ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-1253-2009 Evaluation of the global oceanic isoprene source and its impacts on marine organic carbon aerosol Arnold S. R. 1 Spracklen D. V. 1 Williams J. 2 Yassaa N. 2 3 Sciare J. 4 Bonsang B. 4 Gros V. 4 Peeken I. 5 Lewis A. C. 6 Alvain S. 4 Moulin C. 4 Institute for Climate and Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK Max Planck Institute for Chemistry, Mainz, Germany Now at Faculty of Chemistry, University of Sciences and Technology Houari Boumediene, U.S.T.H.B., Algiers, Algeria IPSL/LSCE, CEA Saclay, Gif-sur-Yvette, France Ifm GEOMAR, Kiel, Germany Department of Chemistry, University of York, York, UK 18 02 2009 9 4 1253 1262 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/9/1253/2009/acp-9-1253-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/1253/2009/acp-9-1253-2009.pdf

We have combined the first satellite maps of the global distribution of phytoplankton functional type and new measurements of phytoplankton-specific isoprene productivities, with available remote marine isoprene observations and a global model, to evaluate our understanding of the marine isoprene source and its impacts on organic aerosol abundances. Using satellite products to scale up data on phytoplankton-specific isoprene productivity to the global oceans, we infer a mean "bottom-up" oceanic isoprene emission of 0.31±0.08 (1σ) Tg/yr. By minimising the mean bias between the model and isoprene observations in the marine atmosphere remote from the continents, we produce a "top-down" oceanic isoprene source estimate of 1.9 Tg/yr. We suggest our reliance on limited atmospheric isoprene data, difficulties in simulating in-situ isoprene production rates in laboratory phytoplankton cultures, and limited knowledge of isoprene production mechanisms across the broad range of phytoplankton communities in the oceans under different environmental conditions as contributors to this difference between the two estimates. Inclusion of secondary organic aerosol (SOA) production from oceanic isoprene in the model with a 2% yield produces small contributions (0.01–1.4%) to observed organic carbon (OC) aerosol mass at three remote marine sites in the Northern and Southern Hemispheres. Based on these findings we suggest an insignificant role for isoprene in modulating remote marine aerosol abundances, giving further support to a recently postulated primary OC source in the remote marine atmosphere.

 References Alvain, S., Moulin, C., Dandonneau, Y., and Breon, F. M.: Remote sensing of phytoplankton groups in case 1 waters from global SeaWiFS imagery, Deep Sea Res. Pt. I, 52, 1989–2004, 2005. Alvain S., Moulin, C., Dandonneau, Y., and Loisel, H.: Seasonal distribution and succession of dominant phytoplankton groups in the global ocean: A satellite view, Global Biogeochem. Cy., 22, GB3001, doi:10.1029/2007GB003154, 2008. Andreae, M. O. and Raemdonck, H.: Dimethyl sulfide in the surface ocean and the marine atmosphere: a global view, Science, 221, 744–747, 1983. Baker, A., Turner, S., Broadgate, W., Thompson, A., McFiggans, G., Vesperini, O., Nightingale, P., Liss, P., and Jickells, T.: Distribution and Sea-Air Fluxes of Biogenic Trace Gases in the Eastern Atlantic Ocean, Global Biogeochem. Cy., 14, 871–886, 2000. Barlow, R. G., Aiken, J., Holligan, P. M., et al.: Phytoplankton pigment and absorption characteristics along meridioal transects in the Atlantic Ocean, Deep Sea Res. Pt. I, 47, 637–660, 2002. Bey, I., Jacob, D., Yantosca, R., Logan, J., Field, B., Fiore, A., Li, Q., Liu ,H., Mickley, L., and Schultz, M.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res., 106(D19), 23073–23095, 2001. Bonsang, B., Gros, V., Yassaa, N., Peeken, I., Bluhm, K., Zoellner, E., Sarda-Esteve, R., and Williams, J.: Isoprene emission from phytoplankton monocultures, Environ. Chem., in preparation, 2009. Bonsang, B., Polle, C., and Lambert, G.: Evidence for marine production of isoprene, Geophys. Res. Lett., 19, 1129–1132, 1992. Broadgate, W. J., Malin, G., Kupper, F. C., Thompson, A., and Liss, P. S.: Isoprene and other non-methane hydrocarbons from seaweeds: a source of reactive hydrocarbons to the atmosphere, Mar. Chem., 88, 61–73, 2004. Broadgate, W., Liss, P., and Penkett, S.: Seasonal Emissions of Isoprene and Other Reactive Hydrocarbon Gases from the Ocean, Geophys. Res. Lett., 24(21), 2675–2678, 1997. Cavalli, F., Facchini, M. C., Decesari, S., et al.: Advances in characterization of sizeresolved organic matter in marine aerosol over the North Atlantic, J. Geophys. Res., 109, D24215, doi:10.1029/2004JD005137, 2004. % %Charlson, R.J., J.E. Lovelock, M.O. Andreae, and S.G. Warren, %(1987), Oceanic phytoplankton, atmospheric sulfur, cloud albedo and climate, %\em Nature, \em 326, 655-661. Claeys, M., Wang, W., Ion, A. C., et al.: Formation of secondary organic aerosols from isoprene and its gas-phase oxidation products through reaction with hydrogen peroxide, Atmos. Environ., 38, 4093–4098, 2004. de Boyer Montegut, C., Madec, G., Fischer, A. S., Lazar, A., and Iudicone, D.: Mixed layer depth over the global ocean: An examination of profile data and a profile-based climatology, J. Geophys. Res., 109, C12003, doi:10.1029/2004JC002378, 2004. Dandonneau, Y., Deschamps, P. Y., Nicolas, J. M., et al.: Seasonal and interannual variability of ocean color and composition of phytoplankton communities in the North Atlantic, equatorial Pacific and South Pacific, Deep-Sea Res. Pt. II, 51, 303–318, 2004. % %Evans, M.J. \em et al., (2000), Evaluation of a Lagrangian box model using %field measurements from EASE(Eastern Atlantic Summer Experiment) %1996. \em Atmos. Env., \em 34, 3843-3863. Ervens, B., Carlton, A. G., Turpin, B. J., Altieri, K. E., Kreidenweis, S. M., and Feingold, G.: Secondary organic aerosol yields from cloud-processing of isoprene oxidation products, Geophys. Res. Lett., 35, L02816, doi:10.1029/2007GL031828, 2008. Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the Earth's atmosphere, Environ. Sci. Technol., 1515–1521, 2007. Gordon, H. R. and Wang, M.: Retrieval of water-leaving radiance and aerosol optical thickness over the oceans with SeaWiFS: a preliminary algorithm, Appl. Opt., 33, 443–452, 1994. Grenfell, J. L.: An analysis of rapid increases in condensation nuclei concentrations at a remote coastal site in Western Ireland, J. Geophys. Res., 104, 13771–13780, 1999. 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, 2006. Henze D. K. and Seinfeld, J. H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, doi:10.1029/2006GL025976, 2006. Hopkins, J. R., Jones, I. D., Lewis, A. C., et al.: Non-methane hydrocarbons in the Arctic boundary layer, Atmos. Environ., 36, 3217–3229, 2002. Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary Organic Aerosol Formation from Isoprene Photooxidation, Environ. Sci. Technol., 40, 1869–1877, doi:10.1021/es0524301, 2006. Lewis, A. C., Carpenter, L., and Pilling, M. J.: Nonmethane hydrocarbons in Southern Ocean boundary layer air, J. Geophys. Res., 106, 4987–4994, 2001. Lewis, A. C., Watson, N., Evans, M. J., Methven, J., Lee, J., Hopkins, J., Purvis, R., Arnold, S. R., McQuaid, J. B., Whalley, L. K., Heard, D. E., Pilling, M. J., Monks ,P. S., Parker, A., Reeves, C. E., Oram, D.,Mills ,G., Stewart, D., Bandy, B., Coe, H., Williams, P., and Crosier, J.: Chemical composition observed over the mid-Atlantic and the detection of pollution signatures far from source regions, J. Geophys. Res., 112, D10S39, doi:10.1029/2006JD007584, 2007. Liao, H., Henze, D. K., Seinfeld, J. H., Wu, S., and Mickley, L. J.: Biogenic secondary organic aerosol over the United States: Comparison of climatological simulations with observations, J. Geophys. Res., 112, D06201, doi:10.1029/2006JD007813, 2007. Marrari, M., Hu , C., and Daly, K.: Validation of SeaWiFS chlorophyll a concentrations in the Southern Ocean: A revisit, Remote Sens. Environ., 105, 367–375, 2006. Mårtensson, E. M., Nilsson, E. D., de Leeuw, G., et al.: Laboratory simulations and parameterization of the primary marine aerosol production, J. Geophys. Res., 108, 4297, doi:10.1029/2002JD002263, 2003. Matsunaga, S., Mochida, M., Saito, T., and Kawamura, K.: In situ measurement of isoprene in the marine air and surface seawater from the western North Pacific, Atmos. Environ., 36, 6051, doi:10.1016/S1352-2310(02)00657-X, 2002. McKay, M. D., Conover, W. J., and Beckman, R. J.: A Comparison of Three Methods for Selecting Values of Input Variables in the Analysis of Output from a Computer Code, Technometrics, 21, 239–245, 1979. Meskhidze, N. and Nenes, A.: Phytoplankton and cloudiness in the Southern Ocean, Science, 314, 1419, doi:10.1126/science.1131779, 2006. Meskhidze, N. and Nenes, A.: Relpy to comment on "Phytoplankton and cloudiness in the Southern Ocean", Science, 317, 42–43, 2007. Milne, P. J., Riemer, D. D., Zika, R. G., et al.: Measurement of vertical distribution of isoprene in surface seawater, its chemical fate, and its emission from several phytoplankton monocultures, Mar. Chem., 48, 237–244, 1995. Moore, R. M. and Wang, L.: The influence of iron fertilization on the fluxes of methyl halides and isoprene from ocean to atmosphere in the SERIES experiment, Deep Sea Res., 53, 2398–2409, 2006. Moore, R., Oram, D., and Penkett, S.: Production of Isoprene by Marine Phytoplankton Cultures, Geophys. Res. Lett., 21, 2507–2510, 1994. Müller, J.-F., Stavrakou, T., Wallens, S., De Smedt, I., Van Roozendael, M., Potosnak, M. J., Rinne, J., Munger, B., Goldstein, A., and Guenther, A. B.: Global isoprene emissions estimated using MEGAN, ECMWF analyses and a detailed canopy environment model, Atmos. Chem. Phys., 8, 1329–1341, 2008. Nilsson, E. D., Mårtensson, E. M., Van Ekeren, J. S., de Leeuw, G., Moerman, M., and O'Dowd, C.: Primary marine aerosol emissions: size resolved eddy covariance measurements with estimates of the sea salt and organic carbon fractions, Atmos. Chem. Phys. Discuss., 7, 13345–13400, 2007. Novakov, T., Corrigan, C., Penner, J., et al.: Organic aerosols in the Caribbean trade winds: A natural source?, J. Geophys. Res., 102, 21307–21313, 1997. O'Dowd, C. and de Leeuw, G.: Marine aerosol production: a review of the current knowledge, Phil. Trans. R. Soc. A, 365, 1753–1774, doi:10.1098/rsta.2007.2043, 2007. O'Dowd, C. D., Facchini, M. C., Cavalli, F., et al.: Biogenically driven organic contribution to marine aerosol, Nature, 431, 676–680, 2004. O'Dowd, C. D., Lowe, J. A., and Smith, M. H.: Coupling of sea-salt and sulphate interactions and its impact on cloud droplet concentration predictions, Geophy. Res. Lett., 26, 1311–1314, 1999. Palmer, P. I. and Shaw, S. L.: Quantifying global marine isoprene fluxes using MODIS chlorophyll observations, Geophys. Res. Lett., 32, L09805, doi:10.1029/2005GL022592, 2005. Park R. J., Jacob, D. J., Chin, M., and Martin, R. V.: Sources of carbonaceous aerosols over the United States and implications for natural visibility, J. Geophys. Res., 108, 4355, doi:10.1029/2002JD003190, 2003. Pio, C., Legrand, M., Oliveira, T., et al.: Climatology of aerosol composition (organic versus inorganic) at nonurban sites on a west-east transect across Europe, J. Geophys. Res., 112(D23), D23S02, doi:10.1029/2006JD008038, 2007. Putaud, J. P., Van Dingenen, R., Mangon, M. I., et al.: Chemical mass closure and assessment of the origin of the submicron aerosol in the marine boundary layer and the free troposphere at Tenerife during ACE-2, Tellus B, 52(2), 141–168, 2000. Roelofs, G. J.: A GCM study of organic matter in marine aerosol and its potential contribution to cloud drop activation, Atmos. Chem. Phys., 8, 709–719, 2008. Raper, J. L., Kleb, M. M., Jacob, D. J., Davis, D. D., Newell, R. E., Fuelberg, H. E., Bendura, R. J., Hoell, J. M., and McNeal, R. J.: Pacific Exploratory Mission in the tropical Pacific: PEM-Tropics B, March–April 1999, J. Geophys. Res., 106, 32401–32425, 2001. Ratte, M., Bujok, O., Spitzy, A., and Rudolph, J.: Photochemical alkene formation in seawater from dissolved organic carbon: Results from laboratory experiments, J. Geophys. Res., 103, 5707–5717, 1998. Sciare, J., Sarda-Estave, R., Favez, O., Oikonomou, K., and Cachier, H.: Seasonal variations of carbonaceous aerosols in the Austral Ocean: Evidence of a marine biogenic origin, J. Geophys. Res.-Atmos., to be submitted, 2009. Shaw, G. E.: Bio-controlled thermostasis involving the sulfur cycle, Clim. Change, 5, 297–303, 1983. Shaw, S. L., Chisholm, S. W., and Prinn, R. G.: Isoprene production by Prochlorococcus, a marine cyanobacterium, and other phytoplankton, Mar. Chem., 80, 227–245, 2003. Simó, R. and Dachs, J.: Global ocean emission of dimethylsulfide predicted from biogeophysical data, Global Biogeochem. Cycles, 16(4), 1078, doi:10.1029/2001GB001829, 2002. Spracklen, D. V., Arnold, S. R., Sciare, J., Carslaw, K. S., and Pio, C.: Globally significant oceanic source of organic carbon aerosol, Geophys. Res. Lett., 35, L12811, doi:10.1029/2008GL033359, 2008. Wingenter, O.: Isoprene, Cloud Droplets, and Phytoplankton, Science, 317, 42–43, 2007. Yassaa, N., Peeken, I., Zöllner, E., Bluhm, K., Arnold, S. R., Spracklen, D. V., Wernli, H., and Williams, J.: Evidence for marine production of monoterpenes, Environ. Chem., 5, 391–401, doi:10.1071/EN08047, 2008. Yokouchi, Y., Li, H.-J., Machida, T., Aoki, S., and Akimoto, H.: Isoprene in the marine boundary layer (Southeast Asian Sea, eastern Indian Ocean, and Southern Ocean): Comparison with dimethyl sulfide and bromoform, J. Geophys. Res., 104, 8067–8076, doi:10.1029/1998JD100013, 1999. Yoon, Y. J., Ceburnis, D., Cavalli, F., et al.: Seasonal characteristics of the physiochemical properties of North Atlantic marine atmospheric aerosols, J. Geophys. Res., 112, D04206, doi:10.1029/2005JD007044, 2007.