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Title: Isoprene photochemistry over the Amazon rainforest

Abstract

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 (HO 2 ) to dominantly 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 HO 2 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, forestedmore » 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.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1253389
Alternate Identifier(s):
OSTI ID: 1336083
Report Number(s):
BNL-112478-2016-JA
Journal ID: ISSN 0027-8424; /pnas/113/22/6125.atom
Grant/Contract Number:  
0; SC00112704
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 22; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; isoprene photochemistry; Amazon; organic hydroperoxides

Citation Formats

Liu, Yingjun, Brito, Joel, Dorris, Matthew R., Rivera-Rios, Jean C., Seco, Roger, Bates, Kelvin H., Artaxo, Paulo, Duvoisin, Jr., Sergio, Keutsch, Frank N., Kim, Saewung, Goldstein, Allen H., Guenther, Alex B., Manzi, Antonio O., Souza, Rodrigo A. F., Springston, Stephen R., Watson, Thomas B., McKinney, Karena A., and Martin, Scot T. Isoprene photochemistry over the Amazon rainforest. United States: N. p., 2016. Web. doi:10.1073/pnas.1524136113.
Liu, Yingjun, Brito, Joel, Dorris, Matthew R., Rivera-Rios, Jean C., Seco, Roger, Bates, Kelvin H., Artaxo, Paulo, Duvoisin, Jr., Sergio, Keutsch, Frank N., Kim, Saewung, Goldstein, Allen H., Guenther, Alex B., Manzi, Antonio O., Souza, Rodrigo A. F., Springston, Stephen R., Watson, Thomas B., McKinney, Karena A., & Martin, Scot T. Isoprene photochemistry over the Amazon rainforest. United States. doi:10.1073/pnas.1524136113.
Liu, Yingjun, Brito, Joel, Dorris, Matthew R., Rivera-Rios, Jean C., Seco, Roger, Bates, Kelvin H., Artaxo, Paulo, Duvoisin, Jr., Sergio, Keutsch, Frank N., Kim, Saewung, Goldstein, Allen H., Guenther, Alex B., Manzi, Antonio O., Souza, Rodrigo A. F., Springston, Stephen R., Watson, Thomas B., McKinney, Karena A., and Martin, Scot T. Mon . "Isoprene photochemistry over the Amazon rainforest". United States. doi:10.1073/pnas.1524136113.
@article{osti_1253389,
title = {Isoprene photochemistry over the Amazon rainforest},
author = {Liu, Yingjun and Brito, Joel and Dorris, Matthew R. and Rivera-Rios, Jean C. and Seco, Roger and Bates, Kelvin H. and Artaxo, Paulo and Duvoisin, Jr., Sergio and Keutsch, Frank N. and Kim, Saewung and Goldstein, Allen H. and Guenther, Alex B. and Manzi, Antonio O. and Souza, Rodrigo A. F. and Springston, Stephen R. and Watson, Thomas B. and McKinney, Karena A. and Martin, Scot T.},
abstractNote = {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 (HO 2 ) to dominantly 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 HO 2 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.},
doi = {10.1073/pnas.1524136113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 22,
volume = 113,
place = {United States},
year = {2016},
month = {5}
}

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DOI: 10.1073/pnas.1524136113

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    Works referencing / citing this record:

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