ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-3909-2012 Seasonal variation in vertical volatile compounds air concentrations within a remote hemiboreal mixed forest Noe S. M. 1 Hüve K. 1 Niinemets Ü. 1 Copolovici L. 1 Department of Plant Physiology, Institute of Agricultural and Environmental Sciences, Estonian University of Life Sciences, Kreutzwaldi 1, 51014 Tartu, Estonia 03 05 2012 12 9 3909 3926 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/12/3909/2012/acp-12-3909-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/3909/2012/acp-12-3909-2012.pdf

The vertical distribution of ambient biogenic volatile organic compounds (BVOC) concentrations within a hemiboreal forest canopy was investigated over a period of one year. Variability in temporal and spatial isoprene concentrations, ranging from 0.1 to 7.5 μg m<sup>−3</sup>, can be mainly explained by biogenic emissions from deciduous trees. Monoterpene concentrations exceeded isoprene largely and ranged from 0.01 to 140 μg m<sup>−3</sup> and during winter time anthropogenic contributions are likely. Variation in monoterpene concentrations were found to be largest right above the ground and the vertical profiles suggest a weak mixing leading to terpene accumulation in the lower canopy. Exceptionally high values were recorded during a heat wave in July 2010 with very high midday temperatures above 30 °C for several weeks. During summer months, monoterpene exceeded isoprene concentrations 6-fold and during winter 12-fold. During summer months, dominance of α-pinene in the lower and of limonene in the upper part of the canopy was observed, both accounting for up to 70% of the total monoterpene concentration. During wintertime, Δ<sup>3</sup>-carene was the dominant species, accounting for 60% of total monoterpene concentration in January. Possible biogenic monoterpene sources beside the foliage are the leaf litter, the soil and also resins exuding from stems. In comparison, the hemiboreal mixed forest canopy showed similar isoprene but higher monoterpene concentrations than the boreal forest and lower isoprene but substantially higher monoterpene concentrations than the temperate mixed forest canopies. These results have major implications for simulating air chemistry and secondary organic aerosol formation within and above hemiboreal forest canopies. Possible effects of in-cartridge oxidation reactions are discussed as our measurement technique did not include oxidant scavenging. A comparison between measurements with and without scavenging oxidants is presented.

 References Aaltonen,~H., Pumpanen,~J., Pihlatie,~M., Hakola,~H., Hellèn,~H., Kulmala,~L., Vesala,~T., and Bäck,~J.: Boreal pine forest floor biogenic volatile organic compound emissions peak in early summer and autumn, Agr. Forest Meteorol., 151, 682–691, 2011. Arneth,~A. and Niinemets, Ü.: Induced BVOCs: how to bug our models?, Trends Plant Sci., 15, 118–125, 2010. Arneth, A., Monson, R. K., Schurgers, G., Niinemets, Ü., and Palmer, P. I.: Why are estimates of global terrestrial isoprene emissions so similar (and why is this not so for monoterpenes)?, Atmos. Chem. Phys., 8, 4605–4620, http://dx.doi.org/10.5194/acp-8-4605-2008doi:10.5194/acp-8-4605-2008, 2008. Arneth,~A., Harrison,~S P., Zaehle,~S., Tsigaridis,~K., Menon,~S., Bartlein, ~P J., Feichter,~J., Korhola,~A., Kulmala,~M., O'Donnell,~D., Schurgers,~G., Sorvari,~S., and Vesala,~T.: Terrestrial biogeochemical feedbacks in the climate system, Nat. Geosci., 3, 525–532, http://dx.doi.org/10.1038/ngeo905doi:10.1038/ngeo905, 2010. Arnts,~R R.: Reduction of biogenic VOC sampling losses from ozone via trans-2-butene addition, Environ. Sci. Technol., 42, 7663–7669, 2008. Atkinson,~R.: Atmospheric chemistry of VOCs and NO<sub>x</sub>, Atmos. Environ., 34, 2063–2101, http://dx.doi.org/10.1016/S1352-2310(99)00460-4doi:10.1016/S1352-2310(99)00460-4, 2000. Atkinson,~R., Aschmann,~S M., and Arey,~J.: Rate constants for the gas-phase reactions of OH and \chemNO_3 radicals and \chemO_3 with sabinene and camphene at $296\pm 2$ K, Atmos. Environ. A-Gen., 24, 2647–2654, http://dx.doi.org/10.1016/0960-1686(90)90144-Cdoi:10.1016/0960-1686(90)90144-C, 1990. Bland,~J M., and Altman,~D G.: Measuring agreement in method comparison studies, Stat. Methods Med. Res., 8, 135–160, 1999 Cai,~H. and Xie,~S D.: Tempo-spatial variation of emission inventories of speciated volatile organic compounds from on-road vehicles in China, Atmos. Chem. Phys., 9, 6983–7002, http://dx.doi.org/10.5194/acp-9-6983-2009doi:10.5194/acp-9-6983-2009, 2009. Calogirou,~A., Larsen,~B R., Brussol,~C., Duane,~M., and Kotzias,~D.: Decomposition of terpenes by ozone during sampling on Tenax, Anal. Chem., 68, 1499–1506, 1996. Ciccioli,~P., Brancaleoni,~E., Possanzini,~M., Brachetti,~A., and Di~Palo,~C.: Physico-Chemical Behaviour of Atmospheric Pollutants, 62–73,~D. Reidel Publishing Co., Dordrecht, The Netherlands, 1984. Copolovici,~L., Filella,~I., Llusia,~J., Niinemets,~Ü., and Peñuelas,~J.: The capacity for thermal protection of photosynthetic electron transport varies for different monoterpenes in \textitQuercus ilex, Plant Physiol., 139, 485–496, 2005. Copolovici,~L., Kännaste,~A., and Niinemets,~Ü.: Gas Chromatography-mass spectrometry method for determination of monoterpene and sesquiterpene emissions from stressed plants, Stud. Univ. Babes-Bol., 54, 329–339, 2009. Davison,~B., Taipale,~R., Langford,~B., Misztal,~P., Fares,~S., Matteucci,~G., Loreto,~F., Cape,~J N., Rinne,~J., and Hewitt,~C N.: Concentrations and fluxes of biogenic volatile organic compounds above a Mediterranean macchia ecosystem in western Italy, Biogeosciences, 6(8), 1655–1670, http://dx.doi.org/10.5194/bg-6-1655-2009doi:10.5194/bg-6-1655-2009, 2009. 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. Fick,~J., Pommer,~L., Andersson,~B., and Nilsson,~C.: Ozone removal in the sampling of parts per billion levels of terpenoid compounds: An evaluation of different scrubber materials, Environ. Sci. Technol., 35, 1458–1462, 2001. Forkel,~R., Klemm,~O., Graus,~M., Rappenglück,~B., Stockwell,~W R., Grabmer,~W., Held,~A., Hansel,~A., and Steinbrecher,~R.: Trace gas exchange and gas phase chemistry in a Norway spruce forest: a study with a coupled 1-dimensional canopy atmospheric chemistry emission model, Atmos. Environ., 40, 28–42, http://dx.doi.org/10.1016/j.atmosenv.2005.11.070doi:10.1016/j.atmosenv.2005.11.070, 2006. Fuentes,~J., Wang,~D., Bowling,~D., Potosnak,~M., Monson,~R., Goliff,~W., and Stockwell,~W.: Biogenic hydrocarbon chemistry within and above a mixed deciduous forest, J. Atmos. Chem., 56, 165–185, 2007. Gray,~C M., Monson,~R K., and Fierer,~N.: Emissions of volatile organic compounds during the decomposition of plant litter, J. Geophys. Res., 115, G03015, http://dx.doi.org/10.1029/2010JG001291doi:10.1029/2010JG001291, 2010. Guenther,~A., Karl,~T., Harley,~P., Wiedinmyer,~C., Palmer,~P I., and 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, http://dx.doi.org/10.5194/acp-6-3181-2006doi:10.5194/acp-6-3181-2006, 2006. 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., Laurila,~T., Hiltunen,~V., Hellén,~H., and Keronen,~P.: Seasonal variation of VOC concentrations above a boreal coniferous forest, Atmos. Environ., 37, 1623–1634, 2003. Hakola,~H., Hellén,~H., Tarvainen,~V., Bäck,~J., Patokoski,~J., and Rinne,~J.: Annual variations of atmospheric VOC concentrations in a boreal forest., Boreal Environ. Res., 14, 722–730, 2009. Harrison,~D., Hunter,~M C., Lewis,~A C., Seakins,~P W., Bonsang,~B., Gros,~V., Kanakidou,~M., Touaty,~M., Kavouras,~I., Mihalopoulos,~N., Stephanou,~E., Alves,~C., Nunes,~T., and Pio,~C.: Ambient isoprene and monoterpene concentrations in a Greek fir (\textitAbies borisii-regis) forest. Reconciliation with emissions measurements and effects on measured OH concentrations, Atmos. Environ., 35, 4699–4711, 2001. Hayward,~S., Muncey,~R J., James,~A E., Halsall,~C J., and Hewitt,~C N.: Monoterpene emissions from soil in a Sitka spruce forest, Atmos. Environ., 35, 4081–4087, 2001. Helmig, D.: Ozone removal techniques in the sampling of atmosphericvolatile organic trace gases, Atmos. Environ., 31, 3635–3651, 1997. Holzinger,~R., Lee,~A., Paw,~K T., and Goldstein,~U A H.: Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds, Atmos. Chem. Phys., 5, 67–75, http://dx.doi.org/10.5194/acp-5-67-2005doi:10.5194/acp-5-67-2005, 2005. Holzinger,~R., Lee,~A., McKay,~M., and Goldstein,~A H.: Seasonal variability of monoterpene emission factors for a ponderosa pine plantation in California, Atmos. Chem. Phys., 6, 1267–1274, http://dx.doi.org/10.5194/acp-6-1267-2006doi:10.5194/acp-6-1267-2006, 2006. Intergovernmental Panel on Climate Change: Fourth Assessment Report: Climate Change 2007: The AR4 Synthesis Report, Geneva: IPCC, available at: http://www.ipcc.ch/ipccreports/ar4-wg1.htm, last access: 3~August~2010, 2007. Isidorov,~V A., Smolewska,~M., Purzyńska-Pugacewicz,~A., and Tyszkiewicz,~Z.: Chemical composition of volatile and extractive compounds of pine and spruce leaf litter in the initial stages of decomposition, Biogeosciences, 7, 2785–2794, http://dx.doi.org/10.5194/bg-7-2785-2010doi:10.5194/bg-7-2785-2010, 2010. Kanakidou,~M., Seinfeld,~J H., Pandis,~S N., Barnes,~I., Dentener,~F J., Facchini,~M C., Van Dingenen,~R., Ervens,~B., Nenes,~A., Nielsen,~C J., Swietlicki,~E., Putaud,~J P., Balkanski,~Y., Fuzzi,~S., Horth,~J., Moortgat,~G K., Winterhalter,~R., Myhre,~C E L., Tsigaridis,~K., Vignati,~E., Stephanou,~E G., and Wilson,~J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, http://dx.doi.org/10.5194/acp-5-1053-2005doi:10.5194/acp-5-1053-2005, 2005. Karl,~T., Potosnak,~M., Guenther,~A., Clark,~D., Walker,~J., Herrick,~J D., and Geron,~C.: Exchange processes of volatile organic compounds above a tropical rain forest: implications for modeling tropospheric chemistry above dense vegetation, J. Geophys. Res., 109, D18306, http://dx.doi.org/10.1029/2004JD004738doi:10.1029/2004JD004738, 2004. Kulmala,~M., Suni,~T., Lehtinen,~K E J., Dal Maso,~M., Boy,~M., Reissell,~A., Rannik,~Ü, Aalto,~P., Keronen,~P., Hakola,~H., Bäck,~J., Hoffmann,~T., Vesala,~T., and Hari,~P.: A new feedback mechanism linking forests, aerosols, and climate, Atmos. Chem. Phys., 4, 557–562, http://dx.doi.org/10.5194/acp-4-557-2004doi:10.5194/acp-4-557-2004, 2004. Lappalainen,~H K., Sevanto,~S., Bäck,~J., Ruuskanen,~T M., Kolari,~P., Taipale,~R., Rinne,~J., Kulmala,~M., and Hari,~P.: Day-time concentrations of biogenic volatile organic compounds in a boreal forest canopy and their relation to environmental and biological factors, Atmos. Chem. Phys., 9, 5447–5459 http://dx.doi.org/10.5194/acp-9-5447-2009doi:10.5194/acp-9-5447-2009, 2009. Lee,~J H., Batterman,~S A., Jia,~C., and Chernyak,~S.: Ozone Artifacts and Carbonyl Ceasurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents, J. Air & Waste Manage. Assoc., 56, 1503–1517, 2006. Lyubovtseva,~Y S., Sogacheva,~L., Dal~Maso,~M., Bonn,~B., Keronen,~P., and Kulmala,~M.: Seasonal variations of trace gases, meteorological parameters, and formation of aerosols in boreal forests., Boreal Environ. Res., 10, 493–510, 2005. Mayrhofer,~S., Teuber,~M., Zimmer,~I., Louis,~S., Fischbach,~R J., and Schnitzler,~J.-P.: Diurnal and seasonal variation of isoprene biosynthesis-related genes in grey poplar leaves, Plant Physiol., 139, 474–484, http://dx.doi.org/10.1104/pp.105.066373doi:10.1104/pp.105.066373, 2005. Metts,~T A.: Heterogeneous reactions of ozone and D-limonene on activated carbon, Indoor Air, 17, 362–371, 2007. Mielke,~L H., Pratt,~K. A., Shepson,~P B., McLuckey,~S A., Wisthaler,~A., and Hansel,~A.: Quantitative Determination of Biogenic Volatile Organic Compounds in the Atmosphere Using Proton-Transfer Reaction Linear Ion Trap Mass Spectrometry, Analyt. Chem., 82, 7952–7957, 2010. Ng,~N L., Kwan,~A J., Surratt,~J D., Chan,~A W H., Chhabra,~P S., Sorooshian,~A., Pye,~H O T., Crounse,~J D., Wennberg,~P O., Flagan,~R C., and Seinfeld,~J H.: Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (\chemNO_3), Atmos. Chem. Phys., 8, 4117–4140, http://dx.doi.org/10.5194/acp-8-4117-2008doi:10.5194/acp-8-4117-2008, 2008. Niinemets,~Ü.: Responses of forest trees to single and multiple environmental stresses from seedlings to mature plants: past stress history, stress interactions, tolerance and acclimation, Forest Ecol. Manag., 260, 1623–1639, 2010a. Niinemets,~Ü.: Mild versus severe stress and BVOCs: thresholds, priming and consequences, Trends Plant Sci., 15, 145–153, 2010b. Niinemets,~Ü., Arneth,~A., Kuhn,~U., Monson,~R K., Peñuelas,~J., and Staudt,~M.: The emission factor of volatile isoprenoids: stress, acclimation, and developmental responses, Biogeosciences, 7, 2203–2223, http://dx.doi.org/10.5194/bg-7-2203-2010doi:10.5194/bg-7-2203-2010, 2010c. Niinemets,~Ü., Monson,~R K., Arneth,~A., Ciccioli,~P., Kesselmeier,~J., Kuhn,~U., Noe,~S M., Peñuelas,~J., and Staudt,~M.: The leaf-level emission factor of volatile isoprenoids: caveats, model algorithms, response shapes and scaling, Biogeosciences, 7, 1809–1832, http://dx.doi.org/10.5194/bg-7-1809-2010doi:10.5194/bg-7-1809-2010, 2010d. Niinemets,~Ü., Kuhn,~U., Harley,~P C., Staudt,~M., Arneth,~A., Cescatti,~A., Ciccioli,~P., Copolovici,~L., Geron,~C., Guenther,~A., Kesselmeier,~J., Lerdau,~M T., Monson,~R K., and Peñuelas,~J.: Estimations of isoprenoid emission capacity from enclosure studies: measurements, data processing, quality and standardized measurement protocols, Biogeosciences, 8, 2209–2246, http://dx.doi.org/10.5194/bg-8-2209-2011doi:10.5194/bg-8-2209-2011, 2011. Nilsson,~S G.: Forests in the temperate-boreal transition: natural and man-made features, Ecol. Bull., 46, 61–71, 1997. Noe,~S M., Copolovici,~L., Niinemets, Ü., and Vaino,~E.: Foliar limonene uptake scales positively with leaf lipid content: \qutnon-emitting species absorb and release monoterpenes., Plant Biol., 10, 129–137, 2008. Noe,~S M., Kimmel,~V., Hüve,~K., Copolovici,~L., Portillo-Estrada,~M., Püttsepp,~Ü., Jõgiste,~K., Niinemets, Ü., Hörtnagl,~L., and Wohlfahrt,~G.: Ecosystem-scale biosphere-atmosphere interactions of a hemiboreal mixed forest stand at Järvselja, Estonia, Forest Ecol. Manag., 262, 71–81, http://dx.doi.org/10.1016/j.foreco.2010.09.013doi:10.1016/j.foreco.2010.09.013, 2010. Pollmann, J., Ortega, J., and Helmig, D.: Analysis of atmospheric sesquiterpenes: Sampling losses and mitigation of ozone interferences, Environ. Sci. Technol., 39, 9620–9629, 2005. Räisänen,~T., Ryyppö,~A., and Kellomäki,~S.: Impact of timber felling on the ambient monoterpene concentration of a Scots pine (\textitPinus sylvestris~L.) forest, Atmos. Environ., 42, 6759–6766, 2008. Räisänen,~T., Ryyppö,~A., and Kellomäki,~S.: Monoterpene emission of a boreal Scots pine (\textitPinus sylvestris~L.) forest, Agr. Forest Meteorol., 149, 808–819, 2009. Ramirez,~K., Lauber,~C., and Fierer,~N.: Microbial consumption and production of volatile organic compounds at the soil-litter interface, Biogeochemistry, 99, 97–107, 2010. Reimann,~S., Calanca,~P., and Hofer,~P.: The anthropogenic contribution to isoprene concentrations in a rural atmosphere, Atmos. Environ., 34, 109–115, 2000. \bibitem[Rinne et~al.(2005)Rinne, Ruuskanen, Reissell, Taipale, Hakola, Kulmala] Rinne:2005it Rinne,~J., Ruuskanen,~T M., Reissell,~A., Taipale~R., Hakola,~H., and Kulmala,~M.: On-line PTR-MS measurements of atmospheric concentrations of volatile organic compounds in a European boreal forest ecosystem, Boreal Environ. Res., 10, 425–436, 2005. Rinne,~H J I., Guenther,~A B., Greenberg,~J P., and Harley,~P C.: Isoprene and monoterpene fluxes measured above Amazonian rainforest and their dependence on light and temperature, Atmos. Environ., 36, 2421–2426, 2002. Rinne,~J., Hakola,~H., Laurila,~T., and Rannik,~Ü.: Canopy scale monoterpene emissions of \textitPinus sylvestris dominated forests, Atmos. Environ., 34, 1099–1107, 2000. Sabillón,~D. and Cremades,~L V.: Diurnal and seasonal variation of monoterpene emission rates for two typical Mediterranean species (\textitPinus pinea and \textitQuercus ilex) from field measurements–relationship with temperature and PAR, Atmos. Environ., 35, 4419–4431, 2001. Sætersdal,~M., Birks,~H J B., and Peglar,~S.: Predicting changes in Fennoscandian vascular-plant species richness as a result of future climatic change, J. Biogeogr., 25, 111–112, 1998. Schurgers,~G., Arneth,~A., Holzinger,~R., and Goldstein,~A H.: Process-based modelling of biogenic monoterpene emissions combining production and release from storage, Atmos. Chem. Phys., 9, 3409–3423, http://dx.doi.org/10.5194/acp-9-3409-2009doi:10.5194/acp-9-3409-2009, 2009. Seinfeld, J H. and Pandis, S N.: Atmospheric Chemistry and Physics, John Wiley and Sons Inc., Hoboken, New Jersey, USA, 2nd edn., 2006. Smolander,~A., Ketola,~R A., Kotiaho,~T., Kanerva,~S., Suominen,~K., and Kitunen,~V.: Volatile monoterpenes in soil atmosphere under birch and conifers: effects on soil N transformations, Soil Biol. Biochem., 38, 3436–3442, 2006. Spirig,~C., Neftel,~A., Ammann,~C., Dommen,~J., Grabmer,~W., Thielmann,~A., Schaub,~A., Beauchamp,~J., Wisthaler,~A., and Hansel,~A.: Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry, Atmos. Chem. Phys., 5, 465–481, http://dx.doi.org/10.5194/acp-5-465-2005doi:10.5194/acp-5-465-2005, 2005. Spracklen,~D V., Bonn,~B., and Carslaw,~K S.: Boreal forests, aerosols and the impacts on clouds and climate, Philos. T. Roy. Soc. A, 366, 4613–4626, 2008. Strong,~C., Fuentes,~J., and Baldocchi,~D.: Reactive hydrocarbon flux footprints during canopy senescence, Agr. Forest Meteorol., 127, 159–173, 2004. Stroud,~C., Makar,~P., Karl,~T., Guenther,~A., Geron,~C., Turnipseed,~A., Nemitz,~E., Baker,~B., Potosnak,~M., and Fuentes,~J D.: Role of canopy-scale photochemistry in modifying biogenic-atmosphere exchange of reactive terpene species: results from the CELTIC field study, J. Geophys. Res., 110, D17303, http://dx.doi.org/10.1029/2005JD005775doi:10.1029/2005JD005775, 2005. Sun,~Z., Copolovici,~L., and Niinemets,~Ü.: Can the capacity for isoprene emission acclimate to environmental modifications during autumn senescence in temperate deciduous tree species \textitPopulus tremula?, J. Plant Res., 125, 263–274, 2012. Theloke,~J. and Friedrich,~R.: Compilation of a database on the composition of anthropogenic VOC emissions for atmospheric modeling in Europe, Atmos. Environ., 41, 4148–4160, 2007. Toome,~M., Randjärv,~P., Copolovici,~L., Niinemets, Ü., Heinsoo,~K., Luik,~A., and Noe,~S M.: Leaf rust induced volatile organic compounds signalling in willow during the infection, Planta, 232, 235–243, 2010. Turtola,~S., Manninen,~A.-M., Rikala,~R., and Kainulainen,~P.: Drought stress alters the concentration of wood terpenoids in Scots pine and Norway spruce seedlings, J. Chem. Ecol., 29, 1981–1995, 2003.