Journal of Atmospheric Chemistry

, Volume 72, Issue 3–4, pp 215–234 | Cite as

Nocturnal isoprene declines in a semi-urban environment

  • David Doughty
  • Jose D. Fuentes
  • Ricardo Sakai
  • Xiao-Ming Hu
  • Kevin Sanchez
Article

Abstract

In environments dominated by biogenic hydrocarbon emissions, the transition from daytime to nighttime is an important period because ambient isoprene levels rapidly decrease. In sub-urban environments with abundant sources of nitrogen oxides, the nighttime isoprene chemistry has implications for the regional nitrogen oxide budget. Given the substantial production of alkyl nitrates from isoprene reactions during the nighttime, nitrogen oxides can then be transported long distances in the form of nitrates. The factors that influence nighttime chemistry of isoprene in environments with abundant sources of nitrogen oxides are not well known. Therefore, the objective of this study was to understand the processes controlling isoprene levels just before and after sunset, in an environment under the influences of moderate concentrations of ambient nitrogen oxides. Utilizing in-situ Proton-Transfer-Reaction Mass Spectrometer measurements, isoprene levels were studied during July to August 2011 in a sub-urban environment outside the metropolis of Washington, D.C., USA. Numerical modeling investigations were also pursued to determine yields of alkyl nitrates. Pre-sunset isoprene rises, observed on eight measured days, were likely related to the cessation of atmospheric turbulence and stabilization of the surface layer. After sunset, nocturnal declines of isoprene, while not fully explained by chemical reactions, depended on the amounts of nitrate radicals in the lower atmosphere. Furthermore, isoprene destruction rates and associated production of alkyl nitrates depended on the amounts of nitrogen oxides. Compared with cases with ambient nitrogen oxides lower than 10 parts per billion, model results showed that twice the amounts of isoprene were destroyed when average nitrogen oxide levels exceeded 30 parts per billion.

Keywords

Biogenic VOC Air Pollution Alkyl Nitrates Isoprene Emission 

Supplementary material

10874_2012_9247_MOESM1_ESM.docx (69 kb)
ESM 1(DOCX 68.5kb)

References

  1. Andronache, C., Chameides, W.L., Rodgers, M.O., Martinez, J., Zimmerman, P., Greenberg, J.: Vertical distribution of isoprene in the lower boundary layer of the rural and urban southern United States. J. Geophys. Res. 99(D8), 16,989–16,999 (1994)CrossRefGoogle Scholar
  2. 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. 107(D3) (2002). doi:10.1029/2000JD000225
  3. Atkinson, R., Arey, J.: Atmospheric degradation of volatile organic compounds. Chem. Rev. 103, 4605–4638 (2003)CrossRefGoogle Scholar
  4. Baldocchi, D., Guenther, A., Harley, P., Klinger, L., Zimmerman, P., Lamb, B., Westberg, H.: The fluxes and air chemistry of isoprene above a deciduous hardwood forest. Phil. Trans. Phys. Sci. Engr. 351, 279–296 (1995)CrossRefGoogle Scholar
  5. 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, 3749–3760 (2001)CrossRefGoogle Scholar
  6. Brown, S.S., de Gouw, J.A., Warneke, C., Ryerson, T.B., Dubé, 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, 3027–3042 (2009)CrossRefGoogle Scholar
  7. Claeys, M., Grahm, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M.O., Artaxo, P., Maenhaut, W.: Formation of secondary organic aerosols through photooxidation of isoprene. Science 303, 1173–1176 (2004)CrossRefGoogle Scholar
  8. Curren, K., Gillespie, T., Steyn, D., Dann, T., Wang, D.: Biogenic isoprene in the lower Fraser valley, British Columbia. J. Geophys. Res. 103(D19), 25,467–25,477 (1998)CrossRefGoogle Scholar
  9. Damian, V., Sandu, A., Damian, M., Potra, F., Carmichael, G.R.: The kinetic PreProcessor KPP - a software environment for solving chemical kinetics. Comput. Chem. Eng. 26, 1567–1579 (2002)CrossRefGoogle Scholar
  10. de Gouw, J., Warneke, C.: Measurements of volatile organic compounds in the earth’s atmosphere using proton-transfer-reaction mass spectrometry. Mass Spec. Rev 26(2), 223–257 (2007). doi:10.1002/mas.20119 CrossRefGoogle Scholar
  11. de Vilà-Guerau Arellano, J., Patton, E.G., Karl, T., van den Dries, K., Barth, M.C., Orlando, J.J.: The role of boundary layer dynamics on the diurnal evolution of isoprene and the hydroxyl radical over tropical forests. J. Geophys. Res. 116(D7) (2011). doi:10.1029/2010JD014857
  12. Dreyfus, G.B., Schade, G.W., Goldstein, A.H.: Observational constraints on the contribution of isoprene oxidation to ozone production on the western slope of the Sierra Nevada. California. J. Geophys. Res. (2002). doi:10.1029/2001JD001490
  13. Faloona, I., Tan, D., Brune, W., Hurst, J., Barket Jr., D., Couch, T.L., Shepson, P., Apel, E., Riemer, D., Thornberry, T., Carroll, M.A., Sillman, S., Keeler, G.J., Sagady, J., Hooper, D., Paterson, K.: Nighttime observations of anomalously high levels of hydroxyl radicals above a deciduous forest canopy. J. Geophys. Res. 106(D20), 24,315–24,333 (2001)CrossRefGoogle Scholar
  14. Farmer, D.K., Perring, A.E., Wooldridge, P.J., Blake, D.R., Baker, A., Meinardi, S., Huey, L.G., Tanner, D., Vargas, O., Cohen, R.C.: Impact of organic nitrates on urban ozone production. Atmos. Chem. Phys. 11, 4085–4094 (2011). doi:10.5194/acp-11-4085-2011 CrossRefGoogle Scholar
  15. Fiore, A.M., Horowitz, L.W., Purves, D.W., Levy II, H., Evans, M.J., Wang, Y., Li, Q., Yantosca, R.M.: Evaluating the contribution of changes in isoprene emissions to surface ozone trends over the eastern United States. J. Geophys. Res. (2005). doi:10.1029/2004JD005485
  16. Fiore, A.M., Levy II, H., Jaffe, D.A.: North American isoprene influence on intercontinental ozone pollution. Atmos. Chem. Phys. 11, 1697–1701 (2011). doi:10.5194/acp-11-1697-2011 CrossRefGoogle Scholar
  17. 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 CrossRefGoogle Scholar
  18. Fuentes, J.D., Wang, D., Neumann, H.H., Gillespie, T.J., Hartog, G.D., Dann, T.F.: Ambient biogenic hydrocarbons and isoprene emissions from a mixed deciduous forest. J. Atmos. Chem. 25, 67–95 (1996)CrossRefGoogle Scholar
  19. Fuentes, J.D., Wang, D., Gu, L.: Seasonal variations in isoprene emissions from a boreal aspen forest. J. Appl. Met. 38, 855–869 (1999)CrossRefGoogle Scholar
  20. 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. Amer. Met. Soc. 81(7), 1537–1576 (2000)CrossRefGoogle Scholar
  21. 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. 100(D12), 25,945–25,963 (1995). doi:10.1029/95JD02607 CrossRefGoogle Scholar
  22. 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. 96(D6), 10,799–10,808 (1991)CrossRefGoogle Scholar
  23. 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. 98(D7), 12,609–12,617 (1993)CrossRefGoogle Scholar
  24. Guenther, A., Karl, T., Harley, P., Weidenmyer, 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)CrossRefGoogle Scholar
  25. Horowitz, L.W., Fiore, A.M., Milly, G.P., Cohen, R.P., Perring, A., Wooldridge, P.J., Hess, P.G., Emmons, L.K., Lamarque, J.-F.: Observational constraints on the chemistry of isoprene nitrates over the eastern United States. J. Geophys. Res. (2007). doi:10.1029/2006JD007747
  26. Hu, X.-M., Doughty, D.C., Sanchez, K.J., Joseph, E.J., Fuentes, J.D.: Ozone variability in the atmospheric boundary layer in Maryland and its implications for vertical transport models. Atmos. Environ 46, 254–264 (2012)CrossRefGoogle Scholar
  27. Huisman, A.J., Hottle, J.R., Galloway, M.M., DiGangi, J.P., Coens, K.L., Choi, W., Faloona, I.C., Gilman, J.B., Kuster, W.C., de Gouw, J., Bouvier-Brown, N.C., Goldstein, A.H., LaFranchi, B.W., Cohen, R.C., Wolfe, G.M., Thornton, J.A., Docherty, K.S., Farmer, D.K., Cubison, M.J., Jimenez, J.L., Mao, J., Brune, W.H., Keutsch, F.N.: Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007. Atmos. Chem. Phys. 11, 8883–8897 (2011). doi:10.5194/acp-11-8883-2011 CrossRefGoogle Scholar
  28. Hurst, J.M., Barket, D.J., Herrera-Gomez, O., Couch, T.L., Shepson, P.B., Faloona, I., Tan, D., Brune, W., Westberg, H., Lamb, B., Biesenthal, T., Young, V., Goldstein, A., Munger, J.W., Thornberry, T., Carroll, M.A.: Investigation of the nighttime decay of isoprene. J. Geophys. Res.-Atmos. 106(D20), 24335–24346 (2001)CrossRefGoogle Scholar
  29. Kaimal, J.C., Finnigan, J.J.: Atmospheric boundary layer flows. Oxford University Press, Oxford (1994)Google Scholar
  30. Karl, T., Guenther, A., Yokelson, R.J., Greenberg, J., Potosnak, M., Blake, D.R., Artaxo, P.: The tropical forest and fire emissions experiment: emission, chemistry, and transport of biogenic volatile organic compounds in the lower atmosphere over Amazonia. J. Geophys. Res. 112(D18) (2007). doi:10.1029/2007JD008539
  31. Kwok, E.S., Aschmann, S.M., Arey, J., Atkinson, R.: Product formation from the reaction of the NO3 radical with isoprene and rate constants for the reactions of methacrolein and methyl vinyl ketone with the NO3 radical. Int. J. Chem. Kin. 28, 925–934 (1996)CrossRefGoogle Scholar
  32. Lamb, B., Westberg, H., Allwine, G., Quarles, T.: Biogenic hydrocarbon emissions from deciduous and coniferous trees in the United States. J. Geophys. Res. 90, 2380–2390 (1985)CrossRefGoogle Scholar
  33. 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, 737–740 (2008)CrossRefGoogle Scholar
  34. Liao, H., Henze, D.K., Seinfeld, J.H., Wu, S., Mickley, L.J.: Biogenic secondary organic aerosol over the United States: comparison of climatological simulations with observations. J. Geophys. Res. 112(D6) (2007). doi:10.1029/2006JD007813
  35. Lindinger, W., Hansel, A., Jordan, A.: On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research. Int. J. Mass Spec. Ion Proc. 173(3), 191–241 (1998). doi:10.1016/S0168-1176(97)00281-4 CrossRefGoogle Scholar
  36. Magnotta, F., Johnston, H.S.: Photodissociation quantum yields for the NO3 free radical. Geophys. Res. Let. 7(10), 769–772 (1980)CrossRefGoogle Scholar
  37. Martin, R.S., Westberg, H., Allwine, E., Ashman, L., Farmer, C., Lamb, B.: Measurement of isoprene and its atmospheric oxidization products in a central Pennsylvania deciduous forest. J. Atmos. Chem. 13, 1–32 (1991)CrossRefGoogle Scholar
  38. Paulot, F., Crounse, J.D., Kjaergaard, H.G., Kroll, J.H., Seinfeld, J.H., Wennberg, P.O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates. Atmos. Chem. Phys. 9, 1479–1501 (2009). doi:10.5194/acp-9-1479-2009 CrossRefGoogle Scholar
  39. Paulson, S.E., Orlando, J.J.: The reactions of ozone with alkenes: an important source of HOx in the boundary layer. Geophys. Res. Let. 23(25), 3727–3730 (1996). doi:10.1029/96GL03477 CrossRefGoogle Scholar
  40. Paulson, S.E., Flagan, R.C., Seinfeld, J.H.: Atmospheric photooxidation of isoprene part 1: the hydroxyl radical and ground state atomic oxygen reactions. Int. J. Chem. Kinet. 24, 79–101 (1992a)CrossRefGoogle Scholar
  41. Paulson, S.E., Flagan, R.C., Seinfeld, J.H.: Atmospheric photooxidation of isoprene part 2: the ozone isoprene reaction. Int. J. Chem. Kinet. 24, 103–125 (1992b)CrossRefGoogle Scholar
  42. Perring, A.E., Wisthaler, A., Graus, M., Wooldridge, P.J., Lockwood, A.L., Mielke, L.H., Shepson, P.B., Hansel, A., Cohen, R.C.: A product study of the isoprene + NO3 reaction. Atmos. Chem. Phys. 9, 4945–4956 (2009). doi:10.5194/acp-9-4945-2009 CrossRefGoogle Scholar
  43. Pugh, T.A.M., MacKenzie, A.R., Langford, B., Nemitz, E., Misztal, P.K., Hewitt, C.N.: The influence of small-scale variations in isoprene concentrations on the atmospheric chemistry over a tropical rainforest. Atmos. Chem. Phys. 11, 4121–4134 (2011). doi:10.5194/acp-11-4121-2011 CrossRefGoogle Scholar
  44. Reeves, C.E., Slemr, J., Oram, D.E., Worton, D., Penkett, S.A., Stewart, D.J., Purvis, R., Watson, N., Hopkins, J., Lewis, A., Methven, J., Blake, D.R., Atlas, E.: Alkyl nitrates in outflow from North America over the North Atlantic during intercontinental transport of ozone and precursors 2004. J. Geophys. Res. 112(D10) (2007). doi:10.1029/2006JD007567
  45. Reimann, S., Pierlugi, C., Hofer, P.: The anthropogenic fraction contribution to isoprene concentrations in a rural atmosphere. Atmos. Environ. 34, 109–115 (2000)CrossRefGoogle Scholar
  46. Ren, X., Brune, W.H., Oliger, A., Metcalf, A.R., Simpas, J.B., Shirley, T., Schwab, J.J., Bai, C., Roychowdhury, U., Li, Y., Cai, C., Demerjian, K.L., He, Y., Xhou, X., Gao, H., Hou, J.: OH, HO2, and OH reactivity during the PMTACR-NY whiteface mountain 2002 campaign: observations and model comparison. J. Geophys. Res. 111(D10) (2006). doi:10.1029/2005JD006126
  47. Rollins, A.W., Kiendler-Scharr, A., Fry, J.L., Brauers, T., Brown, S.S., Dorn, H.P., Dube, W., Fuchs, H., Mesah, A., Mentel, T.F., Rohrer, F., Tillmann, R., Wegener, R., Wooldridge, P., Cohen, R.C.: Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields. Atmos. Chem. Phys. 9, 6685–6703 (2009)CrossRefGoogle Scholar
  48. Sandu, A., Sander, R.: Technical note: simulating chemical systems in Fortran90 and matlab with the kinetic PreProcessor KPP-2.1. Atmos. Chem. Phys 6, 187–195 (2006)CrossRefGoogle Scholar
  49. Sandu, A., Descu, D., Carmichael, G.R.: Direct and adjoint sensitivity analysis of chemical kinetic systems with KPP: I – theory and software tools. Atmos. Environ. 37, 5083–5096 (2003)CrossRefGoogle Scholar
  50. Sharma, U.K., Kajii, Y., Akimoto, H.: Characterization of NMHCs in downtown urban center Kathmandu and rural site nagarkot in Nepal. Atmos. Environ. 34, 3297–3307 (2000). doi:10.1016/S1352-2310(99)00485-9 CrossRefGoogle Scholar
  51. 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. 103(D17), 22,425–22,435 (1998a)CrossRefGoogle Scholar
  52. 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. 103(D17), 22,437–22,447 (1998b)CrossRefGoogle Scholar
  53. Steinbacher, M., Dommen, J., Ordonez, C., Reimann, S., Gruebler, F.C., Staehelin, J., Andreani-Aksoyoglu, S., Prevot, A.S.H.: Volatile organic compounds in the Po basin. Part B: biogenic VOCs. J. Atmos. Chem. 51, 293–315 (2005). doi:10.1007/s10874-005-3577-0 CrossRefGoogle Scholar
  54. Stockwell, W.R., Kirchner, F., Kuhn, M., Seefeld, S.: A new mechanism for regional atmospheric chemistry modeling. J. Geophys. Res. 102, 25847–25879 (1997)CrossRefGoogle Scholar
  55. Stroud, C.A., et al.: Isoprene and its oxidization products, methacrolein and methylvinyl ketone, at an urban forested site during the 1999 southern oxidants study. J. Geophys. Res. 106(D8), 8036–8046 (2001)Google Scholar
  56. Stroud, C.A., et al.: Nighttime isoprene trends at an urban forested site during the 1999 southern oxidant study. J. Geophys. Res. 107(D16), 4291 (2002). doi:10.1029/2001JD000959 Google Scholar
  57. Stroud, C., Makar, P., Karl, T., Guenther, A., Geron, C., Turnipseed, A., Nemitz, E., Baker, B., Potosnak, M., Fuentes, J.: Role of canopy-scale photochemistry in modifying biogenic-atmosphere exchange of reactive terpene species: results from the CELTIC field study, J. Geophys. Res. 110(D17) (2005). doi:10.1029/2005JD005775
  58. Stull, R.B.: An introduction to boundary layer meteorology. Kluwer, Norwell (1988)CrossRefGoogle Scholar
  59. 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, 5261–5272 (2005)CrossRefGoogle Scholar
  60. 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, 6233–6246 (2008). doi:10.1016/j.atmosenv.2008.01.050 CrossRefGoogle Scholar
  61. Weaver, C.P., Liang, X.Z., Zhu, J., Adams, P.J., Amar, P., Avise, J., Caughey, M., Chen, J., Cohen, R.C., Cooter, E., Dawson, J.P., Gilliam, R., Gilliland, A., Goldstein, A.H., Grambsch, A., Grano, D., Guenther, A., Gustafson, W.I., Harley, R.A., He, S., Hemming, B., Hogrefe, C., Huang, H.C., Hunt, S.W., Jacob, D.J., Kinney, P.L., Kunkel, K., Lamarque, J.F., Lamb, B., Larkin, N.K., Leung, L.R., Liao, K.J., Lin, J.T., Lynn, B.H., Manomaiphiboon, K., Mass, C., McKenzie, D., Mickley, L.J., O’Neill, S.M., Nolte, C., Pandis, S.N., Racherla, P.N., Rosenzweig, C., Russell, A.G., Salathe, E., Steiner, A.L., Tagaris, E., Tao, Z., Tonse, S., Wiedinmyer, C., Williams, A., Winner, D.A., Woo, J.H., Wu, S., Wuebbles, D.J.: A preliminary synthesis of modeled climate change impacts on US regional ozone concentrations. Bull. Am. Met. Soc. 90, 1843–1863 (2009). doi:10.1175/2009BAMS2568.1 CrossRefGoogle Scholar
  62. Wesley, M.L.: Parameterization of surface resistance to gaseous dry deposition in regional numerical models. Atmos. Env. 16, 1293–1304 (1989)CrossRefGoogle Scholar
  63. Winer, A.M., Atkinson, R., Pitts, J.N.: Gaseous nitrate radical: possible nighttime atmospheric sink for biogenic organic compounds. Science 224(4645), 156–159 (1984)CrossRefGoogle Scholar
  64. Zimmerman, P.R., Greenberg, J.P., Westberg, C.E.: Measurement of atmospheric hydrocarbons and biogenic emission fluxes in the Amazon boundary layer. J. Geophys. Res. 93, 1407–1416 (1988)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • David Doughty
    • 1
  • Jose D. Fuentes
    • 1
  • Ricardo Sakai
    • 2
  • Xiao-Ming Hu
    • 3
  • Kevin Sanchez
    • 1
  1. 1.Department of MeteorologyThe Pennsylvania State UniversityUniversity ParkUSA
  2. 2.Department of PhysicsHoward UniversityWashingtonUSA
  3. 3.Center for Analysis and Prediction of StormsUniversity of OklahomaNormanUSA

Personalised recommendations