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Checking Oil's I.D.

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Checking Oil's ID

Despite everything, fossil fuels will be with us for a long time. Here's news of a way to make the most of earth's remaining crude oil reserves.

Call it trickle-down science.

Few natural resources are as prized as crude oil. Turns out, it's also by far the most chemically complex of them all—nature makes it in staggering varieties.

Many people are surprised to learn that all crude isn't the same. Oil pumped from one well can be vastly different from oil found only a few miles away. Of late, companies have become increasingly aware of this fact as easily accessible, quality oil reserves have become harder to find and drill.

The phenomenon poses serious supply-side problems, experts say. Every drop of black gold can contain tens of thousands of compounds, some of which can corrode or clog pipes, pollute too much or be too much trouble to drill for. Considering the oil dilemma the U.S. faces today, it's a problem begging for a solution.

A lab run by FSU chemist Alan Marshall may hold the answer. A professor of chemistry and biochemistry, Marshall has spent his career prying secrets from complex substances, using a revolutionary analytical tool he co-invented and has refined over the decades. Now he says he wants to share that ability with oil companies—Knowledge that may eventually help consumers deal with wildly fluctuating prices at the gas pump.

"We want as many people as possible to benefit from what we know," said Marshall, who directs the Ion Cyclotron Resonance program at the National High Magnetic Field Laboratory, headquartered at and partly operated by FSU. "We can't do this all by ourselves, so it's better to have a company that has the responsibility to spread the ideas around."

Mother of Invention

Until recently, oil companies had little need for fancy analyses of their product. They were pumping up the cream of the crude—sweet, light crude, in the parlance of the industry, meaning low in sulfur and low density. It was as simple as canola oil, and easily refined into profitable products from gasoline to heating oil to asphalt.

But with our avid appetite for Texas tea—the world guzzles some 30 billion barrels of it a year, a quarter of that in the U.S.—we've burned up much of the good stuff that's easy to reach. Burgeoning economies in China, India and elsewhere are demanding a greater share. Oil companies have had to turn to the less desirable, less profitable crudes. Consumers, still reeling from recent record high prices for gasoline, diesel fuel and heating oil, have begun to feel the consequences of more expensive exploration and processing.

These sour, heavy crudes are tricky mixtures, Marshall said. Without a careful chemical analysis, an oil company could make some very costly mistakes.

"The petroleum industry is making this transition on the fly," explained Ryan Rodgers, director of environmental, petroleum and forensic applications in Marshall's group. "Sometimes things can go terribly wrong." Rodgers offered the cautionary tale of a refinery built to last for 30 years. Unbeknownst to the operators, their oil was full of acids. Within 18 months, their pipes had rusted through.

Chemical analyses cost money, but the price of ignorance is often higher.

"You didn't need it when the oil was simple and straw-colored and easy to pour," noted Marshall. "But as those rules change, you're going to need to know more about the sample."

Oil companies began coming to Marshall in the 1990s, drawn by the promise of his pioneering work in a field known as ion cyclotron resonance mass spectrometry. Developed by physicists in the 1930s, the technique uses radio waves to bombard fields of electrically charged molecules, or ions, of a wide variety of complex substances. When confined to a high-intensity magnetic field, the ions are forced into distinct orbits, sorted out by molecular weight, by the radio waves. The technique thereby gave scientists a useful, if extremely slow, tool for sorting out the ingredients in a complex substance.

But in 1973, Marshall co-invented (with Melvin Comisarow of the University of British Columbia) a vast improvement on the process. The new method, based on Fourier transform technology dramatically increased the speed of analysis as well as the accuracy. Since joining the High Magnetic Field Laboratory in 1990, Marshall has steadily improved the technique with the aid of the lab's powerful array of magnets. Today, the tool can rapidly identify with uncanny accuracy and resolution.

Thanks to Marshall's aggressive development of the technique—along with Nobel Prize-winning advances in ionization methods—the field of Fourier transform-based spectrometry has exploded over the years. The technique is used to study of a wide range of macromolecules, from proteins to explosives to pharmaceuticals. Petroleum, formed miles beneath the Earth's surface from ancient algae and zooplankton, is the most complex organic material on the planet, and thus a natural target for his analytical tool, Marshall said.

"In 70 million years," said Marshall, "at high temperature and pressure, nature has made just about every possible combination of atoms in these molecules, up to a certain size."

Marshall's group has amassed a database of 60,000 different substances they have detected in crude oil. The group pioneered, and continues to dominate, the field of petroleomics—the study of crude oil.

Bad apples

In some ways, crude oil is actually quite simple, made up mostly of hydrogen and carbon atoms. But they can be arranged in a seemingly infinite variety of ways. And a sprinkling of trouble-causing ingredients (sulfur, nitrogen and oxygen are the primary culprits) keeps things interesting for chemists—and creates headaches for oil companies. In mega molecules dominated by hard-working, hydrogen and carbon, a few bad atoms have the optential to spoil the whole bunch.

Sulfur is a harmful polluter, tightly controlled by the Environmental Protection Agency. Oxygen can rust pipes; nitrogen clogs them up, and pollutes as well.

The first step in getting rid of these problem atoms is finding them. Where in the molecular maze of C's and H's, of chains and rings and double and single bonds, are those offending N's, S's and O's hiding out?

Despite the advances brought by Marshall's technique, it still can take weeks of sorting through the mountain of data produced—studying and calculating, juggling Excel spreadsheets and Access databases—to completely figure out what's in a sample of crude. The speed of Marshall's machines was of little use if it took months to figure out what the data meant. Oil companies needed to make critical decisions much faster than that. "They need the information now," said Rodgers.

Marshall's team eventually solved the problem by developing a set of powerful algorithms that a computer can use to deftly cut through the maze of data quickly and efficiently. The software has the potential to revolutionize the process of characterizing crude oil, Marshall believes.

"If you're interested in sulfur-containing molecules, we can zoom in on just those," explained Marshall. "If it's acids, we can zoom in on just those. So we can pick out particular things, particular components that have the properties you're interested in."

In 2008 Marshall's lab signed a licensing agreement with a California-based software firm, Sierra Analytics. The company's main job is to take the powerful software developed by Marshall's group, put it on the market, and keep it current through close ties with Marshall's team. Sierra Analytics president David Stranz said his customers are floored to find out that manual analyses that previously took months to complete could, with the new software, be churned out in minutes.

That type of turn-around can save oil companies significant time and money. A sample extracted from deep at sea, for example, could be sent ashore for testing. Within days the company would know whether to keep drilling—or cut bait and hunt elsewhere. Companies can also monitor their work in real time, periodically analyzing the oil as they refine it and fine-tuning their techniques accordingly.

"I think the most exciting thing about it is that, for the first time, we're taking research in a very complicated area and making it commercially accessible," said Stranz. "Because of the difficulty of getting the information out of the data, it's been pretty much unattractive for oil companies to get into the business of analyzing this data themselves."

As expertise trickles down from academia to industry, the consumer stands to benefit from not just lower prices, but a cleaner environment, as well. In some of the heavier crude oils, up to half of what's pumped out ends up as trash.

"This stuff doesn't boil," said Rodgers. "If they don't find something to do with this material, they're going to bury it." The more a company knows about its crude oil, the more efficiently and effectively it can process it.

Marshall's technique can also disclose the origin of oil seepages (natural or man-made?) and provide information on how it diffuses in water and degrades on land. And by pinpointing the nitrogen and oxygen in a sample, the reports help companies get rid of these destructive substances, thus lowering the chance of oil spills by preventing blocked and corroded pipes. Rodgers calls it good molecular management.

Lab to Real Life

The collaboration benefits the company with an exciting new product in a market that stands to mushroom as drillable petroleum reserves become harder to find. And it benefits the university by creating greater visibility in a vital worldwide industry for research conducted at the mag lab. Still, those benefits are eclipsed, Marshall says, by the good that will come of getting the powerful new tool in the hands of those who can make the best use of it.

"We don't want to be the only ones in the world that can do this," said Marshall. "We want everybody to be able to do that."

"Helping the oil companies does help at the pump, but it also makes them better stewards of the resources they're taking from the ground," Rodgers said. "So hopefully we're helping them use them as wisely as possible."

Few scientists ever see their basic research bear practical fruit. Marshall, as busy as ever at 64, has experienced that satisfaction. The small ripple of an idea that first occurred to him as a 20-something professor gradually grew into a wave that revolutionized analytical chemistry. That wave has now washed over from academia into industry. If it fulfills its promise, it will ultimately lap across the toes of every consumer on the planet. It's a feat Marshall can be reminded of every time he fills up the tank of his red sports car.

Recalling those early days when his now snowy moustache was still dark brown, Marshall allows himself a satisfied grin.

"We started this in '73," he says, crow's feet crinkling, papers piled high around him in his mag lab corner office. "That's 35 years. Good thing I was 30 at the time."



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