Isoprene photochemistry over the Amazon rainforest

Journal Article · Tue May 31 00:00:00 EDT 2016 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1524136113· OSTI ID:1575422

Liu, Yingjun ^[1]; Brito, J ^[2]; Dorris, Matthew R. ^[3]; Rivera-Rios, Jean ^[4]; Seco, Roger ^[5]; Bates, Kelvin H. ^[6]; Artaxo, Paulo ^[3]; Duvoisin, Sergio ^[7]; Keutsch, Frank N. ^[4]; Kim, Saewung ^[8]; Goldstein, Allen H. ^[9]; Guenther, Alex B. ^[10]; Manzi, Antonio ^[7]; Souza, Rodrigo A. ^[7]; Springston, Stephen R. ^[11]; Watson, Tom B. ^[11]; McKinney, Karena ^[1]; Martin, Scot T. ^[1]; Martin, Scot T. ^[1]

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1. Harvard University
2. University of Sao Paulo, Brazil
3. Universidade de Sao Paulo
4. University of Wisconsin-Madison
5. University of California, Irvine
6. California Institute of Technology
7. Universidade do Estado do Amazonas
8. University of California
9. University of California, Berkeley
10. BATTELLE (PACIFIC NW LAB)
11. Brookhaven National Laboratory

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to domi-nantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1575422
• Report Number(s): PNNL-SA-118324
• Journal Information: Proceedings of the National Academy of Sciences of the United States of America, Vol. 113, Issue 22
• Country of Publication: United States
• Language: English