materials that the wet biological world doesn't have access to, therefore, we can in principle design something better… We decided that in the last couple of years there's been enough advances in science and nanotechnology that we have a shot. In maybe five, ten years, this can really happen in a cost-effective way. And so an Energy Innovation Hub has been started to fund that type of research.

Secretary Chu's speech can be viewed in its entirety on the National Press Club's website.

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Lori Oliwenstein
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Alternative Transportation Programs Honored

Five years ago, Caltech's transportation office had one vanpool and just 150 participants in its Bike-to-Work and Walk-to-Work programs. Today, the university boasts 13 vanpools, 150 carpoolers, and nearly 1100 Bike- and Walk-to-Work participants—along with a wide array of other commuter services, including transit subsidies, telework and flextime options, Zipcar rentals, secure bike-storage facilities, and more. Caltech's commuter- and environmentally friendly programs haven't gone without notice. Indeed, the university recently was singled out for a corporate Blue Diamond Award by the Los Angeles County Metropolitan Transportation Authority. The award is given annually to a company that has proven itself a leader in ridesharing, with an active and visible presence in the commuter transportation field.

"Ridesharing has a number of benefits for Caltech employees, including reduced commuting costs, more commuting options, increased personal time, decreased stress, better health, and the chance to make new friends," says Kristina Valenzuela, Caltech's employee transportation coordinator, who accepted the Blue Diamond Award on behalf of the university at a ceremony in September. "Caltech as a whole benefits by retaining employees, increasing employee productivity, reducing congestion, and improving air quality around the campus," she says.

Valenzuela—who is herself in a commuter vanpool ("I do practice what I preach," she says)—continues to explore innovative alternative transportation options. In September, for example, the Rideshare office instituted a folding bike loaner program on campus. For a $20 refundable deposit, Caltech students, faculty, and staff can rent one of two folding bikes from the Parking office at 515 S. Wilson, plus a helmet and lock, "to do errands, go to meetings or just enjoy a bike ride," she says.

Not content to rest on her success, Valenzuela plans to soon expand the bikeshare program and also hopes to install a one-stop bicycle parking area and service facility on campus. "I've applied for a grant to put a Bikestation here on campus," she says. "If the grant is approved, this will be a stand-alone secure bicycle parking facility. The facility will be fully self-contained with a solar electrical system and will offer bicycle commuters service amenities such as lockers and work bench area for small repairs, a free air station, and a hand washing area."

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Kathy Svitil
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Caltech/JPL Experiments Improve Accuracy of Ozone Predictions in Air-Quality Models

Team says current models may underestimate ozone levels; findings made by characterizing rates of key chemical reactions

PASADENA, Calif.—A team of scientists led by researchers from the California Institute of Technology (Caltech) and NASA's Jet Propulsion Laboratory (JPL) have fully characterized a key chemical reaction that affects the formation of pollutants in smoggy air. The findings suggest that in the most polluted parts of Los Angeles—and on the most polluted days in those areas—current models are underestimating ozone levels, by between 5 to 10 percent.

The results—published in this week's issue of the journal Science—are likely to have "a small but significant impact on the predictions of computer models used to assess air quality, regulate emissions, and estimate the health impact of air pollution, " says Mitchio Okumura, professor of chemical physics at Caltech and one of the principal investigators on the research.

“This work demonstrates how important accurate laboratory measurements are to our understanding of the atmosphere,” added JPL Senior Research Scientist Stanley P. Sander, who led that team's effort.

The key reaction in question in this research is the reaction between nitrogen dioxide, NO2, and the hydroxyl radical, OH. In the presence of sunlight, these two, along with volatile organic compounds (VOCs), play important roles in the chemical reactions that form ozone.

Until the last decade or so, it was thought that NO2 and OH combine only to make nitric acid, HONO2, a fairly stable molecule with a long lifespan in the atmosphere. "HONO2, or nitric acid, dissolves in rainwater, so that the molecules get washed away," Okumura explains. "It's basically a sink for these radicals, taking them out of the ozone equation and thus slowing down the rate of ozone formation."

Chemists had suspected, however, that a second reaction might occur as well: one that creates a compound called HOONO (pronounced WHO-no), otherwise known as peroxynitrous acid. HOONO is much less stable in the atmosphere, falling apart quickly after being created, and thus releasing the OH and NO2 back for use in the ozone-creation cycle.

But what was not known with any reasonable certainty—until now—is how fast these reactions occur, and how much HONO2 is created relative to the amount of HOONO created. Those relative amounts are known as the branching ratio, so called because OH and NO2 can chemically transform, or branch, into either HONO2 or HOONO.

Enter the Caltech and JPL teams. The JPL team took the lead on measuring the rate at which the OH + NO2 reaction produces both HONO2 and HOONO. They did this using "an advanced chemical reactor built at JPL that was designed to measure reaction rates with very high accuracy," says Sander.

Once the scientists had determined the combined reaction rate for the two possible products—coming up with rates that are on the higher rather than the lower end of the scale of previous estimates—the Caltech group took the lead to try to uncover the branching ratio, or the ratio of the rates of the two separate processes.

Using a powerful laser measurement technique called cavity ringdown spectroscopy, the team was able to detect both products being created in the lab in real time, says Okumura. "We could start the reaction and watch, within microseconds, the products being formed," he says. "That allowed us to measure the species immediately after they were formed, and before they got lost in other side reactions. That is what allowed us to figure out the branching ratio."

Because HOONO was not a well-studied molecule, another key was using state-of-the-art theoretical calculations; for this, the authors enlisted Anne McCoy, professor of chemistry at The Ohio State University. “Solving this atmospheric chemistry problem required us to use many tools from modern chemical physics,” says Okumura.

"This work was the synthesis of two very different and difficult experiments," adds Andrew Mollner, the Science paper's first author and a former Caltech graduate student who is now at the Aerospace Corporation. "While neither experiment in isolation provided definitive results, by combining the two data sets, the parameters needed for air-quality models could be precisely determined."

In the end, what they found was that the loss of OH and NO2 is slower than what was previously thought—although the reactions are fast, fewer of the radicals are going into the nitric acid sink than had been supposed, and more of it is ending up as HOONO. "This means less of the OH and NO2 go away, leading to proportionately more ozone, mostly in polluted areas," Okumura says.

Just how much more? To try to get a handle on how their results might affect predictions of ozone levels, they turned to Robert Harley, professor of environmental engineering at the University of California, Berkeley, and William Carter, a research chemist at the University of California, Riverside—both experts in atmospheric modeling—to look at the ratio's impact on predictions of ozone concentrations in various parts of Los Angeles during the summer of 2010.

The result: "In the most polluted areas of L.A.," says Okumura, "they calculated up to 10 percent more ozone production when they used the new rate for nitric acid formation."

Okumura adds that this strong effect would only occur during the times of the year when it's most polluted, not all year long. Still, he says, considering the significant health hazards ozone can have—recent research has reported that a 10 part-per-billion increase in ozone concentration may lead to a four percent increase in deaths from respiratory causes—any increase in expected ozone levels will be important to "people who regulate emissions and evaluate health risks." The precision of these results reduces the uncertainty in the models—an important step in the ongoing effort to improve the accuracy of the models used by those policymakers.

Okumura believes that this work will cause other scientists to reevaluate recommendations made to modelers as to the best parameters to use. For the team, however, the next step is to start looking at "a wider range of atmospheric conditions where this reaction may also be very important."

Sander agrees. "The present work focused on atmospheric conditions related to urban smog—i.e., relatively warm temperatures and high atmospheric pressure," he says. "But the OH + NO2 reaction is important at many other altitudes. Future work by the two groups will focus on the parts of the atmosphere affected by long-range transport of pollution by high-altitude winds (the middle and upper troposphere) and where ozone depletion from man-made substances is important (the stratosphere)."

In addition to Okumura, Sander, Mollner, McCoy, Harley, and Carter, the other authors on the Science paper, "Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide," are postdoctoral fellow Lin Feng and graduate student Matthew Sprague, both from Caltech; former JPL postdoctoral researchers Sivakumaran Valluvadasan, William Bloss, and Daniel Milligan; and postdoctoral fellow Philip Martien from the University of California, Berkeley.

Their work was supported by grants from NASA, the California Air Resources Board, and the National Science Foundation, and by a NASA Earth Systems Science Fellowship and a Department of Defense National Defense Science and Engineering Graduate Fellowship.

JPL is a federally funded research and development facility managed by Caltech for NASA.

Writer: 
Lori Oliwenstein
Writer: 

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