2015 Progress Report: Impacts of Anthropogenic Emissions in the Southeastern U.S. on Heterogeneous Chemistry of Isoprene-Derived Epoxides Leading to Secondary Organic Aerosol Formation

EPA Grant Number: R835404
Title: Impacts of Anthropogenic Emissions in the Southeastern U.S. on Heterogeneous Chemistry of Isoprene-Derived Epoxides Leading to Secondary Organic Aerosol Formation
Investigators: Surratt, Jason D.
Institution: University of North Carolina at Chapel Hill
EPA Project Officer: Chung, Serena
Project Period: April 1, 2013 through March 31, 2016 (Extended to March 31, 2017)
Project Period Covered by this Report: April 1, 2015 through March 31,2016
Project Amount: $300,000
RFA: Anthropogenic Influences on Organic Aerosol Formation and Regional Climate Implications (2012) RFA Text |  Recipients Lists
Research Category: Air Quality and Air Toxics , Global Climate Change , Climate Change , Air

Objective:

The underlying hypothesis of this study is that anthropogenic emissions enhance isoprene secondary organic aerosol (SOA) formation through the heterogeneous chemistry of isoprene-derived epoxides, possibly leading to light-absorbing SOA in the southeastern United States. The specific objectives to evaluate this hypothesis include: (1) leverage our ongoing Look Rock, Tennessee, field site during the community-led Southern Oxidant & Aerosol Study (SOAS) in summer 2013 to evaluate how isoprene SOA formation chemistry varies between regional- and urban-influenced air masses; (2) evaluate the effects of relative humidity, aerosol acidity and seed aerosol type on the heterogeneous chemistry of isoprene-derived epoxides leading to SOA and how this might yield light-absorbing aerosol constituents (i.e., brown carbon); (3) evaluate gaseous yields of epoxides from isoprene oxidation under varying initial levels of nitric oxide; (4) experimentally determine the isoprene epoxydiols (IEPOX) and methacrylic acid epoxides (MAE) reaction probability per collision with aerosol particles, γ(IEPOX) and γ(MAE), and its dependence upon aerosol composition in order to help improve parameterization of isoprene-derived SOA formation in models; and (5) determine the source of isoprene SOA at the Look Rock, Tennessee, ground site observed during SOAS 2013 that occurs through non-epoxide routes.

Progress Summary:

We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

SOA was generated in an indoor smog chamber from isoprene ozonolysis under dark conditions in the presence of non-acidified or acidified sulfate seed aerosol. The effect of OH radicals on SOA chemical composition was investigated using diethyl ether as an OH radical scavenger. Analysis revealed the formation of highly oxidized compounds, including organosulfates (OS) and 2-methylterols, which were significantly enhanced in the presence of acidified sulfate seed aerosol. OS identified in the chamber experiments also were observed and quantified in summertime fine aerosol collected from two rural locations in the southeastern United States during the 2013 SOAS.  Furthermore, 34 gaseous oligomeric compounds resulting from the addition of stabilized Criegee intermediates with either organic hydroperoxides or carboxylic acids were identified using iodide chemical ionization high-resolution mass spectrometry. Large reactive uptakes onto acidified sulfate aerosol were observed for most of the characterized gaseous oligomeric species, whereas the presence of organic coatings and the lack of aerosol water significantly reduced or halted the reactive uptake of these species. These results indicate that multiphase chemistry of epoxides and/or hydroperoxides could be significantly influenced by the chemical composition of the seed aerosols. Moreover, in addition to functionalization and accretion, decomposition and revolatilization should be considered in the formation and aging of SOA.

SOA formation from the oxidation of authentic 1,2-ISOPOOH under low-NOx  conditions was systematically examined with varying aerosol compositions and relative humidity. High yields of highly oxidized compounds, including multifunctional OS and hydroperoxides, were chemically characterized in both laboratory-generated SOA and fine aerosol samples collected from the southeastern United States. IEPOX-derived SOA constituents were observed in all experiments, but their concentrations were only enhanced in the presence of acidified sulfate aerosol, consistent with prior work. High-resolution aerosol mass spectrometry reveals that 1,2-ISOPOOH-derived SOA formed through non-IEPOX routes exhibits a notable mass spectrum with a characteristic fragment ion at m/z 91. This laboratory-generated mass spectrum is strongly correlated with a factor recently resolved by positive matrix factorization of aerosol mass spectrometer data collected in areas dominated by isoprene emissions, suggesting that the non-IEPOX pathway could contribute to ambient SOA measured in the Southeastern United States.

Future Activities:

We currently are summarizing recent findings on isoprene-derived hydroperoxides for publication purposes.   


Journal Articles on this Report : 16 Displayed | Download in RIS Format

Other project views: All 36 publications 16 publications in selected types All 16 journal articles
Type Citation Project Document Sources
Journal Article Barbosa TS, Riva M, Chen Y, da Silva CM, Ameida JCS, Zhang Z, Gold A, Arbilla G, Bauerfeldt GF, Surratt JD. Chemical characterization of organosulfates from the hydroxyl radical-initiated oxidation and ozonolysis of cis-3-hexen-1-ol. Atmospheric Environment 2017;162:141-151. R835404 (2015)
R835404 (Final)
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  • Journal Article Budisulistiorini SH, Li X, Bairai ST, Renfro J, Liu Y, Liu YJ, McKinney KA, Martin ST, McNeill VF, Pye HOT, Nenes A, Neff ME, Stone EA, Mueller S, Knote C, Shaw SL, Zhang Z, Gold A, Surratt JD. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site. Atmospheric Chemistry and Physics 2015;15(15):8871-8888. R835404 (2014)
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    R835401 (2014)
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  • Journal Article Budisulistiorini SH, Nenes A, Carlton AG, Surratt JD, McNeill VF, Pye HOT. Simulating aqueous-phase isoprene-epoxydiol (IEPOX) secondary organic aerosol production during the 2013 Southern Oxidant and Aerosol Study (SOAS). Environmental Science & Technology 2017;51(9):5026-5034. R835404 (2015)
    R835404 (Final)
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  • Journal Article Gaston CJ, Riedel TP, Zhang Z, Gold A, Surratt JD, Thornton JA. Reactive uptake of an isoprene-derived epoxydiol to submicron aerosol particles. Environmental Science & Technology 2014;48(19):11178-11186. R835404 (2014)
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  • Journal Article Hu WW, Campuzano-Jost P, Palm BB, Day DA, Ortega AM, Hayes PL, Krechmer JE, Chen Q, Kuwata M, Liu YJ, de Sa SS, McKinney K, Martin ST, Hu M, Budisulistiorini SH, Riva M, Surratt JD, St. Clair JM, Isaacman-Van Wertz G, Yee LD, Goldstein AH, Carbone S, Brito J, Artaxo P, de Gouw JA, Koss A, Whisthaler A, Mikoviny T, Karl T, Kaser L, Jud W, Hansel A, Docherty KS, Alexander ML, Robinson NH, Coe H, Allan JD, Canagaratna MR, Paulot F, Jimenez JL. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements. Atmospheric Chemistry and Physics 2015;15(20):11807-11833. R835404 (2014)
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  • Journal Article Kristensen K, Cui T, Zhang H, Gold A, Glasius M, Surratt JD. Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity. Atmospheric Chemistry and Physics 2014;14(8):4201-4218. R835404 (2013)
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  • Journal Article Lin Y-H, Budisulistiorini SH, Chu K, Siejack RA, Zhang H, Riva M, Zhang Z, Gold A, Kautzman KE, Surratt JD. Light-absorbing oligomer formation in secondary organic aerosol from reactive uptake of isoprene epoxydiols. Environmental Science & Technology 2014;48(20):12012-12021. R835404 (2013)
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  • Journal Article Liu J, D'Ambro EL, Lee BH, Lopez-Hilfiker FD, Zaveri RA, Rivera-Rios JC, Keutsch FN, Iyer S, Kurten T, Zhang Z, Gold A, Surratt JD, Shilling JE, Thornton JA. Efficient isoprene secondary organic aerosol formation from a non-IEPOX pathway. Environmental Science & Technology 2016;50(18):9872-9880. R835404 (2015)
    R835404 (Final)
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  • Journal Article Pye HOT, Murphy BN, Xu L, Ng NL, Carlton AG, Guo H, Weber R, Vasilakos P, Appel KW, Budisulistiorini SH, Surratt JD, Nenes A, Hu W, Jimenez JL, Isaacman-VanWertz G, Misztal PK, Goldstein AH. On the implications of aerosol liquid water and phase separation for organic aerosol mass. Atmospheric Chemistry and Physics 2017;17(1):343-369. R835404 (2015)
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  • Journal Article Rattanavaraha W, Chu K, Budisulistiorini SH, Riva M, Lin Y-H, Edgerton ES, Baumann K, Shaw SL, Guo H, King L, Weber RJ, Neff ME, Stone EA, Offenberg JH, Zhang Z, Gold A, Surratt JD. Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study. Atmospheric Chemistry and Physics 2016;16(8):4897-4914. R835404 (2014)
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  • Journal Article Riedel TP, Lin Y-H, Budisulistiorini SH, Gaston CJ, Thornton JA, Zhang Z, Vizuete W, Gold A, Surratt JD. Heterogeneous reactions of isoprene-derived epoxides:reaction probabilities and molar secondary organic aerosol yield estimates. Environmental Science & Technology Letters 2015;2(2):38-42. R835404 (2014)
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  • Journal Article Riedel TP, Lin Y-H, Zhang Z, Chu K, Thornton JA, Vizuete W, Gold A, Surratt JD. Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols. Atmospheric Chemistry and Physics 2016;16(3):1245-1254. R835404 (2014)
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  • Journal Article Riva M, Budisulistiorini SH, Zhang Z, Gold A, Surratt JD. Chemical characterization of secondary organic aerosol constituents from isoprene ozonolysis in the presence of acidic aerosol. Atmospheric Environment 2016;130:5-13. R835404 (2014)
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  • Journal Article Riva M, Budisulistiorini SH, Chen Y, Zhang Z, D'Ambro EL, Zhang X, Gold A, Turpin BJ, Thornton JA, Canagaratna MR, Surratt JD. Chemical characterization of secondary organic aerosol from oxidation of isoprene hydroxyhydroperoxides. Environmental Science & Technology 2016;50(18):9889-9899. R835404 (2015)
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  • Journal Article Riva M, Budisulistiorini SH, Zhang Z, Gold A, Thornton JA, Turpin BJ, Surratt JD. Multiphase reactivity of gaseous hydroperoxide oligomers produced from isoprene ozonolysis in the presence of acidified aerosols. Atmospheric Environment 2017;152:314-322. R835404 (2015)
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  • Journal Article Zhang H, Zhang Z, Cui T, Lin Y-H, Bhathela NA, Ortega J, Worton DR, Goldstein AH, Guenther A, Jimenez JL, Gold A, Surratt JD. Secondary organic aerosol formation via 2-methyl-3-buten-2-ol photooxidation: evidence of acid-catalyzed reactive uptake of epoxides. Environmental Science & Technology Letters 2014;1(4):242-247. R835404 (2013)
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  • Supplemental Keywords:

    atmosphere, particulates, biogenic volatile organic compounds, terpenes

    Relevant Websites:

    UNC Gillings School of Public Health: Jason D. Surratt, PhD Exit

    Progress and Final Reports:

    Original Abstract
    2013 Progress Report
    2014 Progress Report
    Final Report