Observations of sesquiterpenes and their oxidation products in central Amazonia during the wet and dry seasons

Yee, Lindsay D.; Isaacman-VanWertz, Gabriel; Wernis, Rebecca A.; Meng, Meng; Rivera, Ventura; Kreisberg, Nathan M.; Hering, Susanne V.; Bering, Mads S.; Glasius, Marianne; Upshur, Mary Alice; Gray Bé, Ariana; Thomson, Regan J.; Geiger, Franz M.; Offenberg, John H.; Lewandowski, Michael; Kourtchev, Ivan; Kalberer, Markus; de Sá, Suzane; Martin, Scot T.; Alexander, M. Lizabeth; Palm, Brett B.; Hu, Weiwei; Campuzano-Jost, Pedro; Day, Douglas A.; Jimenez, Jose L.; Liu, Yingjun; McKinney, Karena A.; Artaxo, Paulo; Viegas, Juarez; Manzi, Antonio; Oliveira, Maria B.; de Souza, Rodrigo; Machado, Luiz A.  T.; Longo, Karla; Goldstein, Allen H.

doi:10.5194/acp-18-10433-2018

Title: Observations of sesquiterpenes and their oxidation products in central Amazonia during the wet and dry seasons

Journal Article · Mon Jul 23 00:00:00 EDT 2018 · Atmospheric Chemistry and Physics (Online)

DOI:https://doi.org/10.5194/acp-18-10433-2018· OSTI ID:1593306

^[1]; Isaacman-VanWertz, Gabriel ^[1]; Wernis, Rebecca A. ^[1]; Meng, Meng ^[1]; Rivera, Ventura ^[1];

^[2];

^[2]; Bering, Mads S. ^[3];

^[3]; Upshur, Mary Alice ^[4]; Gray Bé, Ariana ^[4];

^[4]; Geiger, Franz M. ^[4];

^[5]; Lewandowski, Michael ^[5]; Kourtchev, Ivan ^[6];

^[6]; de Sá, Suzane ^[7]; Martin, Scot T. ^[7]; Alexander, M. Lizabeth ^[8] more »

Univ. of California, Berkeley, CA (United States)
Aerosol Dynamics, Inc., Berkeley, CA (United States)
Aarhus Univ. (Denmark)
Northwestern Univ., Evanston, IL (United States)
Research Triangle Park, NC (United States)
Univ. of Cambridge (United Kingdom)
Harvard Univ., Cambridge, MA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Colorado, Boulder, CO (United States)
Univ. of Sao Paulo (Brazil)
Instituto Nacional de Pesquisas da Amazonia, Manaus, AM (Brazil)
Universidade do Estado do Amazonas, Manaus, AM (Brazil)
Instituto Nacional de Pesquisas Espiacais, São José dos Campos, SP (Brazil)
Instituto Nacional de Pesquisas Espiacais, Cachoeira Paulista, SP (Brazil)

Biogenic volatile organic compounds (BVOCs) from the Amazon forest region represent the largest source of organic carbon emissions to the atmosphere globally. These BVOC emissions dominantly consist of volatile and intermediate-volatility terpenoid compounds that undergo chemical transformations in the atmosphere to form oxygenated condensable gases and secondary organic aerosol (SOA). We collected quartz filter samples with 12 h time resolution and performed hourly in situ measurements with a semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) at a rural site ("T3") located to the west of the urban center of Manaus, Brazil as part of the Green Ocean Amazon (GoAmazon2014/5) field campaign to measure intermediate-volatility and semi-volatile BVOCs and their oxidation products during the wet and dry seasons. We speciated and quantified 30 sesquiterpenes and 4 diterpenes with mean concentrations in the range 0.01–6.04 ng m^-3 (1–670 ppqv). We estimate that sesquiterpenes contribute approximately 14 and 12 % to the total reactive loss of O₃ via reaction with isoprene or terpenes during the wet and dry seasons, respectively. This is reduced from ~50–70 % for within-canopy reactive O₃ loss attributed to the ozonolysis of highly reactive sesquiterpenes (e.g., β-caryophyllene) that are reacted away before reaching our measurement site. We further identify a suite of their oxidation products in the gas and particle phases and explore their role in biogenic SOA formation in the central Amazon region. Synthesized authentic standards were also used to quantify gas- and particle-phase oxidation products derived from β-caryophyllene. Using tracer-based scaling methods for these products, we roughly estimate that sesquiterpene oxidation contributes at least 0.4–5 % (median 1 %) of total submicron OA mass. However, this is likely a low-end estimate, as evidence for additional unaccounted sesquiterpenes and their oxidation products clearly exists. By comparing our field data to laboratory-based sesquiterpene oxidation experiments we confirm that more than 40 additional observed compounds produced through sesquiterpene oxidation are present in Amazonian SOA, warranting further efforts towards more complete quantification.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF); Brazilian National Council for Scientific and Technological Development (CNPq); USEPA; National Aeronautics and Space Administration (NASA); Alexander von Humboldt Foundation

Grant/Contract Number:: AC05-76RL01830; SC0014040; SC0004698; SC0016559; 1332998; CHE-1607640

OSTI ID:: 1593306

Alternate ID(s):: OSTI ID: 1657284

Report Number(s):: PNNL-SA-138448; TRN: US2100903

Journal Information:: Atmospheric Chemistry and Physics (Online), Vol. 18, Issue 14; ISSN 1680-7324

Publisher:: European Geosciences UnionCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 46 works

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