References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-12-10425-2012

Diel cycles of isoprenoids in the emissions of Norway spruce, four Scots pine chemotypes, and in Boreal forest ambient air during HUMPPA-COPEC-2010

Yassaa

¹ ² Song

¹ Lelieveld

¹ Vanhatalo

³ Bäck

³ Williams

Department of Air Chemistry, Max-Planck Institute for Chemistry, Mainz, Germany

USTHB, University of Sciences and Technology Houari Boumediene, Faculty of Chemistry, BP 32 El-Alia Bab-Ezzouar, 16111 Algiers, Algeria

Department of Forest Sciences, University of Helsinki, Finland

20 04 2012

12 4 10425 10460

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Branch enclosure based emission rates of monoterpenes and sesquiterpenes from four Scots pines (Pinus sylvestris) and one Norway spruce (Picea abies), as well as the ambient mixing ratios of monoterpenes were determined during the HUMPPA-COPEC 2010 summer campaign. Differences in chemical composition and in emission strength were observed between the different trees, which confirmed that they represented different chemotypes. The chemotypes of Scots pine can be classified according to species with high, no and intermediate content of Δ-3-carene. The "non-Δ-3-carene" chemotype was found to be the strongest emitter of monoterpenes. From this chemotype, β-myrcene, a very reactive monoterpene, was the dominant species accounting for more than 32% of the total emission rates of isoprenoids followed by β-phellandrene (~27%). Myrcene fluxes ranged from 0.8 to 24 μg g−1 (dw) h−1. α-Farnesene was the dominant sesquiterpene species, with average emission rates of 318 ng g−1 (dw) h−1. In the high Δ-3-carene chemotype, more than 48% of the total monoterpene emission was Δ-3-carene. The average Δ-3-carene emission rate, circa 609 ng g−1 (dw) h−1 reported here is consistent with the previously reported summer season value. The monoterpene emissions from spruce were dominated by limonene (35%), β-phellandrene (15%), α-pinene (14%) and eucalyptol (9%). Total spruce monoterpene emissions ranged from 0.55 up to 12.2 μg g−1 (dw) h−1. Overall the total terpene flux (monoterpenes + sesquiterpenes) from all studied tree species varied from 230 ng g−1 (dw) h−1 up to 66 μg g−1 (dw) h−1. Total ambient monoterpenes (including α-pinene, Δ-3-carene, β-pinene and β-myrcene) measured during the campaign varied in mixing ratio from a few pptv to over one ppbv. The most abundant biogenic VOCs measured above the canopy were α-pinene and Δ-3-carene, and these two compounds together contributed more than 50% of the total monoterpenes. The ambient data reflect the emission rate, atmospheric reactivity and tree type abundance. The diel cycles of isoprenoid mixing ratios showed high levels during the night-time which is consistent with continued low nocturnal emission and a low and stable boundary layer. The chirality of α-pinene was dominated by (+)-enantiomers both in the direct emission and in the atmosphere. The two highest emitters showed no enantiomeric preference for α-pinene emissions, whereas the two lowest emitting pines emitted more (+)-enantiomer. The spruce emissions were dominated by (−)-enantiomer. The exceptionally hot temperatures in the summer of 2010 led to relatively strong emissions of monoterpenes, greater diversity in chemical composition and high ambient mixing ratios.

References 1

Atkinson,~R. and Arey,~J.: Gas-phase tropospheric chemistry of biogenic volatile organiccompounds: a~review, Atmos. Environ., 37, S197–S219, 2003.

Bäck,~J., Hari,~P., Hakola,~H., Juurola,~E., and Kulmala,~M.: Dynamics of monoterpene emissions in \textitPinus sylvestris during early spring, Boreal Environ. Res., 10, 409–424, 2005.

Bäck, J., Aalto, J., Henriksson, M., Hakola, H., He, Q., and Boy, M.: Chemodiversity of a Scots pine stand and implications for terpene air concentrations, Biogeosciences, 9, 689–702, http://dx.doi.org/10.5194/bg-9-689-2012doi:10.5194/bg-9-689-2012, 2012.

Ciccioli,~P., Fabozzi,~C., Brancaleoni,~E., Cecinato,~A., Frattoni,~M., Loreto,~F., Kesselmeier,~J., Schafer,~L., Bode,~K., Torres,~L., and Fugit,~J L.: Use of the isoprene algorithm for predicting the monoterpene emission from the Mediterranean holm oak \textitQuercus ilex~L.: Performance and limits of this approach,~J. Geophys. Res., 102, 23319–23328, 1997.

Claeys,~M., Graham,~B., Vas,~G., Wang,~W., Vermeylen,~R., Pashynska,~V., Cafmeyer,~J., Guyon,~P., Andreae,~M O., Artaxo,~P., and Maenhaut, W.: Formations of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, 2004.

Copolovici,~L., Filella,~I., Llusia,~J., Niinemets,~U., and Penuelas,~J.: The capacity for thermal protection of photosynthetic electron Transport varies for different monoterpenes in \textitQuercus ilex, Plant Physiol., 139, 485–496, 2005.

Eerdekens,~G., Yassaa,~N., Sinha,~V., Aalto,~P P., Aufmhoff,~H., Arnold,~F., Fiedler,~V., Kulmala,~M., and Williams,~J.: VOC measurements within a boreal forest during spring 2005: on the occurrence of elevated monoterpene concentrations during night time intense particle concentration events, Atmos. Chem. Phys., 9, 8331–8350, http://dx.doi.org/10.5194/acp-9-8331-2009doi:10.5194/acp-9-8331-2009, 2009.

Ghirardo,~A., Koch,~K., Taipale,~R., Zimmer,~I., Schnitizler,~J P., and Rinne,~J.: Determination of \textitde novo and pool emissions of terpenes from four common boreal/alpine trees by \chem^13CO_2 labelling and PTR-MS analysis, Plant, Cell Environ., 33, 781–792, 2010.

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., and Zimmerman,~P.: A~global-model of natural volatile organic compound emissions,~J. Geophys. Res., 100, 8873–8892, 1995.

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

Hakola,~H., Laurila,~T., Rinne,~J., and Puhto,~K.: The ambient concentrations of biogenic hydrocarbons at a~Northern European, boreal site, Atmos. Environ., 34, 4971–4982, 2000.

Hakola,~H., Tarvainen,~V., Bäck,~J., Ranta,~H., Bonn,~B., Rinne,~J., and Kulmala,~M.: Seasonal variation of mono- and sesquiterpene emission rates of Scots pine, Biogeosciences, 3, 93–101, http://dx.doi.org/10.5194/bg-3-93-2006doi:10.5194/bg-3-93-2006, 2006.

Ivesniemi,~H., Levula,~J., Ojansuu,~R., Kolari,~P., Kulmala,~L., Pumpanen,~J., Launiainen,~S., Vesala,~T., and Nikinmaa,~E.: Long-term measurements of the carbon balance of a~boreal Scots pine dominated forest ecosystem, Boreal Environ. Res., 14, 731–753, 2009.

Janson,~R.: Monoterpene emissions from Scots Pine and Norwegian Spruce,~J. Geophys. Res., 98, 2839–2850, 1993.

Janson,~R. and De Serves,~C.: Acetone and monoterpene emissions from the boreal forest in Northern Europe, Atmos. Environ., 35,4629–4637, 2001.

Kaplan,~J O., Folberth,~G., and Hauglustaine,~D A.: Role of methane and biogenic volatile organic compound sources in late glacial and Holocene fluctuations of atmospheric methane concentrations, Global Biogeochem. Cy., 20, GB2016, doi10.1029/2005gb002590, 2006.

Komenda,~M. and Koppmann,~R.: Monoterpene emissions from Scots pine (\textitPinus sylvestris): Field studies ofemission rate variabilities,~J. Geophys. Res., 107, D13, http://dx.doi.org/10.1029/2001JD000691doi:10.1029/2001JD000691, 2002.

Komenda,~M., Kobel,~K., Koppmann,~R., and Wildt,~J.: Comparability of biogenic VOC emission rate measurements under laboratory and ambient conditions at the example of monoterpene emissions from Scots pine (\textitPinus sylvestris), J. Atmos. Chem., 45, 1–23, 2003.

Kulmala,~M., Vehkamäki,~H., Petäjä,~T., Dal Maso,~M., Lauri,~A., Kerminen,~V.-M., Birmili,~W., and McMurry,~P H.: Formation and growth rates of ultrafine atmospheric particles: A~review of observations,~J. Aerosol Sci., 35, 143–176, 2004.

Lindfors,~V. and Laurila,~T : Biogenic volatile organic compound (VOC) emissions from forests in Finland, Boreal Environ. Res., 5, 95–113, 2000.

Lindfors,~V., Laurila,~T., Hakola,~H., Steinbrecher,~R., and Rinne,~J.: Modeling speciated terpenoid emissions from the European boreal forest, Atmos. Environ., 34, 4983–4996, 2000.

Loreto,~F., Förster,~A., Durr,~M., Csiky,~O., and Seufert,~G.: On the monoterpene emission under heat stress and on the increased thermotolerance of leaves of \textitQuercus ilex~L. fumigated with selected monoterpenes, Plant Cell Environ., 21, 101–107, 1998.

Martin,~D., Tholl,~D., Gershenzon,~J., and Bohlmann,~J.: Methyl jasmonate induces traumatic resin ducts, terpenoid resin biosynthesis, and terpenoid accumulation in developing xylem of Norway spruce stems, Plant Physiol., 129, 1–16, 2002.

Mogensen, D., Smolander, S., Sogachev, A., Zhou, L., Sinha, V., Guenther, A., Williams, J., Nieminen, T., Kajos, M. K., Rinne, J., Kulmala, M., and Boy, M.: Modelling atmospheric OH-reactivity in a boreal forest ecosystem, Atmos. Chem. Phys., 11, 9709–9719, http://dx.doi.org/10.5194/acp-11-9709-2011doi:10.5194/acp-11-9709-2011, 2011.

Persson,~M., Borgkarlson,~A K., and Norin,~T.: Enantiomeric composition of 6 chiral monoterpene hydrocarbons in different tissues of Pica-Abies, Phytochem., 33, 303–307, 1993.

Pollmann,~J., Ortega,~J., and Helmig,~D.: Analysis of atmospheric sesquiterpenes: sampling losses and mitigation of ozone interference, Environ. Sci. Technol., 39, 9620–9629, 2005.

Rinne,~J., Hakola,~H., and Laurila,~T.: Vertical fluxes of monoterpenes above a~Scots pine stand in the boreal vegetation zone, Phys. Chem. Earth (B), 24, 711–715, 1999.

Rinne,~J., Hakola,~H., Laurila,~T., and Rannik, Ü.: Canopy scale monoterpene emissions of Pinussylvestris dominated forests, Atmos. Environ., 34, 1099–1107, 2000.

Rinne,~J., Taipale,~R., Markkanen,~T., Ruuskanen,~T M., Hellén,~H., Kajos,~M K., Vesala,~T., and Kulmala,~M.: Hydrocarbon fluxes above a Scots pine forest canopy: measurements and modeling, Atmos. Chem. Phys., 7, 3361–3372, http://dx.doi.org/10.5194/acp-7-3361-2007doi:10.5194/acp-7-3361-2007, 2007.

Shao,~M., Czapiewski,~K V., Heiden,~A C., Kobel,~K., Komenda,~M., Koppman,~R., and Wildt,~J.: Volatile organic compound emissions from Scots pine: Mechanisms and description by algorithms,~J. Geophys. Res., 106, 20483–20491, 2001.

Singsaas,~E L., Lerdau,~M., Winter,~K., and Sharkey,~T D.: Isoprene increases thermotolerance of isoprene-emitting species, Plant Physiol., 115, 1413–1420, 1997.

Song,~W., Williams,~J., Yassaa,~N., Martinez,~M., Adame,~J A., Hidalgo,~P J., Bozem,~H., and Lelieveld,~J.: 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.

Stokes,~G Y., Chen,~E H., Buchbinder,~A M., Paxton,~W F., Keeley,~A., and Geiger,~F M., Atmospheric Heterogeneous stereochemistry J. Am. Chem. Soc., 131(38), 13733–13737, http://dx.doi.org/10.1021/ja904206tdoi:10.1021/ja904206t, 2009.

Thoss,~V., O'Reilly-Wapstra,~J., and Iason,~G R.: Assessment and implications of intraspecific and phenological variability in monoterpenes of Scots pine (\textitPinus sylvestris) foliage, J. Chem. Ecol., 33, 477–491, 2007.

Tunved,~P., Hansson,~H C., Kerminen,~V M., Ström,~J., Dal Maso,~M., Lihavainen,~H., Viisanen,~Y., Aalto,~P P., Komppula,~M., and Kulmala,~M.: High natural aerosol loading over boreal forests, Science, 312, 261–263, 2006.

Williams,~J.: Organic trace gases: an overview, Environ. Chem., 1, 125–136, 2004.

Williams,~J., Yassaa,~N., Bartenbach,~S., and Lelieveld,~J.: Mirror image hydrocarbons from Tropical and Boreal forests, Atmos. Chem. Phys., 7, 973–980, http://dx.doi.org/10.5194/acp-7-973-2007doi:10.5194/acp-7-973-2007, 2007.

Williams,~J., Crowley,~J., Fischer,~H., Harder,~H., Martinez,~M., Petäjä,~T., Rinne,~J., Bäck,~J., Boy,~M., Dal~Maso,~M., Hakala,~J., Kajos,~M., Keronen,~P., Rantala,~P., Aalto,~J., Aaltonen,~H., Paatero,~J., Vesala,~T., Hakola,~H., Levula,~J., Pohja,~T., Herrmann,~F., Auld,~J., Mesarchaki,~E., Song,~W., Yassaa,~N., Nölscher,~A., Johnson,~A M., Custer,~T., Sinha,~V., Thieser,~J., Pouvesle,~N., Taraborrelli,~D., Tang,~M J., Bozem,~H., Hosaynali-Beygi,~Z., Axinte,~R., Oswald,~R., Novelli,~A., Kubistin,~D., Hens,~K., Javed,~U., Trawny,~K., Breitenberger,~C., Hidalgo,~P J., Ebben,~C J., Geiger,~F M., Corrigan,~A L., Russell,~L M., Ouwersloot,~H G., Vilà-Guerau~de~Arellano,~J., Ganzeveld,~L., Vogel,~A., Beck,~M., Bayerle,~A., Kampf,~C J., Bertelmann,~M., Köllner,~F., Hoffmann,~T., Valverde,~J., González,~D., Riekkola,~M.-L., Kulmala,~M., and Lelieveld,~J.: The summertime Boreal forest field \mboxmeasurement intensive (HUMPPA-COPEC-2010): an overview of meteorological and \mboxchemical influences, Atmos. Chem. Phys., 11, 10599–10618, http://dx.doi.org/10.5194/acp-11-10599-2011doi:10.5194/acp-11-10599-2011, 2011.

Yassaa,~N. and Williams,~J.: Analysis of enantiomeric and non-enantiomeric monoterpenes in plant emissions using portable dynamic air sampling/solid-phase microextraction (PDAS-SPME) and chiral gas chromatography/mass spectrometry, Atmos. Environ., 39, 4875–4884, 2005.

Yassaa,~N. and Williams,~J.: Enantiomeric monoterpene emissions from natural and damaged Scots pine in a~boreal coniferous forest measured using solid-phase microextraction and gas chromatography/mass spectrometry,~J. Chromatogr. A, 1141, 138–144, 2007.

Yassaa,~N., Brancaleoni,~E., Frattoni,~M., and Ciccioli,~P.: Trace level determination of enantiomericmonoterpenes in terrestrial plant emission and in the atmosphere using a~β-cyclodextrin capillary column coupled with thermal desorption and mass spectrometry,~J. Chromatogr. A, 915, 185–197, 2001.

Yassaa,~N., Custer,~T., Song,~W., Pech,~F., Kesselmeier,~J., and Williams,~J.: Quantitative and enantioselective analysis of monoterpenes from plant chambers and in ambient air using SPME, Atmos. Meas. Tech., 3, 1615–1627, http://dx.doi.org/10.5194/amt-3-1615-2010doi:10.5194/amt-3-1615-2010, 2010.