One of the most important natural aerosol systems at the global level is marine aerosol that comprises both organic and inorganic components of primary and secondary origin. The present paper reviews some new results on primary and secondary organic marine aerosol, achieved during the EU project MAP (Marine Aerosol Production), comparing them with those reported in the recent literature. Marine aerosol samples collected at the coastal site of Mace Head, Ireland, show a chemical composition trend that is influenced by the oceanic biological activity cycle, in agreement with other observations. Laboratory experiments show that sea-spray aerosol from biologically active sea water can be highly enriched in organics, and the authors highlight the need for further studies on the atmospheric fate of such primary organics. With regard to the secondary fraction of organic aerosol, the average chemical composition and molecular tracer (methanesulfonic-acid, amines) distribution could be successfully characterized by adopting a multitechnique analytical approach. 1. Introduction The literature contains a great deal of evidence that large sectors of the marine atmosphere are influenced by continental outflows (natural or anthropogenic) and by ship exhaust emissions [1, 2]. However, the ocean is an important source of fine particles, and in background marine regions aerosol populations are dominated by natural marine particles [3, 4]. Given the ocean’s extension, marine aerosol constitutes one of the most important natural aerosol systems at the global level. It contributes significantly to the Earth’s radiative budget, biogeochemical cycling, with impacts on ecosystems and also on regional air quality [5]. The knowledge of particle chemical composition, as a function of size, is necessary for understanding and predicting the marine aerosol properties relevant to climate, for example, their ability to act as cloud condensation nuclei (CCN) and to influence the cloud droplet number concentration (CDNC) over background ocean regions. In recent years, particular interest has focused on the marine aerosol organic fraction, its biogenic origin and the possible sources and mechanisms responsible for the high concentrations of organics observed in the submicron size fraction [6–8]. Figure 1 summarizes schematically the main potential formation pathways of organic aerosol in the marine boundary layer (MBL). Marine aerosol can derive both from primary or secondary processes. Primary aerosol production derives from the interaction of wind with the ocean surface and results in
References
[1]
G. Chen, L. G. Huey, M. Trainer, et al., “An investigation of the chemistry of ship emission plumes during ITCT 2002,” Journal of Geophysical Research D, vol. 110, no. 10, Article ID D10S90, 15 pages, 2005.
[2]
J. Huang, P. Minnis, B. Chen, et al., “Long-range transport and vertical structure of Asian dust from CALIPSO and surface measurements during PACDEX,” Journal of Geophysical Research D, vol. 113, no. 23, Article ID D23212, 2008.
[3]
D. V. Spracklen, S. R. Arnold, J. Sciare, K. S. Carslaw, and C. Pio, “Globally significant oceanic source of organic carbon aerosol,” Geophysical Research Letters, vol. 35, no. 12, Article ID L12811, 2008.
[4]
E. Vignati, M. C. Facchini, M. Rinaldi, et al., “Global scale emission and distribution of sea-spray aerosol: sea-salt and organic enrichment,” Atmospheric Environment, vol. 44, no. 5, pp. 670–677, 2010.
[5]
C. D. O'Dowd and G. de Leeuw, “Marine aerosol production: a review of the current knowledge,” Philosophical Transactions of the Royal Society A, vol. 365, no. 1856, pp. 1753–1774, 2007.
[6]
C. D. O'Dowd, M. C. Facchini, F. Cavalli, et al., “Biogenically driven organic contribution to marine aerosol,” Nature, vol. 431, no. 7009, pp. 676–680, 2004.
[7]
N. Meskhidze and A. Nenes, “Phytoplankton and cloudiness in the southern ocean,” Science, vol. 314, no. 5804, pp. 1419–1423, 2006.
[8]
E. K. Bigg, “Sources, nature and influence on climate of marine airborne particles,” Environmental Chemistry, vol. 4, no. 3, pp. 155–161, 2007.
[9]
D. C. Blanchard, “Sea-to-air transport of surface active material,” Science, vol. 146, no. 3642, pp. 396–397, 1964.
[10]
C. Oppo, S. Bellandi, N. Degli Innocenti, et al., “Surfactant components of marine organic matter as agents for biogeochemical fractionation and pollutant transport via marine aerosols,” Marine Chemistry, vol. 63, no. 3-4, pp. 235–253, 1999.
[11]
T. L. Eliason, J. B. Gilman, and V. Vaida, “Oxidation of organic films relevant to atmospheric aerosols,” Atmospheric Environment, vol. 38, no. 9, pp. 1367–1378, 2004.
[12]
S. F. Maria, L. M. Russell, M. K. Gilles, and S. C. B. Myneni, “Organic aerosol growth mechanisms and their climate-forcing implications,” Science, vol. 306, no. 5703, pp. 1921–1924, 2004.
[13]
B. Ervens, C. George, J. E. Williams, et al., “CAPRAM 2.4 (MODAC mechanism): an extended and condensed tropospheric aqueous phase mechanism and its application,” Journal of Geophysical Research D, vol. 108, no. 14, pp. 1–21, article 4426, 2003.
[14]
P. Warneck, “In-cloud chemistry opens pathway to the formation of oxalic acid in the marine atmosphere,” Atmospheric Environment, vol. 37, no. 17, pp. 2423–2427, 2003.
[15]
G. E. Shaw, “Bio-controlled thermostasis involving the sulfur cycle,” Climatic Change, vol. 5, no. 3, pp. 297–303, 1983.
[16]
R. J. Charlson, J. E. Lovelock, M. O. Andreae, and S. G. Warren, “Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate,” Nature, vol. 326, no. 6114, pp. 655–661, 1987.
[17]
F. Cavalli, M. C. Facchini, S. Decesari, et al., “Advances in characterization of size-resolved organic matter in marine aerosol over the North Atlantic,” Journal of Geophysical Research D, vol. 109, no. 24, pp. 1–14, 2004.
[18]
S. S. Yum and J. G. Hudson, “Wintertime/summertime contrasts of cloud condensation nuclei and cloud microphysics over the Southern Ocean,” Journal of Geophysical Research D, vol. 109, no. 6, Article ID D06204, 14 pages, 2004.
[19]
A. Sorooshian, L. T. Padrò, A. Nenes, et al., “On the link between ocean biota emissions, aerosol, and maritime clouds: airborne, ground, and satellite measurements off the coast of California,” Global Biogeochemical Cycles, vol. 23, Article ID GB4007, 15 pages, 2009.
[20]
M. C. Facchini, S. Decesari, M. Rinaldi, et al., “Important source of marine secondary organic aerosol from biogenic amines,” Environmental Science and Technology, vol. 42, no. 24, pp. 9116–9121, 2008.
[21]
M. Rinaldi, M. C. Facchini, S. Decesari, et al., “On the representativeness of coastal aerosol studies to open ocean studies: Mace Head-a case study,” Atmospheric Chemistry and Physics, vol. 9, no. 24, pp. 9635–9646, 2009.
[22]
M. C. Facchini, M. Rinaldi, S. Decesari, et al., “Primary submicron marine aerosol dominated by insoluble organic colloids and aggregates,” Geophysical Research Letters, vol. 35, no. 17, Article ID L17814, 2008.
[23]
S. Decesari, M. C. Facchini, S. Fuzzi, and E. Tagliavini, “Characterization of water-soluble organic compounds in atmospheric aerosol: a new approach,” Journal of Geophysical Research D, vol. 105, no. D1, pp. 1481–1489, 2000.
[24]
V. Mancinelli, M. Rinaldi, E. Finessi, et al., “An anion-exchange high-performance liquid chromatography method coupled to total organic carbon determination for the analysis of water-soluble organic aerosols,” Journal of Chromatography A, vol. 1149, no. 2, pp. 385–389, 2007.
[25]
D. Ceburnis, C. D. O'Dowd, G. S. Jennings, et al., “Marine aerosol chemistry gradients: elucidating primary and secondary processes and fluxes,” Geophysical Research Letters, vol. 35, no. 7, Article ID L07804, 2008.
[26]
Y. J. Yoon, D. Ceburnis, F. Cavalli, et al., “Seasonal characteristics of the physicochemical properties of North Atlantic marine atmospheric aerosols,” Journal of Geophysical Research D, vol. 112, no. 4, Article ID D04206, 2007.
[27]
H. Mukai, Y. Yokouchi, and M. Suzuki, “Seasonal variation of methanesulfonic acid in the atmosphere over the Oki Islands in the Sea of Japan,” Atmospheric Environment, vol. 29, no. 14, pp. 1637–1648, 1995.
[28]
S.-M. Li, L. A. Barrie, and D. Toom, “Seasonal variations of methanesulfonate, non-sea-salt sulfate, and sulfur dioxide at three sites in Canada,” Journal of Geophysical Research D, vol. 101, no. 2, pp. 4165–4173, 1996.
[29]
D. L. Savoie, R. Arimoto, W. C. Keene, J. M. Prospera, R. A. Duce, and J. N. Galloway, “Marine biogenic and anthropogenic contributions to non-sea-salt sulfate in the marine boundary layer over the North Atlantic Ocean,” Journal of Geophysical Research D, vol. 107, no. 18, pp. 1–21, article 4356, 2002.
[30]
T. W. Andreae, M. O. Andreae, and G. Schebeske, “Biogenic sulfur emissions and aerosols over the tropical South Atlantic 1. Dimethylsulfide in seawater and in the atmospheric boundary layer,” Journal of Geophysical Research, vol. 99, no. D11, pp. 1–22, article 819, 1994.
[31]
W. A. H. Asman, R. M. Harrison, and C. J. Ottley, “Estimation of the net air-sea flux of ammonia over the southern bight of the North Sea,” Atmospheric Environment, vol. 28, no. 22, pp. 3647–3654, 1994.
[32]
I. Barnes, J. Hjorth, and N. Mihalapoulos, “Dimethyl sulfide and dimethyl sulfoxide and their oxidation in the atmosphere,” Chemical Reviews, vol. 106, no. 3, pp. 940–975, 2006.
[33]
J. Sciare, O. Favez, R. Sarda-Estève, K. Oikonomou, H. Cachier, and V. Kazan, “Long-term observations of carbonaceous aerosols in the Austral Ocean atmosphere: evidence of a biogenic marine organic source,” Journal of Geophysical Research D, vol. 114, no. 15, Article ID D15302, 2009.
[34]
W. C. Keene, H. Maring, J. R. Maben, et al., “Chemical and physical characteristics of nascent aerosols produced by bursting bubbles at a model air-sea interface,” Journal of Geophysical Research D, vol. 112, no. 21, Article ID D21202, 2007.
[35]
R. L. Modini, B. Harris, and Z. D. Ristovski, “The organic fraction of bubble-generated, accumulation mode Sea Spray Aerosol (SSA),” Atmospheric Chemistry and Physics Discussions, vol. 9, no. 5, pp. 21399–21424, 2009.
[36]
E. K. Bigg and C. Leck, “The composition of fragments of bubbles bursting at the ocean surface,” Journal of Geophysical Research D, vol. 113, no. 11, Article ID D11209, 2008.
[37]
N. Kovac, O. Bajt, J. Faganeli, B. Sket, and B. Orel, “Study of macroaggregate composition using FT-IR and -NMR spectroscopy,” Marine Chemistry, vol. 78, no. 4, pp. 205–215, 2002.
[38]
J. Zhou, K. Mopper, and U. Passow, “The role of surface-active carbohydrates in the formation of transparent exopolymer particles by bubble adsorption of seawater,” Limnology and Oceanography, vol. 43, no. 8, pp. 1860–1871, 1998.
[39]
L. M. Russell, L. N. Hawkins, A. A. Frossard, P. K. Quinn, and T. S. Bates, “Carbohydrate-like composition of submicron atmospheric particles and their production from ocean bubble bursting,” Proceedings of the National Academy of Sciences of the United States of America, vol. 107, no. 15, pp. 6652–6657, 2010.
[40]
X. Zhou, A. J. Davis, D. J. Kieber, et al., “Photochemical production of hydroxyl radical and hydroperoxides in water extracts of nascent marine aerosols produced by bursting bubbles from Sargasso seawater,” Geophysical Research Letters, vol. 35, no. 20, Article ID L20803, 2008.
[41]
J. L. Jimenez, M. R. Canagaratna, N. M. Donahue, et al., “Evolution of organic aerosols in the atmosphere,” Science, vol. 326, no. 5959, pp. 1525–1529, 2009.
[42]
K. Mopper and R. G. Zika, “Free amino acids in marine rains: evidence for oxidation and potential role in nitrogen cycling,” Nature, vol. 325, no. 6101, pp. 246–249, 1987.
[43]
P. J. Milne and R. G. Zika, “Amino acid nitrogen in atmospheric aerosols: occurrence, sources and photochemical modification,” Journal of Atmospheric Chemistry, vol. 16, no. 4, pp. 361–398, 1993.
[44]
K. Gorzelska and J. N. Galloway, “Amine nitrogen in the atmospheric environment over the North Atlantic Ocean,” Global Biogeochemical Cycles, vol. 4, no. 3, pp. 309–333, 1990.
[45]
S. W. Gibb, R. F. C. Mantoura, and P. S. Liss, “Ocean-atmosphere exchange and atmospheric speciation of ammonia and methylamines in the region of the NW Arabian Sea,” Global Biogeochemical Cycles, vol. 13, no. 1, pp. 161–178, 1999.
[46]
S. M. Murphy, A. Sorooshian, J. H. Kroll, et al., “Secondary aerosol formation from atmospheric reactions of aliphatic amines,” Atmospheric Chemistry and Physics, vol. 7, no. 9, pp. 2313–2337, 2007.
[47]
S. Angeling, D. T. Suess, and K. A. Prather, “Formation of aerosol particles from reactions of secondary and tertiary alkylamines: characterization by aerosol time-of-flight mass spectrometry,” Environmental Science and Technology, vol. 35, no. 15, pp. 3130–3138, 2001.
[48]
P. V. Tan, G. J. Evans, J. Tsai, et al., “On-line analysis of urban particulate matter focusing on elevated wintertime aerosol concentrations,” Environmental Science and Technology, vol. 36, no. 16, pp. 3512–3518, 2002.
[49]
D. A. Hansell and C. A. Carlson, Biogeochemistry of Marine Dissolved Organic Matter, Academic Press, New York, NY, USA, 2002.
[50]
M. Johnson, R. Sanders, V. Avgoustidi, et al., “Ammonium accumulation during a silicate-limited diatom bloom indicates the potential for ammonia emission events,” Marine Chemistry, vol. 106, no. 1-2, pp. 63–75, 2007.
[51]
C. Müller, Y. Iinuma, J. Karstensen, et al., “Seasonal variation of aliphatic amines in marine sub-micrometer particles at the Cape Verde Islands,” Atmospheric Chemistry and Physics, vol. 9, no. 24, pp. 9587–9597, 2009.
[52]
K. Kawamura and F. Sakaguchi, “Molecular distributions of water soluble dicarboxylic acids in marine aerosols over the Pacific Ocean including tropics,” Journal of Geophysical Research, vol. 104, no. D3, pp. 3501–3509, 1999.
[53]
M. Claeys, W. Wang, R. Vermeylen, et al., “Chemical characterisation of marine aerosol at Amsterdam Island during the austral summer of 2006-2007,” Journal of Aerosol Science, vol. 41, no. 1, pp. 13–22, 2010.
[54]
C. D. O'Dowd, B. Langmann, S. Varghese, C. Scannell, D. Ceburnis, and M. C. Facchini, “A combined organic-inorganic sea-spray source function,” Geophysical Research Letters, vol. 35, no. 1, Article ID L01801, 2008.
[55]
H. Coe, J. D. Allan, M. R. Alfarra, et al., “Chemical and physical characteristics of aerosol particles at a remote coastal location, Mace Head, Ireland, during NAMBLEX,” Atmospheric Chemistry and Physics, vol. 6, no. 11, pp. 3289–3301, 2006.
[56]
S. R. Zorn, F. Drewnick, M. Schott, T. Hoffmann, and S. Borrmann, “Characterization of the South Atlantic marine boundary layer aerosol using an aerodyne aerosol mass spectrometer,” Atmospheric Chemistry and Physics, vol. 8, no. 16, pp. 4711–4728, 2008.
[57]
J. D. Allan, D. O. Topping, N. Good, et al., “Composition and properties of atmospheric particles in the eastern Atlantic and impacts on gas phase uptake rates,” Atmospheric Chemistry and Physics, vol. 9, no. 23, pp. 9299–9314, 2009.
