The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydroperoxyl-dominant conditions for <5% relative humidity and at 20 °C in the presence of highly acidic to completely neutralized sulfate particles. Isoprene photooxidation was separated from SOM production by using two continuously mixed flow reactors connected in series and operated at steady state. Two online mass spectrometers separately sampled the gas and particle phases in the reactor outflow. The loss of specific gas-phase species as contributors to the production of SOM was thereby quantified. The produced SOM mass concentration was directly proportional to the loss of isoprene epoxydiol (IEPOX) isomers from the gas phase. IEPOX isomers lost from the gas phase accounted for (46 ± 11)% of the produced SOM mass concentration. The IEPOX isomers comprised (59 ± 21)% (molecular count) of the loss of monitored gas-phase species. The implication is that for the investigated reaction conditions the SOM production pathways tied to IEPOX isomers accounted for half of the SOM mass concentration.
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ACS Earth Space Chem
December 2024
Université Paris-Est Créteil and Université Paris Cité, CNRS, LISA, Créteil F-94010, France.
Hydroxyacetone (HA) is an atmospheric oxidation product of isoprene and other organic precursors that can form brown carbon (BrC). Measured bulk aqueous-phase reaction rates of HA with ammonium sulfate, methylamine, and glycine suggest that these reactions cannot compete with aqueous-phase hydroxyl radical oxidation. In cloud chamber photooxidation experiments with either gaseous or particulate HA in the presence of the same N-containing species, BrC formation was minor, with similar mass absorption coefficients at 365 nm (<0.
View Article and Find Full Text PDFEnviron Pollut
December 2024
Key Laboratory of Aerosol Chemistry and Physics, State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences, Xi'an, 710061, China; National Observation and Research Station of Regional Ecological Environment Change and Comprehensive Management in the Guanzhong Plain, Xi'an, 710061, China. Electronic address:
The molecular composition of organic aerosols in ambient PM was investigated at the northern foothills of Qinling Mountain region in central China during the summer of 2022. The molecular characteristics of organic matter were analyzed using ultrahigh performance liquid chromatography coupled with high-resolution Orbitrap mass spectrometry. The number of molecular formula assignments was dominated by organosulfur species (OrgS, on average 28-47% in total).
View Article and Find Full Text PDFSci Total Environ
December 2024
School of Environment and Energy Engineering, Anhui Jianzhu University, 230009 Hefei, China. Electronic address:
The climate-active gas isoprene (CH) is one of the most abundant biogenic volatile organic compounds (VOCs). Soil is one of the significant sinks for isoprene, yet the role played by the naturally abundant birnessite in the soil surface layer during the oxidation of isoprene remains largely unknown. This study investigates the reactions of isoprene with triclinic and hexagonal birnessite on the Earth's surface environments.
View Article and Find Full Text PDFChemosphere
November 2024
School of Environmental Engineering, Henan University of Technology, Zhengzhou, Henan, 450001, China.
Isoprene epoxydiol (IEPOX) is an important reactive gas-phase intermediate produced by the photooxidation of isoprene under low NO conditions, playing a key role in the formation of secondary organic aerosols (SOA). Previous studies have mostly focused on the liquid-phase reactions of IEPOX within aerosols; however, interfacial heterogeneous chemical reactions are equally important in SOA formation. This study systematically explores the reaction mechanisms of IEPOX at the acidic aerosol interface and in the bulk phase using classical molecular dynamics (MD) and ab initio molecular dynamics simulations (AIMD).
View Article and Find Full Text PDFAtmos Environ (1994)
June 2024
Center for Computational Toxicology and Exposure, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, USA.
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