Skip to main content
SpringerLink
Log in

Winter and summer characterization of biogenic enantiomeric monoterpenes and anthropogenic BTEX compounds at a Mediterranean Stone Pine forest site

  • Published:
Journal of Atmospheric Chemistry Aims and scope Submit manuscript

Abstract

Measurements of biogenic gases including enantiomeric monoterpenes and isoprene, and anthropogenic gases such as benzene, toluene, ethylbenzene, ortho-, meta- and para- xylene (BTEX) compounds were made by GC-MS in November and December 2008 within a stone pine (Pinus pinea L) forest located on the Southwest coast of Spain (37.10°N, 6.70°W). Mixing ratios of the biogenic species were found to be low (mean circa 10 pptv) consistent with previously observed low wintertime regional forest emission rates. In contrast, anthropogenic species were significantly higher (mean 10–156 pptv), the dominant emissions originating from the city of Huelva and associated petrochemical activities, located 25 km north west of the measurement site. In wintertime the monoterpene (−)-α-pinene was found to be in slight enantiomeric excess over (+)-α-pinene at night but by day the measured ratio was closer to one i.e. racemic. Samples taken the following summer in the same location showed much higher monoterpene mixing ratios and revealed a strong enantiomeric excess of (−)-α-pinene. This indicates a strong seasonal variance in the enantiomeric emission ratio which is not manifested in the day/night temperature cycles in wintertime. Mixing ratios of the xylene isomers (meta- and para-) and ethylbenzene, which are all well resolved on the beta-cyclodextrin column, were exploited to estimate average OH radical exposures to VOCs from the Huelva industrial area. These were compared to empirical estimates of OH based on JNO2 measured at the site. The deficiencies of each estimation method are discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Atkinson, R., Arey, J.: Atmospheric degradation of volatile organic compounds. Chem. Rev. 103(12), 4605–4638 (2003). doi:10.1021/Cr0206420

    Article  Google Scholar 

  • Ehhalt, D.H., Rohrer, F.: Dependence of the OH concentration on solar UV. J. Geophys. Res.-Atmos. 105(D3), 3565–3571 (2000)

    Article  Google Scholar 

  • Fuentes, J.D., Lerdau, M., Atkinson, R., Baldocchi, D., Bottenheim, J.W., Ciccioli, P., Lamb, B., Geron, C., Gu, L., Guenther, A., Sharkey, T.D., Stockwell, W.: Biogenic hydrocarbons in the atmospheric boundary layer: a review. Bull. Am. Meteorol. Soc. 81(7), 1537–1575 (2000)

    Article  Google Scholar 

  • Grote, R., Keenan, T., Lavoir, A.V., Staudt, M.: Process-based simulation of seasonality and drought stress in monoterpene emission models. Biogeosciences 7(1), 257–274 (2010)

    Article  Google Scholar 

  • Guenther, A.B., Zimmerman, P.R., Harley, P.C., Monson, R.K., Fall, R.: Isoprene and monoterpene emission rate variability—model evaluations and sensitivity analyses. J. Geophys. Res.-Atmos. 98(D7), 12609–12617 (1993)

    Article  Google Scholar 

  • Guenther, A., Hewitt, C.N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., Mckay, W.A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., Zimmerman, P.: A global-model of natural volatile organic-compound emissions. J. Geophys. Res.-Atmos. 100(D5), 8873–8892 (1995)

    Article  Google Scholar 

  • Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P.I., Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature). Atmos. Chem. Phys. 6, 3181–3210 (2006)

    Article  Google Scholar 

  • Jacob, D.J., Field, B.D., Jin, E.M., Bey, I., Li, Q.B., Logan, J.A., Yantosca, R.M., Singh, H.B.: Atmospheric budget of acetone. J. Geophys. Res.-Atmos. 107(10), − (2002)

  • Keenan, T., Niinemets, U., Sabate, S., Gracia, C., Penuelas, J.: Seasonality of monoterpene emission potentials in Quercus ilex and Pinus pinea: Implications for regional VOC emissions modeling. J. Geophys. Res-Atmos. 114, − (2009)

  • Kesselmeier, J., Staudt, M.: Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology. J. Atmos. Chem. 33(1), 23–88 (1999)

    Article  Google Scholar 

  • Lelieveld, J., Peters, W., Dentener, F.J., Krol, M.C.: Stability of tropospheric hydroxyl chemistry. J. Geophys. Res.-Atmos. 107(D23), − (2002)

  • Lelieveld, J., Butler, T.M., Crowley, J.N., Dillon, T.J., Fischer, H., Ganzeveld, L., Harder, H., Lawrence, M.G., Martinez, M., Taraborrelli, D., Williams, J.: Atmospheric oxidation capacity sustained by a tropical forest. Nature 452(7188), 737–740 (2008). doi:10.1038/Nature06870

    Article  Google Scholar 

  • Lerdau, M., Litvak, M., Palmer, P., Monson, R.: Controls over monoterpene emissions from boreal forest conifers. Tree Physiol. 17(8–9), 563–569 (1997)

    Google Scholar 

  • Loreto, F., Fischbach, R.J., Schnitzler, J.P., Ciccioli, P., Brancaleoni, E., Calfapietra, C., Seufert, G.: Monoterpene emission and monoterpene synthase activities in the Mediterranean evergreen oak Quercus ilex L. grown at elevated CO2 concentrations. Global Change Biology 7(6), 709–717 (2001)

    Article  Google Scholar 

  • Martin, D., Tholl, D., Gershenzon, J., Bohlmann, J.: Methyl jasmonate induces traumatic resin ducts, terpenoid resin biosynthesis, and terpenoid accumulation in developing xylem of Norway spruce stems. Plant Physiol. 129(3), 1003–1018 (2002). doi:10.1104/Pp.011001

    Article  Google Scholar 

  • McKinney, K.A., Lee, B.H., Vasta, A., Pho, T.V., Munger, J.W.: Emissions of isoprenoids and oxygenated biogenic volatile organic compounds from a New England mixed forest. Atmos. Chem. Phys. 11(10), 4807–4831 (2011). doi:10.5194/acp-11-4807-2011

    Article  Google Scholar 

  • Monson, R.K., Lerdau, M.T., Sharkey, T.D., Schimel, D.S., Fall, R.: Biological aspects of constructing volatile organic-compound emission inventories. Atmos. Environ. 29(21), 2989–3002 (1995)

    Article  Google Scholar 

  • Norin, T.: Chiral chemodiversity and its role for biological activity. Some observations from studies on insect/insect and insect/plant relationships. Pure Appl. Chem. 68(11), 2043–2049 (1996)

    Article  Google Scholar 

  • Roberts, J.M., Fehsenfeld, F.C., Liu, S.C., Bollinger, M.J., Hahn, C., Albritton, D.L., Sievers, R.E.: Measurements of aromatic hydrocarbon ratios and nox concentrations in the rural troposphere—observation of air-mass photochemical aging and nox removal. Atmos. Environ. 18(11), 2421–2432 (1984)

    Article  Google Scholar 

  • Rohrer, F., Berresheim, H.: Strong correlation between levels of tropospheric hydroxyl radicals and solar ultraviolet radiation. Nature 442(7099), 184–187 (2006). doi:10.1038/Nature04924

    Article  Google Scholar 

  • Sabillon, D., Cremades, L.V.: Diurnal and seasonal variation of monoterpene emission rates for two typical Mediterranean species (Pinus pinea and Quercus ilex) from field measurements-relationship with temperature and PAR. Atmos. Environ. 35(26), 4419–4431 (2001)

    Article  Google Scholar 

  • Staudt, M., Bertin, N., Hansen, U., Seufert, G., Ciccioli, P., Foster, P., Frenzel, B., Fugit, J.L.: Seasonal and diurnal patterns of monoterpene emissions from Pinus pinea (L.) under field conditions. Atmos Environ 31, 145–156 (1997)

    Article  Google Scholar 

  • Staudt, M., Bertin, N., Frenzel, B., Seufert, G.: Seasonal variation in amount and composition of monoterpenes emitted by young Pinus pinea trees—Implications for emission modeling. J. Atmos. Chem. 35(1), 77–99 (2000)

    Article  Google Scholar 

  • Stokes, G.Y., Chen, E.H., Buchbinder, A.M., Paxton, W.F., Keeley, A., Geiger, F.M.: Atmospheric heterogeneous stereochemistry. J. Am. Chem. Soc. 131(38), 13733–13737 (2009). doi:10.1021/Ja904206t

    Article  Google Scholar 

  • Street, R.A., Hewitt, C.N., Mennicken, S.: Isoprene and monoterpene emissions from a Eucalyptus plantation in Portugal. J Geophys Res-Atmos 102(D13), 15875–15887 (1997)

    Article  Google Scholar 

  • Williams, J.: Organic trace gases in the atmosphere: An overview. Environ. Chem. 1(3), 125–136 (2004)

    Article  Google Scholar 

  • Williams, J., Yassaa, N., Bartenbach, S., Lelieveld, J.: Mirror image hydrocarbons from Tropical and Boreal forests. Atmos. Chem. Phys. 7, 973–980 (2007)

    Article  Google Scholar 

  • Winters, A.J., Adams, M.A., Bleby, T.M., Rennenberg, H., Steigner, D., Steinbrecher, R., Kreuzwieser, J.: Emissions of isoprene, monoterpene and short-chained carbonyl compounds from Eucalyptus spp. in southern Australia. Atmos Environ 43(19), 3035–3043 (2009)

    Article  Google Scholar 

  • Yassaa, N., Brancaleoni, E., Frattoni, M., Ciccioli, P.: Trace level determination of enantiomeric monoterpenes in terrestrial plant emission and in the atmosphere using a beta-cyclodextrin capillary column coupled with thermal desorption and mass spectrometry. J. Chromatogr. A 915(1–2), 185–197 (2001)

    Article  Google Scholar 

  • Yassaa, N., Brancaleoni, E., Frattoni, M., Ciccioli, P.: Isomeric analysis of BTEXs in the atmosphere using beta-cyclodextrin capillary chromatography coupled with thermal desorption and mass spectrometry. Chemosphere 63(3), 502–508 (2006)

    Article  Google Scholar 

Download references

Acknowledgements

We would like to thank INTA for hosting the campaign and the entire DOMINO team for the assistance and professionalism during the campaign.

Author information

Authors and Affiliations

  1. Max Planck Institut für Chemie, Mainz, Germany

    Wei Song, Jonathan Williams, Monica Martinez, Heiko Bozem & Jos Lelieveld

  2. University of Sciences and Technology Houari Boumediene, Algiers, Algeria

    Noureddine Yassaa

  3. Atmospheric Research and Instrumentation Branch, Atmospheric Sounding Station ‘El Arenosillo’, National Institute for Aerospace Technology (INTA), Huelva, Spain

    José Antonio Adame Carnero

  4. Dpt. Biología Ambiental y Salud Pública, University of Huelva, Huelva, Spain

    Pablo J. Hidalgo

Authors
  1. Wei Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jonathan Williams
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Noureddine Yassaa
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Monica Martinez
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. José Antonio Adame Carnero
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Pablo J. Hidalgo
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Heiko Bozem
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jos Lelieveld
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jonathan Williams.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Song, W., Williams, J., Yassaa, N. et al. Winter and summer characterization of biogenic enantiomeric monoterpenes and anthropogenic BTEX compounds at a Mediterranean Stone Pine forest site. J Atmos Chem 68, 233–250 (2011). https://doi.org/10.1007/s10874-012-9219-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10874-012-9219-4

Keywords

Search

Navigation