03/05/2008
Atmospheres
Frank Sherwood Rowland and I share a number of things in common. We were both born in 1927. He skipped fourth grade while I skipped first and 12th grades. We both entered college in 1943, he at Ohio Wesleyan, I at Dickinson. We both loved baseball; I got my varsity letter in baseball at Dickinson and he not only played semipro ball in Canada but also managed a team that won the Canadian championship. In graduate school, we both worked with radioactive atoms, he with bromine and I with sulfur. There are some differences, however. He stands 6 feet 5 inches while I’m only 5 feet 8 inches (used to be 5’10”). Oh, Rowland was awarded a Nobel Prize; I’ve gotten a couple of awards but none anywhere near the prestige or importance of a Nobel.
What prompted this column on Rowland is an article by Bette Hileman on the man titled “A Giant Among Chemists” in the December 24, 2007 issue of Chemical and Engineering News (C&EN). I’ve probably written about Rowland in an earlier column but in these days of concern about global warming and with many still questioning its existence, it’s worth recalling Rowland’s work over three decades ago that showed man can put things into the atmosphere with global consequences. The 1995 Nobel Prize in Chemistry was awarded to Rowland, Mario Molina and Paul Crutzen for their work showing how chlorofluorocarbons (CFCs), notably Freon used in refrigeration, aerosol sprays and the like, destroy ozone in the stratosphere.
In 1972, Rowland attended a conference in Florida where work by a British scientist, James Lovelock, was reported. Lovelock had detected CFCs in the atmosphere in an amount almost equal to all the CFCs ever produced to that point. It was assumed at the time that the CFCs were inert and were of no threat in the atmosphere. Rowland, however, realized that if the CFCs reached the stratosphere, up there some 8 to 30 miles above the earth, it would be a different story. Specifically, he believed that short-wavelength ultraviolet radiation would break down the CFCs.
In late 1973, Rowland and Molina, a postdoc in Rowland’s group at the University of California, Irvine, calculated that the UV radiation would cause the CFCs to lose chlorine atoms. These chlorine atoms would then react in a sort of chain reaction with the ozone and lead to a reduction in the amount of ozone in the ozone layer that protects us earthlings, as well as other plant and animal life, from the powerful UV radiation. They calculated that, if CFC production continued at the rate at the time, 7 to 13 percent of the ozone layer would be lost. Actually, the rate of CFC production was then rising at about 10 percent a year and the researchers predicted the ozone layer losses would be even greater.
Rowland and Molina realized the importance of their calculations and submitted a paper to the journal Nature. The paper was published in June that year. Crutzen, a meteorologist, was among a group of scientists who confirmed the calculations shortly afterward. By 1976, the scientific community and Congress got into the act and the U.S. banned nonessential uses of CFCs in aerosol propellants. However, Europe and Japan continued using CFCs as aerosol propellants and CFCs were still being used worldwide as refrigerants.
Reminiscent of today’s skeptics on global warming, there was strong resistance to the calculations from the CFC industry, not surprising, but also from some scientists and government officials. The argument was that these were only calculations and that there was no proof that the ozone layer was being affected. Unbelievably, it turned out that the data was there all along. The British Antarctic Survey had been measuring the total amount of ozone in the atmosphere for decades. The unbelievable part is that the instrument used to measure the ozone was programmed to reject what were considered “outliers” in the data. That is, any measurement that seemed too high or too low was eliminated from the final output of the instrument!
Well, in 1984, ten years after the publication of the paper in Nature, Joseph Farman and his colleagues at the British Antarctic Survey decided to look at the raw data from the instrument and, sure enough, they found that since the 1960s the ozone layer was greatly reduced and in 1985 they published a paper in Nature showing a 40 percent reduction in the ozone layer in late September. Their results were confirmed the next year by satellite data. By 1987, the world finally was convinced and the path to a total halt in the use of CFC and other ozone-depleting compounds had begun.
All this is history. I was intrigued that, at my age, 80-year-old Rowland is still at UC Irvine and he and another chemist, Donald Blake, head a research group that still studies the atmosphere. Only now they define two atmospheres – the conventional one and another they call the “inner atmosphere”. They continue to study the trace amounts of various compounds such as methane in the atmosphere and have postulated that ups and downs in methane concentrations are related to such factors as uncapped old oil and gas wells and to burning of biomass, e.g., forest fires. Decreases in the amount of methane are thought most likely to be due to capping of leaks in the oil and gas wells. On the other hand there have been periods of increases in both methane and ethane, which are attributed to large conflagrations such as the 1997 fires in Indonesia.
The Irvine group has also been studying the inner atmosphere of breath. Specifically, they want to know what we breathe in and out. Two of their studies involved diabetics and cystic fibrosis patients. The atmosphere has a concentration of a compound called carbonyl sulfide, roughly at a level of about 600 parts per trillion (ppt). Normally a healthy person breathes in the 600 ppt and exhales only about 350 ppt of the compound. On the other hand, cystic fibrosis patients exhale about 490 ppt of the compound. The speculation is that bacteria in the lungs of the CF patients make carbonyl sulfide, accounting for the higher level in their breath. Thus there’s the possibility that measuring the breath could lead to a method of measuring the amount of bacteria in the CF lungs.
In diabetics, the group has found that as the blood sugar goes up in diabetics there is an increase in the compound methyl nitrate in the breath. If a convenient test for methyl nitrate can be developed, there’s a chance that it could replace the need for sampling of blood. At 80, Rowland is still making contributions on a global as well as on a very personal scale.
Finally, I want to thank readers Charles K and Steve G, a former neighbor, for their interest in my wife’s condition. I’m happy to say that this week I got her out to the mall for a walk, her first since her fall on January 9. And yesterday we attended a mall walkers luncheon at a Chinese restaurant in the area, her first meal out since coming home from rehab. That meant yesterday I didn’t have to cook. Things are looking up!
Allen F. Bortrum
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