Volume 83, Number 34 p. 9 |
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ATMOSPHERIC CHEMISTRY |
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Radioactive carbon monoxide is used to trace key atmospheric "cleanser" |
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Until now, scientists have inferred atmospheric levels of the radical, which has a lifetime of one second, largely by measuring concentrations of methyl chloroform, a man-made molecule that reacts almost exclusively with OH. Nobel Laureate F. Sherwood Rowland, chemistry professor at the University of California, Irvine, introduced the method in the early 1980s. But methyl chloroform, an ozone-depleting compound, has been banned, and its concentrations in the atmosphere are dwindling. The new study by Martin R. Manning, a director of the United Nations Intergovernmental Panel on Climate Change support unit at the National Oceanic & Atmospheric Administration in Boulder, Colo., and colleagues makes use of 14CO, a rare atmospheric gas also oxidized by OH. Like methyl chloroform, CO levels presumably decrease when there's more OH around.
Manning's group collected an enormous trove of 14CO measurements, spanning 13 years, from the Southern Hemisphere, in Baring Head, New Zealand, and in Antarctica (Nature 2005, 436, 1001). Overall, they find, there's been no large rise or drop in atmospheric OH. The researchers can infer fluctuations in OH levels lasting a period of a few months, however. The Pinatubo eruption, as well as a rash of forest fires in Indonesia in 1997, led to OH declines as large as 20%, they report. Their findings are similar to OH levels inferred from methyl chloroform measurements reported by atmospheric chemistry professor Ronald G. Prinn at Massachusetts Institute of Technology and colleagues (Geophys. Res. Lett. 2005, 32, 07809). "This is a very interesting measurement" that Manning's group has produced, Rowland says. "14CO should become the principal diagnostic tool for monitoring the oxidative capacity of the atmosphere," say Patrick Jöckel and Carl A. M. Brenninkmeijer of Max Planck Institute for Chemistry in Mainz, Germany, in a commentary accompanying the Nature report. "This tracer is a cosmic dowry for atmospheric chemists." Manning says a confluence of technological and modeling advances made the work possible--most notably, the capability to accurately determine how much 14CO is produced in the atmosphere. Protons in cosmic rays hitting Earth's atmosphere produce neutrons, which react with 14N nuclei to produce excited 14C, which quickly reacts with O2 to form 14CO. Complicating matters is the 11-year cycle of solar activity that affects cosmic radiation. The amounts of 14CO produced are also extremely small--only about 10 atoms per cm3--requiring sensitive detector technology. Jos Lelieveld, director of the atmospheric chemistry department at Max Planck Institute for Chemistry, who also calls the work "very interesting," and Rowland both note that further measurements and modeling will be needed to nail down the inherent complexity and uncertainty of atmospheric OH. |
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