Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation. Fuchs, H., Hofzumahaus, A., Rohrer, F., Bohn, B., Brauers, T., Dorn, H., Häseler, R., Holland, F., Kaminski, M., Li, X., Lu, K., Nehr, S., Tillmann, R., Wegener, R., & Wahner, A. Nature Geoscience, 6(12):1023-1026, Nature Publishing Group, 10, 2013.
Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation [pdf]Paper  Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation [link]Website  abstract   bibtex   
Most pollutants in the Earth’s atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene1–8. Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed5,9–11. Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain12–14. Here,we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene- derived peroxy radicals postulated by quantum chemical calculations9–11. Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions
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 title = {Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation},
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 abstract = {Most pollutants in the Earth’s atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene1–8. Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed5,9–11. Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain12–14. Here,we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene- derived peroxy radicals postulated by quantum chemical calculations9–11. Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions},
 bibtype = {article},
 author = {Fuchs, H. and Hofzumahaus, A. and Rohrer, F. and Bohn, B. and Brauers, T. and Dorn, H-P. and Häseler, R. and Holland, F. and Kaminski, M. and Li, X. and Lu, K. and Nehr, S. and Tillmann, R. and Wegener, R. and Wahner, A.},
 journal = {Nature Geoscience},
 number = {12}
}
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