Abstract
Hydrocarbon species and related meteorological and chemical variables were measured within and immediately above a loblolly pine forest in North Carolina, USA during 15–18 July 2003. The degree of photochemical processing within the forest canopy of biogenic hydrocarbons emitted at the foliage level is investigated with the aid of a one-dimensional photochemical model. Such in-canopy photochemical processes remain poorly understood largely due to limited observations of plant-emitted gases, chemical reactions, and yields of photochemical reactions inside plant canopies. These hydrocarbons are vented into the overlying atmospheric boundary layer and participate in regional-scale photochemical processes. At the forested site, isoprene was the dominant sink for hydroxyl radicals and ozone precursor among all the volatile organic compounds. Abundances of many hydrocarbons peaked in the early morning and late afternoon/early evening due to local emissions, while reaching minima at mid-day due to intense turbulent mixing and vigorous photochemistry. Methyl vinyl ketone and methacrolein, which were produced mostly from isoprene oxidation, had elevated mixing ratios during noontime in addition to maximum levels in the early morning and early evening. Abundances of species with dominant biogenic origin (e.g., isoprene, α-pinene, β-pinene, and limonene) were higher within the canopy than above the forest. For the species produced in the atmospheric boundary layer due to photochemical reactions, abundances residing away from the canopy were higher than those just above the canopy in response to photochemical production and/or transport associated with advection. Within the forest canopy photochemical reactions destroyed approximately 10 % of the locally emitted isoprene. Chemically more reactive species such as limonene experienced greater rates of removal in response to in-canopy chemical processing. Model sensitivity studies indicated that nitrogen oxides limited the formation of oxidants at the forested study site.
Similar content being viewed by others
Notes
NOX = nitric oxide (NO) + nitrogen dioxide (NO2)
References
Andreae, M.O., Artaxo, P., Brandao, C., Carswell, F.E., Ciccioli, P., da Costa, A.L., Culf, A.D., Esteves, J.L., Gash, J.H.C., Grace, J., Kabat, P., Lelieveld, J., Malhi, Y., Manzi, A.O., Meixner, F.X., Nobre, A.D., Nobre, C., Ruivo, M.D.L.P., Silva-Dias, M.A., Stefani, P., Valentini, R., von Jouanne, J., Waterloo, M.J.: Biogeochemical cycling of carbon, water, energy, trace gases, and aerosols in Amazonia: the LBA-EUSTACH experiments. J. Geophys. Res. Atmos. 107(D20), 8066 (2002). doi:10.1029/2001jd000524
Apel, E.C., Riemer, D.D., Hills, A., Baugh, W., Orlando, J., Faloona, I., Tan, D., Brune, W., Lamb, B., Westberg, H., Carroll, M.A., Thornberry, T., Geron, C.D: Measurement and interpretation of isoprene fluxes and isoprene, methacrolein, and methyl vinyl ketone mixing ratios at the PROPHET site during the 1998 Intensive. J. Geophys. Res. Atmos. 107(D3), (2002). doi:10.1029/2000jd000225
Atkinson, R.: Atmospheric chemistry of VOCs and NOx. Atmos. Environ. 34, 2063–2101 (2000). doi:10.1016/S1352-2310(99)00460-4
Atkinson, R., Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review. Atmos. Environ. 37, S197–S219 (2003). doi:10.1016/S1352-2310(03)00391-1
Baldocchi, D.: A Multi-layer model for estimating sulfur-dioxide deposition to a deciduous oak forest canopy. Atmos. Environ. 22(5), 869–884 (1988). doi:10.1016/0004-6981(88)90264-8
Barr, J.G., Fuentes, J.D., Bottenheim, J.W.: Radiative forcing of phytogenic aerosols. J. Geophys. Res. Atmos. 108(D15), 4466 (2003). doi:10.1029/2002jd002978
Beare, R.J., MacVean, M.K., Holtslag, A.A.M., Cuxart, J., Esau, I., Golaz, J.C., Jimenez, M.A., Khairoutdinov, M., Kosovic, B., Lewellen, D., Lund, T.S., Lundquist, J.K., McCabe, A., Moene, A.F., Noh, Y., Raasch, S., Sullivan, P.: An intercomparison of large-eddy simulations of the stable boundary layer. Bound.-Lay. Meteorol. 118(2), 247–272 (2006). doi:10.1007/s10546-004-2820-6
Biesenthal, T.A., Shepson, P.B.: Observations of anthropogenic inputs of the isoprene oxidation products methyl vinyl ketone and methacrolein to the atmosphere. Geophys. Res. Lett. 24(11), 1375–1378 (1997). doi:10.1029/97gl01337
Biesenthal, T.A., Wu, Q., Shepson, P.B., Wiebe, H.A., Anlauf, K.G., Mackay, G.I.: A study of relationships between isoprene, its oxidation products, and ozone, in the Lower Fraser Valley, BC. Atmos. Environ. 31(14), 2049–2058 (1997). doi:10.1016/S1352-2310(96)00318-4
Biesenthal, T.A., Bottenheim, J.W., Shepson, P.B., Brickell, P.C.: The chemistry of biogenic hydrocarbons at a rural site in eastern Canada. J. Geophys. Res. Atmos. 103(D19), 25487–25498 (1998). doi:10.1029/98jd01848
Borbon, A., Fontaine, H., Veillerot, M., Locoge, N., Galloo, J.C., Guillermo, R.: An investigation into the traffic-related fraction of isoprene at an urban location. Atmos. Environ. 35(22), 3749–3760 (2001). doi:10.1016/S1352-2310(01)00170-4
Bottenheim, J.W., Shepherd, M.F.: C2-C6 hydrocarbon measurements at 4 rural locations across Canada. Atmos. Environ. 29(6), 647–664 (1995). doi:10.1016/1352-2310(94)00318-F
Boy, M., Sogachev, A., Lauros, J., Zhou, L., Guenther, A., Smolander, S.: SOSA—a new model to simulate the concentrations of organic vapours and sulphuric acid inside the ABL - part 1: model description and initial evaluation. Atmos. Chem. Phys. 11(1), 43–51 (2011). doi:10.5194/acp-11-43-2011
Brown, S.S., Degouw, J.A., Warneke, C., Ryerson, T.B., Dube, W.P., Atlas, E., Weber, R.J., Peltier, R.E., Neuman, J.A., Roberts, J.M., Swanson, A., Flocke, F., McKeen, S.A., Brioude, J., Sommariva, R., Trainer, M., Fehsenfeld, F.C., Ravishankara, A.R.: Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol. Atmos. Chem. Phys. 9(9), 3027–3042 (2009)
Browne, E.C., Cohen, R.C.: Effects of biogenic nitrate chemistry on the NOx lifetime in remote continental regions. Atmos. Chem. Phys. 12(24), 11917–11932 (2012). doi:10.5194/acp-12-11917-2012
Bryan, A.M., Bertman, S.B., Carroll, M.A., Dusanter, S., Edwards, G.D., Forkel, R., Griffith, S., Guenther, A.B.., Hansen, R.F., Helmig, D., Jobson, B.T., Keutsch, F.N., Lefer, B.L., Pressley, S.N., Shepson, P.B., Stevens, P.S., Steiner, A.L.: In-canopy gas-phase chemistry during CABINEX 2009: sensitivity of a 1-D canopy model to vertical mixing and isoprene chemistry. Atmos. Chem. Phys. 12(18), 8829–8849 (2012). doi:10.5194/acp-12-8829-2012
Carter, W.P.L., Atkinson, R.: Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx. Int. J. Chem. Kinet. 28(7), 497–530 (1996). doi:10.1002/(Sici)1097-4601(1996)28:7<497::Aid-Kin4>3.3.Co;2–7
Chameides, W.L., Lindsay, R.W., Richardson, J., Kiang, C.S.: The role of biogenic hydrocarbons in urban photochemical smog - Atlanta as a case-study. Science 241(4872), 1473–1475 (1988). doi:10.1126/science.3420404
Chan, A.W.H., Chan, M.N., Surratt, J.D., Chhabra, P.S., Loza, C.L., Crounse, J.D., Yee, L.D., Flagan, R.C., Wennberg, P.O., Seinfeld, J.H.: Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation. Atmos. Chem. Phys. 10(15), 7169–7188 (2010). doi:10.5194/acp-10-7169-2010
Chang, C.C., Chen, T.Y., Lin, C.Y., Yuan, C.S., Liu, S.C.: Effects of reactive hydrocarbons on ozone formation in southern Taiwan. Atmos. Environ. 39(16), 2867–2878 (2005). doi:10.1016/j.atmosenv.2004.12.042
Cheng, H.R., Guo, H., Saunders, S.M., Lam, S.H.M., Jiang, F., Wang, X.M., Simpson, I.J., Blake, D.R., Louie, P.K.K., Wang, T.J.: Assessing photochemical ozone formation in the Pearl River Delta with a photochemical trajectory model. Atmos. Environ. 44(34), 4199–4208 (2010). doi:10.1016/j.atmosenv.2010.07.019
Curren, K., Gillespie, T., Steyn, D., Dann, T., Wang, D.: Biogenic isoprene in the Lower Fraser Valley, British Columbia. J. Geophys. Res. Atmos. 103(D19), 25467–25477 (1998)
Cuxart, J., Holtslag, A.A.M., Beare, R.J., Bazile, E., Beljaars, A., Cheng, A., Conangla, L., Ek, M., Freedman, F., Hamdi, R., Kerstein, A., Kitagawa, H., Lenderink, G., Lewellen, D., Mailhot, J., Mauritsen, T., Perov, V., Schayes, G., Steeneveld, G.J., Svensson, G., Taylor, P., Weng, W., Wunsch, S., Xu, K.M.: Single-column model intercomparison for a stably stratified atmospheric boundary layer. Bound.-Lay. Meteorol. 118(2), 273–303 (2006). doi:10.1007/s10546-005-3780-1
de Gouw, J.A., Middlebrook, A.M., Warneke, C., Goldan, P.D., Kuster, W.C., Roberts, J.M., Fehsenfeld, F.C., Worsnop, D.R., Canagaratna, M.R., Pszenny, A.A.P., Keene, W.C., Marchewka, M., Bertman, S.B., Bates, T.S.: Budget of organic carbon in a polluted atmosphere: results from the New England air quality study in 2002. J. Geophys. Res. Atmos. 110(D16), D16305 (2005). doi:10.1029/2004jd005623
Derwent, R.G., Jenkin, M.E., Saunders, S.M., Pilling, M.J.: Photochemical ozone creation potentials for organic compounds in northwest Europe calculated with a master chemical mechanism. Atmos. Environ. 32(14–15), 2429–2441 (1998). doi:10.1016/S1352-2310(98)00053-3
Doughty, D., Fuentes, J., Sakai, R., Hu, X.-M., Sanchez, K.: Nocturnal isoprene declines in a semi-urban environment. J. Atmos. Chem. 1–20 (2013). doi:10.1007/s10874-012-9247-0
Durana, N., Navazo, M., Gomez, M.C., Alonso, L., Garcia, J.A., Ilardia, J.L., Gangoiti, G., Iza, J.: Long term hourly measurement of 62 non-methane hydrocarbons in an urban area: main results and contribution of non-traffic sources. Atmos. Environ. 40(16), 2860–2872 (2006). doi:10.1016/j.atmosenv.2006.01.005
Farmer, D.K., Cohen, R.C.: Observations of HNO3, ∑AN, ∑PN and NO2 fluxes: evidence for rapid HOx chemistry within a pine forest canopy. Atmos. Chem. Phys. 8(14), 3899–3917 (2008)
Finnigan, J.: Turbulence in plant canopies. Annu. Rev. Fluid Mech. 32, 519–571 (2000). doi:10.1146/annurev.fluid.32.1.519
Fitzjarrald, D.R., Acevedo, O.C., Moore, K.E.: Climatic consequences of leaf presence in the eastern United States. J. Climate 14(4), 598–614 (2001). doi:10.1175/1520-0442(2001)014<0598:Ccolpi>2.0.Co;2
Forkel, R., Klemm, O., Graus, M., Rappengluck, B., Stockwell, W.R., Grabmer, W., Held, A., Hansel, A., 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, S28–S42 (2006). doi:10.1016/j.atmosenv.2005.11.070
Fowler, D., Pilegaard, K., Sutton, M.A., Ambus, P., Raivonen, M., Duyzer, J., Simpson, D., Fagerli, H., Fuzzi, S., Schjoerring, J.K., Granier, C., Neftel, A., Isaksen, I.S.A., Laj, P., Maione, M., Monks, P.S., Burkhardt, J., Daemmgen, U., Neirynck, J., Personne, E., Wichink-Kruit, R., Butterbach-Bahl, K., Flechard, C., Tuovinen, J.P., Coyle, M., Gerosa, G., Loubet, B., Altimir, N., Gruenhage, L., Ammann, C., Cieslik, S., Paoletti, E., Mikkelsen, T.N., Ro-Poulsen, H., Cellier, P., Cape, J.N., Horvath, L., Loreto, F., Niinemets, U., Palmer, P.I., Rinne, J., Misztal, P., Nemitz, E., Nilsson, D., Pryor, S., Gallagher, M.W., Vesala, T., Skiba, U., Brueggemann, N., Zechmeister-Boltenstern, S., Williams, J., O’Dowd, C., Facchini, M.C., de Leeuw, G., Flossman, A., Chaumerliac, N., Erisman, J.W.: Atmospheric composition change: ecosystems-atmosphere interactions. Atmos. Environ. 43(33), 5193–5267 (2009). doi:10.1016/j.atmosenv.2009.07.068
Fuentes, J.D., Wang, D., Neumann, H.H., Gillespie, T.J., DenHartog, G., Dann, T.F.: Ambient biogenic hydrocarbons and isoprene emissions from a mixed deciduous forest. J. Atmos. Chem. 25(1), 67–95 (1996). doi:10.1007/Bf00053286
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). doi:10.1175/1520-0477(2000)081<1537:Bhitab>2.3.Co;2
Fuentes, J.D., Hayden, B.P., Garstang, M., Lerdau, M., Fitzjarrald, D., Baldocchi, D.D., Monson, R., Lamb, B., Geron, C.: New directions: VOCs and biosphere-atmosphere feedbacks. Atmos. Environ. 35(1), 189–191 (2001). doi:10.1016/S1352-2310(00)00365-4
Fuentes, J.D., Wang, D., Bowling, D.R., Potosnak, M., Monson, R.K., Goliff, W.S., Stockwell, W.R.: Biogenic hydrocarbon chemistry within and above a mixed deciduous forest. J. Atmos. Chem. 56(2), 165–185 (2007). doi:10.1007/s10874-006-9048-4
Ganzeveld, L.N., Lelieveld, J., Dentener, F.J., Krol, M.C., Roelofs, G.J.: Atmosphere-biosphere trace gas exchanges simulated with a single-column model. J. Geophys. Res. Atmos. 107(D16), (2002). doi: 10.1029/2001jd000684
Gao, W., Wesely, M.L., Doskey, P.V.: Numerical modeling of the turbulent-diffusion and chemistry of Nox, O3, isoprene, and other reactive trace gases in and above a forest canopy. J. Geophys. Res. Atmos. 98(D10), 18339–18353 (1993). doi:10.1029/93jd01862
Geron, C.: Carbonaceous aerosol characteristics over a Pinus taeda plantation: results from the CELTIC experiment. Atmos. Environ. 45(3), 794–801 (2011). doi:10.1016/j.atmosenv.2010.07.015
Geron, C., Guenther, A., Sharkey, T., Arnts, R.R.: Temporal variability in basal isoprene emission factor. Tree Physiol. 20(12), 799–805 (2000)
Geron, C., Harley, P., Guenther, A.: Isoprene emission capacity for US tree species. Atmos. Environ. 35(19), 3341–3352 (2001). doi:10.1016/S1352-2310(00)00407-6
Goldan, P.D., Kuster, W.C., Fehsenfeld, F.C., Montzka, S.A.: Hydrocarbon measurements in the southeastern United States: the Rural Oxidants in the Southern Environment (ROSE) program 1990. J. Geophys. Res. Atmos. 100(D12), 25945–25963 (1995a). doi:10.1029/95jd02607
Goldan, P.D., Trainer, M., Kuster, W.C., Parrish, D.D., Carpenter, J., Roberts, J.M., Yee, J.E., Fehsenfeld, F.C.: Measurements of hydrocarbons, oxygenated hydrocarbons, carbon-monoxide, and nitrogen-oxides in an urban basin in Colorado—implications for emission inventories. J. Geophys. Res. Atmos. 100(D11), 22771–22783 (1995b). doi:10.1029/95jd01369
Goldstein, A.H., McKay, M., Kurpius, M.R., Schade, G.W., Lee, A., Holzinger, R., Rasmussen, R.A.: Forest thinning experiment confirms ozone deposition to forest canopy is dominated by reaction with biogenic VOCs. Geophys. Res. Lett. 31(22), L22106 (2004). doi:10.1029/2004gl021259
Grant, D.D., Fuentes, J.D., Chan, S., Stockwell, W.R., Wang, D., Ndiaye, S.A.: Volatile organic compounds at a rural site in western Senegal. J. Atmos. Chem. 60(1), 19–35 (2008). doi:10.1007/s10874-008-9106-1
Guenther, A.B.., Monson, R.K., Fall, R.: Isoprene and monoterpene emission rate variability—observations with eucalyptus and emission rate algorithm development. J. Geophys. Res. Atmos. 96(D6), 10799–10808 (1991). doi:10.1029/91jd00960
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). doi:10.1029/93jd00527
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). doi:10.1029/94jd02950
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)
Gut, A., van Dijk, S.M., Scheibe, M., Rummel, U., Welling, M., Ammann, C., Meixner, F.X., Kirkman, G.A., Andreae, M.O., Lehmann, B.E.: NO emission from an Amazonian rain forest soil: continuous measurements of NO flux and soil concentration. J. Geophys. Res. Atmos. 107(D20), 8057 (2002). doi:10.1029/2001jd000521
Hallquist, M., Wenger, J.C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N.M., George, C., Goldstein, A.H., Hamilton, J.F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M.E., Jimenez, J.L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, T.F., Monod, A., Prevot, A.S.H., Seinfeld, J.H., Surratt, J.D., Szmigielski, R., Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues. Atmos. Chem. Phys. 9(14), 5155–5236 (2009)
Hellen, H., Tykka, T., Hakola, H.: Importance of monoterpenes and isoprene in urban air in northern Europe. Atmos. Environ. 59, 59–66 (2012). doi:10.1016/j.atmosenv.2012.04.049
Helmig, D., Ortega, J., Guenther, A., Herrick, J.D., Geron, C.: Sesquiterpene emissions from loblolly pine and their potential contribution to biogenic aerosol formation in the Southeastern US. Atmos. Environ. 40(22), 4150–4157 (2006). doi:10.1016/j.atmosenv.2006.02.035
Holzinger, R., Lee, A., Paw, K.T., Goldstein, A.H.: Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds. Atmos. Chem. Phys. 5, 67–75 (2005)
Hu, X.-M. (2008), Incorporation of the model of aerosol dynamics, reaction, ionization, and dissolution (MADRID) into the Weather Research and Forecasting Model with Chemistry (WRF/Chem): Model development and retrospective applications, Ph.D. dissertation, N. C. State Univ., Raleigh, July
Hu, X.-M., Doughty, D.C., Sanchez, K.J., Joseph, E., Fuentes, J.D.: Ozone variability in the atmospheric boundary layer in Maryland and its implications for vertical transport model. Atmos. Environ. 46, 354–364 (2012). doi:10.1016/j.atmosenv.2011.09.054
Hu, X.-M., Klein, P.M., Xue, M., Zhang, F., Doughty, D.C., Forkel, R., Joseph, E., Fuentes, J.D.: Impact of the vertical mixing induced by low-level jets on boundary layer ozone concentration. Atmos. Environ. 70, 123–130 (2013). doi:10.1016/j.atmosenv.2012.12.046
Jonsson, A., Persson, K.A., Grigoriadis, V.: Measurements of some low molecular-weight oxygenated, aromatic, and chlorinated hydrocarbons in ambient air and in vehicle emissions. Environ. Int. 11(2–4), 383–392 (1985). doi:10.1016/0160-4120(85)90033-9
Karl, T., Potosnak, M., Guenther, A., Clark, D., Walker, J., Herrick, J.D., Geron, C.: Exchange processes of volatile organic compounds above a tropical rain forest: implications for modeling tropospheric chemistry above dense vegetation. J. Geophys. Res. Atmos. 109(D18), D18306 (2004). doi:10.1029/2004jd004738
Karl, T., Guenther, A., Turnipseed, A., Tyndall, G., Artaxo, P., Martin, S.: Rapid formation of isoprene photo-oxidation products observed in Amazonia. Atmos. Chem. Phys. 9(20), 7753–7767 (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). doi:10.1023/A:1006127516791
Kesselmeier, J., Kuhn, U., Rottenberger, S., Biesenthal, T., Wolf, A., Schebeske, G., Andreae, M.O., Ciccioli, P., Brancaleoni, E., Frattoni, M., Oliva, S.T., Botelho, M.L., Silva, C.M.A., Tavares, T.M.: Concentrations and species composition of atmospheric volatile organic compounds (VOCs) as observed during the wet and dry season in Rondonia (Amazonia). J. Geophys. Res. Atmos. 107(D20), 8053 (2002). doi:10.1029/2000jd000267
Kiefer, M.T., Zhong, S., Heilman, W.E., Charney, J.J., Bian, X.: Evaluation of an ARPS-based canopy flow modeling system for use in future operational smoke prediction efforts. J. Geophys. Res. Atmos. (2013). doi:10.1002/jgrd.50491
Kurpius, M.R., Goldstein, A.H.: Gas-phase chemistry dominates O3 loss to a forest, implying a source of aerosols and hydroxyl radicals to the atmosphere. Geophys. Res. Lett. 30(7), 1371 (2003). doi:10.1029/2002gl016785
Lamb, B., Guenther, A., Gay, D., Westberg, H.: A national inventory of biogenic hydrocarbon emissions. Atmos. Environ. 21(8), 1695–1705 (1987). doi:10.1016/0004-6981(87)90108-9
Lee, B.-S., Wang, J.-L.: Concentration variation of isoprene and its implications for peak ozone concentration. Atmos. Environ. 40(28), 5486–5495 (2006). doi:10.1016/j.atmosenv.2006.03.035
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
Liao, H., Henze, D.K., Seinfeld, J.H., Wu, S.L., Mickley, L.J.: Biogenic secondary organic aerosol over the United States: comparison of climatological simulations with observations. J. Geophys. Res. Atmos. 112(D6), D06201 (2007). doi:10.1029/2006jd007813
Lin, Y.H., Zhang, H.F., Pye, H.O.T., Zhang, Z.F., Marth, W.J., Park, S., Arashiro, M., Cui, T.Q., Budisulistiorini, H., Sexton, K.G., Vizuete, W., Xie, Y., Luecken, D.J., Piletic, I.R., Edney, E.O., Bartolotti, L.J., Gold, A., Surratt, J.D.: Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides. Proc. Natl. Acad. Sci. U. S. A. 110(17), 6718–6723 (2013). doi:10.1073/pnas.1221150110
Makar, P.A., Fuentes, J.D., Wang, D., Staebler, R.M., Wiebe, H.A.: Chemical processing of biogenic hydrocarbons within and above a temperate deciduous forest. J. Geophys. Res. Atmos. 104(D3), 3581–3603 (1999). doi:10.1029/1998jd100065
Mao, J., Paulot, F., Jacob, D.J., Cohen, R.C., Crounse, J.D., Wennberg, P.O., Keller, C.A., Hudman, R.C., Barkley, M.P., Horowitz, L.W.: Ozone and organic nitrates over the eastern united states: sensitivity to isoprene chemistry. J. Geophys. Res. Atmos. (2013). doi:10.1002/jgrd.50817
Montzka, S.A., Trainer, M., Goldan, P.D., Kuster, W.C., Fehsenfeld, F.C.: Isoprene and its oxidation-products, methyl vinyl ketone and methacrolein, in the rural troposphere. J. Geophys. Res. Atmos. 98(D1), 1101–1111 (1993). doi:10.1029/92jd02382
Papiez, M.R., Potosnak, M.J., Goliff, W.S., Guenther, A.B.., Matsunaga, S.N., Stockwell, W.R.: The impacts of reactive terpene emissions from plants on air quality in Las Vegas, Nevada. Atmos. Environ. 43(27), 4109–4123 (2009). doi:10.1016/j.atmosenv.2009.05.048
Park, C., Schade, G.W., Boedeker, I.: Flux measurements of volatile organic compounds by the relaxed eddy accumulation method combined with a GC-FID system in urban Houston, Texas. Atmos. Environ. 44(21–22), 2605–2614 (2010). doi:10.1016/j.atmosenv.2010.04.016
Park, C., Schade, G.W., Boedeker, I.: Characteristics of the flux of isoprene and its oxidation products in an urban area. J. Geophys. Res. Atmos. 116, (2011). doi:10.1029/2011jd015856
Parrish, D.D., Stohl, A., Forster, C., Atlas, E.L., Blake, D.R., Goldan, P.D., Kuster, W.C., de Gouw, J.A.: Effects of mixing on evolution of hydrocarbon ratios in the troposphere. J. Geophys. Res. Atmos. 112(D10), D10S34 (2007). doi:10.1029/2006jd007583
Paulot, F., Crounse, J.D., Kjaergaard, H.G., Kurten, A., St Clair, J.M., Seinfeld, J.H., Wennberg, P.O.: Unexpected epoxide formation in the gas-phase photooxidation of isoprene. Science 325(5941), 730–733 (2009). doi:10.1126/science.1172910
Perring, A.E., Bertram, T.H., Farmer, D.K., Wooldridge, P.J., Dibb, J., Blake, N.J., Blake, D.R., Singh, H.B., Fuelberg, H., Diskin, G., Sachse, G., Cohen, R.C.: The production and persistence of sigma RONO2 in the Mexico City plume. Atmos. Chem. Phys. 10(15), 7215–7229 (2010). doi:10.5194/acp-10-7215-2010
Pierce, T., Geron, C., Bender, L., Dennis, R., Tonnesen, G., Guenther, A.: Influence of increased isoprene emissions on regional ozone modeling. J. Geophys. Res. Atmos. 103(D19), 25611–25629 (1998). doi:10.1029/98jd01804
Pratt, K.A., Mielke, L.H., Shepson, P.B., Bryan, A.M., Steiner, A.L., Ortega, J., Daly, R., Helmig, D., Vogel, C.S., Griffith, S., Dusanter, S., Stevens, P.S., Alaghmand, M.: Contributions of individual reactive biogenic volatile organic compounds to organic nitrates above a mixed forest. Atmos. Chem. Phys. 12(21), 10125–10143 (2012). doi:10.5194/acp-12-10125-2012
Reimann, S., Calanca, P., Hofer, P.: The anthropogenic contribution to isoprene concentrations in a rural atmosphere. Atmos. Environ. 34(1), 109–115 (2000). doi:10.1016/S1352-2310(99)00285-X
Riemer, D., Pos, W., Milne, P., Farmer, C., Zika, R., Apel, E., Olszyna, K., Kliendienst, T., Lonneman, W., Bertman, S., Shepson, P., Starn, T.: Observations of nonmethane hydrocarbons and oxygenated volatile organic compounds at a rural site in the southeastern United States. J. Geophys. Res. Atmos. 103(D21), 28111–28128 (1998). doi:10.1029/98jd02677
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). doi:10.1016/0004-6981(84)90012-X
Roberts, J.M., Williams, J., Baumann, K., Buhr, M.P., Goldan, P.D., Holloway, J., Hubler, G., Kuster, W.C., McKeen, S.A., Ryerson, T.B., Trainer, M., Williams, E.J., Fehsenfeld, F.C., Bertman, S.B., Nouaime, G., Seaver, C., Grodzinsky, G., Rodgers, M., Young, V.L.: Measurements of PAN, PPN, and MPAN made during the 1994 and 1995 Nashville intensives of the Southern Oxidant study: implications for regional ozone production from biogenic hydrocarbons. J. Geophys. Res. Atmos. 103(D17), 22473–22490 (1998). doi:10.1029/98jd01637
Roberts, J.M., Marchewka, M., Bertman, S.B., Goldan, P., Kuster, W., de Gouw, J., Warneke, C., Williams, E., Lerner, B., Murphy, P., Apel, E., Fehsenfeld, F.C.: Analysis of the isoprene chemistry observed during the New England Air Quality Study (NEAQS) 2002 intensive experiment. J. Geophys. Res. Atmos. 111(D23), D23S12 (2006). doi:10.1029/2006jd007570
Rudolph, J., Johnen, F.J.: Measurements of light atmospheric hydrocarbons over the Atlantic in regions of low biological-activity. J. Geophys. Res. Atmos. 95(D12), 20583–20591 (1990). doi:10.1029/Jd095id12p20583
Rummel, U., Ammann, C., Kirkman, G.A., Moura, M.A.L., Foken, T., Andreae, M.O., Meixner, F.X.: Seasonal variation of ozone deposition to a tropical rain forest in southwest Amazonia. Atmos. Chem. Phys. 7(20), 5415–5435 (2007)
Schnitzhofer, R., Beauchamp, J., Dunkl, J., Wisthaler, A., Weber, A., Hansel, A.: Long-term measurements of CO, NO, NO2, benzene, toluene and PM10 at a motorway location in an Austrian valley. Atmos. Environ. 42(5), 1012–1024 (2008). doi:10.1016/j.atmosenv.2007.10.004
Seinfeld, J.H., Pandis, S.N.: Atmospheric chemistry and physics: from air pollution to climate change, p. 1326. John Wiley, New York (1998)
Sharma, U.K., Kajii, Y., Akimoto, H.: Characterization of NMHCs in downtown urban center Kathmandu and rural site Nagarkot in Nepal. Atmos. Environ. 34(20), 3297–3307 (2000). doi:10.1016/S1352-2310(99)00485-9
So, K.L., Wang, T.: C3-C12 non-methane hydrocarbons in subtropical Hong Kong: spatial-temporal variations, source-receptor relationships and photochemical reactivity. Sci. Total Environ. 328(1–3), 161–174 (2004). doi:10.1016/j.scitotnev.2004.01.029
Starn, T.K., Shepson, P.B., Bertman, S.B., White, J.S., Splawn, B.G., Riemer, D.D., Zika, R.G., Olszyna, K.: Observations of isoprene chemistry and its role in ozone production at a semirural site during the 1995 Southern oxidants study. J. Geophys. Res. Atmos. 103(D17), 22425–22435 (1998a). doi:10.1029/98jd01279
Starn, T.K., Shepson, P.B., Bertman, S.B., Riemer, D.D., Zika, R.G., Olszyna, K.: Nighttime isoprene chemistry at an urban-impacted forest site. J. Geophys. Res. Atmos. 103(D17), 22437–22447 (1998b). doi:10.1029/98jd01201
Stockwell, W.R., Kirchner, F., Kuhn, M., Seefeld, S.: A new mechanism for regional atmospheric chemistry modeling. J. Geophys. Res. Atmos. 102(D22), 25847–25879 (1997). doi:10.1029/97jd00849
Stroud, C.A., Roberts, J.M., Goldan, P.D., Kuster, W.C., Murphy, P.C., Williams, E.J., Hereid, D., Parrish, D., Sueper, D., Trainer, M., Fehsenfeld, F.C., Apel, E.C., Riemer, D., Wert, B., Henry, B., Fried, A., Martinez-Harder, M., Harder, H., Brune, W.H., Li, G., Xie, H., Young, V.L.: Isoprene and its oxidation products, methacrolein and methylvinyl ketone, at an urban forested site during the 1999 southern oxidants study. J. Geophys. Res. Atmos. 106(D8), 8035–8046 (2001). doi:10.1029/2000jd900628
Stroud, C.A., Roberts, J.M., Williams, E.J., Hereid, D., Angevine, W.M., Fehsenfeld, F.C., Wisthaler, A., Hansel, A., Martinez-Harder, M., Harder, H., Brune, W.H., Hoenninger, G., Stutz, J., White, A.B..: Nighttime isoprene trends at an urban forested site during the 1999 southern oxidant study. J. Geophys. Res. Atmos. 107(D16), 4291 (2002). doi:10.1029/2001jd000959
Stroud, C., Makar, P., Karl, T., Guenther, A., Geron, C., Turnipseed, A., Nemitz, E., Baker, B., Potosnak, M., 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. Atmos. 110(D17), D17303 (2005). doi:10.1029/2005jd005775
Stroud, C.A., Nenes, A., Jimenez, J.L., DeCarlo, P.F., Huffman, J.A., Bruintjes, R., Nemitz, E., Delia, A.E., Toohey, D.W., Guenther, A.B.., Nandi, S.: Cloud activating properties of aerosol observed during CELTIC. J. Atmos. Sci. 64(2), 441–459 (2007). doi:10.1175/Jas3843.1
Szidat, S., Jenk, T.M., Synal, H.-A., Kalberer, M., Wacker, L., Hajdas, I., Kasper-Giebl, A., Baltensperger, U.: Contributions of fossil fuel, biomass-burning, and biogenic emissions to carbonaceous aerosols in Zurich as traced by 14C. J. Geophys. Res. Atmos. 111(D7), D07206 (2006). doi:10.1029/2005jd006590
Utiyama, M., Fukuyama, T., Maruo, Y.Y., Ichino, T., Izumi, K., Hara, H., Takano, K., Suzuki, H., Aoki, M.: Formation and deposition of ozone in a red pine forest. Water Air Soil Poll. 151(1–4), 53–70 (2004). doi:10.1023/B:Wate.0000009891.12108.B9
von Schneidemesser, E., Monks, P.S., Gros, V., Gauduin, J., Sanchez, O.: How important is biogenic isoprene in an urban environment? A study in London and Paris. Geophys. Res. Lett. 38, (2011). doi:10.1029/2011gl048647
Walton, S., Gallagher, M.W., Duyzer, J.H.: Use of a detailed model to study the exchange of NOx and O3 above and below a deciduous canopy. Atmos. Environ. 31(18), 2915–2931 (1997). doi:10.1016/S1352-2310(97)00126-X
Wang, D., Fuentes, J.D., Travers, D., Dann, T., Connolly, T.: Non-methane hydrocarbons and carbonyls in the Lower Fraser Valley during PACIFIC 2001. Atmos. Environ. 39(29), 5261–5272 (2005). doi:10.1016/j.atmosenv.2005.05.035
Wang, J.L., Wang, C.H., Lai, C.H., Chang, C.C., Liu, Y., Zhang, Y.H., Liu, S., Shao, M.: Characterization of ozone precursors in the Pearl River Delta by time series observation of non-methane hydrocarbons. Atmos. Environ. 42(25), 6233–6246 (2008). doi:10.1016/j.atmosenv.2008.01.050
Wang, J.-L., Chew, C., Chang, C.-Y., Liao, W.-C., Lung, S.-C.C., Chen, W.-N., Lee, P.-J., Lin, P.-H., Chang, C.-C.: Biogenic isoprene in subtropical urban settings and implications for air quality. Atmos. Environ. (2013). doi:10.1016/j.atmosenv.2013.06.055
Weber, R.J., Sullivan, A.P., Peltier, R.E., Russell, A., Yan, B., Zheng, M., de Gouw, J., Warneke, C., Brock, C., Holloway, J.S., Atlas, E.L., Edgerton, E.: A study of secondary organic aerosol formation in the anthropogenic-influenced southeastern United States. J. Geophys. Res. Atmos. 112(D13), (2007). doi:10.1029/2007jd008408
Williams, E.J., Hutchinson, G.L., Fehsenfeld, F.C.: NOx and N2O emissions from soil. Glob. Biogeochem. Cycles 6(4), 351–388 (1992). doi:10.1029/92gb02124
Wolfe, G.M., Thornton, J.A.: The Chemistry of Atmosphere-Forest Exchange (CAFE) model - part 1: model description and characterization. Atmos. Chem. Phys. 11(1), 77–101 (2011). doi:10.5194/acp-11-77-2011
Wolfe, G.M., Thornton, J.A., Bouvier-Brown, N.C., Goldstein, A.H., Park, J.H., Mckay, M., Matross, D.M., Mao, J., Brune, W.H., LaFranchi, B.W., Browne, E.C., Min, K.E., Wooldridge, P.J., Cohen, R.C., Crounse, J.D., Faloona, I.C., Gilman, J.B., Kuster, W.C., de Gouw, J.A., Huisman, A., Keutsch, F.N.: The Chemistry of Atmosphere-Forest Exchange (CAFE) model - part 2: application to BEARPEX-2007 observations. Atmos. Chem. Phys. 11(3), 1269–1294 (2011). doi:10.5194/acp-11-1269-2011
Xie, X., Shao, M., Liu, Y., Lu, S.H., Chang, C.C., Chen, Z.M.: Estimate of initial isoprene contribution to ozone formation potential in Beijing, China. Atmos. Environ. 42(24), 6000–6010 (2008). doi:10.1016/j.atmosenv.2008.03.035
Zhao, Y., Kreisberg, N.M., Worton, D.R., Isaacman, G., Gentner, D.R., Chan, A.W.H., Weber, R.J., Liu, S., Day, D.A., Russell, L.M., Hering, S.V., Goldstein, A.H.: Sources of organic aerosol investigated using organic compounds as tracers measured during CalNex in Bakersfield. J. Geophys. Res. Atmos. 2012JD019248, (2013). doi:10.1002/jgrd.50825
Acknowledgments
The Pennsylvania State University provided support to XH to participate in this research. JDF received funding from the U.S. National Science Foundation (grant number ATM 0939455) to partake in this research. Three anonymous reviewers provided helpful comments that improved the manuscript.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Supplement A-1
(PDF 577 kb)
Rights and permissions
About this article
Cite this article
Hu, XM., Fuentes, J.D., Toohey, D. et al. Chemical processing within and above a loblolly pine forest in North Carolina, USA. J Atmos Chem 72, 235–259 (2015). https://doi.org/10.1007/s10874-013-9276-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10874-013-9276-3