Research

NSF-Funded Research

This website reports on studies that were conducted during the NSF-funded project “Integrated Experimental and Modeling Studies of the Chemistry of Organic Aerosol Formation from the Atmospheric Oxidation of Hydrocarbons (AGS-1420007).” The PI was Professor Paul Ziemann.

Scientists interested in knowing more about the experiments or the results should contact Professor Ziemann (paul.ziemann@colorado.edu) to request additional information, data, or archived particle samples, or to discuss the work. Depending on the nature of the request we should be able to accommodate most requests within a few weeks to months. The general expectation for experimental data is that one to two years will be needed after the completion of the project (summer 2016) to allow time for students to compete data analysis and associated modeling, write and publish research results, and complete their thesis dissertations. After this period, but sooner if possible, it is expected that most data files collected during the project and corresponding meta-data will be made available to interested scientists upon request as described above. Until then this site will be regularly updated as new manuscripts are published and data are available.

The overall objective of the experimental and modeling program was to develop quantitative chemical mechanisms for the gas-phase and heterogeneous/multiphase reactions involved in the formation of secondary organic aerosol (SOA) from the OH radical-initiated reactions of selected alkanes, alkenes, and their first-generation reaction products over a range of conditions, and to use these mechanisms with information on gas-particle-wall partitioning to develop comprehensive models for SOA formation and oxidative aging. The study has provided valuable new methods for chemical analysis of complex organic aerosols, identity and yields of products of important classes of volatile organic compound (VOC) reactions, and gas- and particle-phase reaction mechanisms, which can be used to improve SOA and air quality models and evaluate and improve chamber studies.

The data produced in this project are primarily the chemical composition of gases and particles and particle size distributions measured for environmental chamber reactions carried out in the Ziemann laboratory at UC-Riverside and CU-Boulder. The following experiments were conducted: n-hexadecane, 1-tetradecene, 2-methyl-1-tetradecene, 2-, 3-, 4-, 5-, 6-dodecanone, and 1-, 2-, 3-, 4-, 5-docanol with OH/NOx; n-pentadecane with OH; 1-pentadecene with NO3; and a-pinene with O3. Data were acquired from the following real-time measurements made during experiments and offline measurements of collected gas and particle samples made after experiments. Real-time analysis: thermal desorption particle beam mass spectrometry (TDPBMS), scanning mobility particle sizing (SMPS), O3, and NO-NOx. Offline analysis: Temperature-programmed thermal desorption (TPTD), high-performance liquid chromatography (HPLC) with UV-Vis and TDPBMS detection, chemical ionization ion trap mass spectrometry, gas chromatography with flame ionization detection (GC-FID), derivatization-spectrophotometric functional group analysis, and Fourier transform infrared (FTIR) spectroscopy. Data on the following experimental conditions were also collected: Initial concentration of VOC and oxidant precursors (CH3ONO/NO, tetramethylethene, O3) and seed particles, RH, and temperature. Some unused filter samples have also been archived by storing in a -20C freezer. Modeling data include KinSim kinetic models and simulations of environmental chamber experiments, and results of modeling conducted in collaboration with Professor Bernard Aumont using the GECKO-A model.

The following papers based wholly or in part on results of this project have been published or submitted.

  • Yeh, G.K., Ziemann, P.J., 2014. Alkyl nitrate formation from the reactions of C8−C14 n‑alkanes with OH radicals in the presence of NOx: Measured yields with essential corrections for gas−wall partitioning. Journal of Physical Chemistry A, 118, 8147-8157.

  • Yeh, G.K., Ziemann, P.J., 2014. Identification and yields of 1,4-hydroxynitrates formed from the reactions of C8−C16 n‑alkanes with OH radicals in the presence of NOx. Journal of Physical Chemistry A, 118, 8797-8806.

  • Yeh, G. K., Ziemann, P.J., 2015. Gas-wall partitioning of oxygenated organic compounds: Measurements, structure–activity relationships, and correlation with gas chromatographic retention factor. Aerosol Science and Technology, 49, 726-737.

  • Yeh, G.K., Claflin, M.S., Ziemann, P.J., 2015. Products and mechanism of the reaction of 1‑pentadecene with NO3 radicals and the effect of a −ONO2 group on alkoxy radical decomposition. Journal of Physical Chemistry A, 119, 10684-10696.

  • Waxman, E.M., Elm, J., Kurtén, T., Mikkelsen, K.V., Ziemann, P.J., Volkamer, R., 2015. Glyoxal and methylglyoxal setschenow salting constants in sulfate, nitrate, and chloride solutions: Measurements and Gibbs energies. Environmental Science and Technology, 49, 11500-11508.

  • La, Y.S., Camredon, M., Ziemann, P. J., Valorso, R., Matsunaga, A., Lannuque, V., Lee-Taylor, J., Hodzic, A., Madronich, S., Aumont, B, 2016. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation. Atmospheric Chemistry and Physics, 16, 1417–1431.

  • Krechmer, J.E., Pagonis, D., Ziemann, P.J., Jimenez, J.L., 2016. Quantification of gas-wall partitioning in teflon environmental chambers using rapid bursts of low-volatility oxidized species generated in situ. Environmental Science and Technology, 50, 5757–5765.

  • Algrim, L.B., Ziemann, P.J., 2016. Effect of the keto group on yields and composition of organic aerosol formed from OH radical-initiated reactions of ketones in the presence of NOx. Journal of Physical Chemistry A, 120, 6978–6989.

  • Ranney, A.P., Ziemann, P.J., 2016. Microscale spectrophotometric methods for quantification of functional groups in oxidized organic aerosol. Aerosol Science and Technology, 50, 881–892.

  • Ranney, A.P., Ziemann, P.J., 2016. Kinetics of acid-catalyzed dehydration of cyclic hemiacetals in aerosol particles in equilibrium with nitric acid vapor. Journal of Physical Chemistry A, 120, 2561–2568.

  • Ranney, A.P., Ziemann, P.J., 2016. Identification and quantification of oxidized organic aerosol compounds using derivatization, liquid chromatography, and chemical ionization mass spectrometry. Aerosol Science and Technology, 51, 342–353.