Real-time detection of highly oxidized organosulfates and BSOA marker compounds during the F-BEACh 2014 field study

Other literature type, Article English OPEN
Brüggemann, Martin ; Poulain, Laurent ; Held, Andreas ; Stelzer, Torsten ; Zuth, Christoph ; Richters, Stefanie ; Mutzel, Anke ; Pinxteren, Dominik ; Iinuma, Yoshiteru ; Katkevica, Sarmite ; Rabe, René ; Herrmann, Hartmut ; Hoffmann, Thorsten (2017)
  • Publisher: Copernicus Publications
  • Journal: (issn: 1680-7324, eissn: 1680-7324)
  • Related identifiers: doi: 10.5194/acp-17-1453-2017
  • Subject: Chemistry | QD1-999 | Physics | QC1-999

The chemical composition of ambient organic aerosols was analyzed using complementary mass spectrometric techniques during a field study in central Europe in July 2014 (Fichtelgebirge &ndash; Biogenic Emission and Aerosol Chemistry, F-BEACh 2014). Among several common biogenic secondary organic aerosol (BSOA) marker compounds, 93 acidic oxygenated hydrocarbons were detected with elevated abundances and were thus attributed to be characteristic for the organic aerosol mass at the site. Monoterpene measurements exhibited median mixing ratios of 1.6 and 0.8 ppb<sub>V</sub> for in and above canopy levels respectively. Nonetheless, concentrations for early-generation oxidation products were rather low, e.g., pinic acid (<i>c</i>  =  4.7 (±2.5) ng m<sup>−3</sup>). In contrast, high concentrations were found for later-generation photooxidation products such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA, <i>c</i>  =  13.8 (±9.0) ng m<sup>−3</sup>) and 3-carboxyheptanedioic acid (<i>c</i>  =  10.2 (±6.6) ng m<sup>−3</sup>), suggesting that aged aerosol masses were present during the campaign period. In agreement, HYSPLIT trajectory calculations indicate that most of the arriving air masses traveled long distances (&gt; &thinsp;1500 km) over land with high solar radiation. <br><br> In addition, around 47 % of the detected compounds from filter sample analysis contained sulfur, confirming a rather high anthropogenic impact on biogenic emissions and their oxidation processes. Among the sulfur-containing compounds, several organosulfates, nitrooxy organosulfates, and highly oxidized organosulfates (HOOS) were tentatively identified by high-resolution mass spectrometry. Correlations among HOOS, sulfate, and highly oxidized multifunctional organic compounds (HOMs) support the hypothesis of previous studies that HOOS are formed by reactions of gas-phase HOMs with particulate sulfate. Moreover, periods with high relative humidity indicate that aqueous-phase chemistry might play a major role in HOOS production. However, for dryer periods, coinciding signals for HOOS and gas-phase peroxyradicals (RO<sub>2</sub><sup>&bullet;</sup>) were observed, suggesting RO<sub>2</sub><sup>&bullet;</sup> to be involved in HOOS formation.</p>
  • References (89)
    89 references, page 1 of 9

    Aiken, A. C., Salcedo, D., Cubison, M. J., Huffman, J. A., DeCarlo, P. F., Ulbrich, I. M., Docherty, K. S., Sueper, D., Kimmel, J. R., Worsnop, D. R., Trimborn, A., Northway, M., Stone, E. A., Schauer, J. J., Volkamer, R. M., Fortner, E., de Foy, B., Wang, J., Laskin, A., Shutthanandan, V., Zheng, J., Zhang, R., Gaffney, J., Marley, N. A., Paredes-Miranda, G., Arnott, W. P., Molina, L. T., Sosa, G., and Jimenez, J. L.: Mexico City aerosol analysis during MILAGRO using high resolution aerosol mass spectrometry at the urban supersite (T0) - Part 1: Fine particle composition and organic source apportionment, Atmos. Chem. Phys., 9, 6633-6653, doi:10.5194/acp-9-6633-2009, 2009.

    Altieri, K. E., Turpin, B. J., and Seitzinger, S. P.: Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FTICR mass spectrometry, Atmos. Chem. Phys., 9, 2533-2542, doi:10.5194/acp-9-2533-2009, 2009.

    Baltensperger, U., Dommen, J., Alfarra, R.R., Duplissy, J., Gaeggeler, K., Metzger, A., Facchini, M. C.., Decesari, S., Finessi, E., Reinnig, C., Schott, M., Warnke, J., Hoffmann, T., Klatzer, B., Puxbaum, H., Geiser, M., Savi, M., Lang, D., Kalberer, M., and Geiser, T.: Combined Determination of the Chemical Composition and of Health Effects of Secondary Organic Aerosols: The POLYSOA Project, J. Aerosol Med. Pulm. Drug. Deliv., 21, 145-154, doi:10.1089/jamp.2007.0655, 2008.

    Beck, M. and Hoffmann, T.: A detailed MSn study for the molecular identification of a dimer formed from oxidation of pinene, Atmos. Environ., 130, 120-126, doi:10.1016/j.atmosenv.2015.09.012, 2016.

    Berndt, T., Jokinen, T., Sipilä, M., Mauldin, R. L., Herrmann, H., Stratmann, F., Junninen, H., and Kulmala, M.: H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: Influence of water vapour content and temperature, Atmos. Environ., 89, 603-612, doi:10.1016/j.atmosenv.2014.02.062, 2014.

    Brüggemann, M., Karu, E., Stelzer, T., and Hoffmann, T.: RealTime Analysis of Ambient Organic Aerosols Using Aerosol Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (AeroFAPA-MS), Environ. Sci. Technol., 49, 5571-5578, doi:10.1021/es506186c, 2015.

    Canagaratna, M., Jayne, J., Jimenez, J., Allan, J., Alfarra, M., Zhang, Q., Onasch, T., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L., Trimborn, A., Northway, M., DeCarlo, P., Kolb, C., Davidovits, P., and Worsnop, D.: Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer, Mass Spectrom. Rev., 26, 185-222, doi:10.1002/mas.20115, 2007.

    Chan, M. N., Surratt, J. D., Chan, A. W. H., Schilling, K., Offenberg, J. H., Lewandowski, M., Edney, E. O., Kleindienst, T. E., Jaoui, M., Edgerton, E. S., Tanner, R. L., Shaw, S. L., Zheng, M., Knipping, E. M., and Seinfeld, J. H.: Influence of aerosol acidity on the chemical composition of secondary organic aerosol from -caryophyllene, Atmos. Chem. Phys., 11, 1735-1751, doi:10.5194/acp-11-1735-2011, 2011.

    Claeys, M., Iinuma, Y., Szmigielski, R., Surratt, J. D., Blockhuys, F., van Alsenoy, C., Böge, O., Sierau, B., Gómez-González, Y., Vermeylen, R., van der Veken, P., Shahgholi, M., Chan, A. W. H., Herrmann, H., Seinfeld, J. H., and Maenhaut, W.: Terpenylic Acid and Related Compounds from the Oxidation of -Pinene: Implications for New Particle Formation and Growth above Forests, Environ. Sci. Technol., 43, 6976-6982, doi:10.1021/es9007596, 2009.

    Crounse, J. D., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., and Wennberg, P. O.: Autoxidation of Organic Compounds in the Atmosphere, J. Phys. Chem. Lett., 4, 3513-3520, doi:10.1021/jz4019207, 2013.

  • Related Research Results (1)
  • Metrics
    No metrics available
Share - Bookmark