ACP Atmospheric Chemistry and Physics ACP Atmos. Chem. Phys. 1680-7324 Copernicus Publications Göttingen, Germany 10.5194/acp-14-7499-2014 Air–sea fluxes of oxygenated volatile organic compounds across the Atlantic Ocean Yang M. https://orcid.org/0000-0002-8321-5984 1 Beale R. 1 Liss P. https://orcid.org/0000-0002-4492-2803 2 3 Johnson M. https://orcid.org/0000-0002-4706-8294 2 4 Blomquist B. https://orcid.org/0000-0002-3366-6269 5 Nightingale P. https://orcid.org/0000-0001-7177-5469 1 Plymouth Marine Laboratory, Prospect Place, Plymouth, UK School of Environmental Sciences, University of East Anglia, Norwich, UK Department of Oceanography, Texas A & M University, College Station, TX, USA Centre for Environment, Fisheries and Aquaculture Science, Lowestoft, UK Department of Oceanography, University of Hawaii, Honolulu, HI, USA 24 07 2014 14 14 7499 7517 Copyright: © 2014 M. Yang et al. 2014 This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/ This article is available from https://acp.copernicus.org/articles/14/7499/2014/acp-14-7499-2014.html The full text article is available as a PDF file from https://acp.copernicus.org/articles/14/7499/2014/acp-14-7499-2014.pdf

We present air–sea fluxes of oxygenated volatile organics compounds (OVOCs) quantified by eddy covariance (EC) during the Atlantic Meridional Transect cruise in 2012. Measurements of acetone, acetaldehyde, and methanol in air as well as in water were made in several different oceanic provinces and over a wide range of wind speeds (1–18 m s<sup>−1</sup>). The ocean appears to be a net sink for acetone in the higher latitudes of the North Atlantic but a source in the subtropics. In the South Atlantic, seawater acetone was near saturation relative to the atmosphere, resulting in essentially zero net flux. For acetaldehyde, the two-layer model predicts a small oceanic emission, which was not well resolved by the EC method. Chemical enhancement of air–sea acetaldehyde exchange due to aqueous hydration appears to be minor. The deposition velocity of methanol correlates linearly with the transfer velocity of sensible heat, confirming predominant airside control. We examine the relationships between the OVOC concentrations in air as well as in water, and quantify the gross emission and deposition fluxes of these gases.

 National Science Foundation OISE-1064405 References Bariteau, L., Helmig, D., Fairall, C. W., Hare, J. E., Hueber, J., and Lang, E. K.: Determination of oceanic ozone deposition by ship-borne eddy covariance flux measurements, Atmos. Meas. Tech., 3, 441–455, <a href="http://dx.doi.org/10.5194/amt-3-441-2010">https://doi.org/10.5194/amt-3-441-2010</a>, 2010. Beale, R., Dixon, J., Liss, P., and Nightingale, P.: Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry, Anal. Chim. Acta 706, 128–134, 2011. Beale, R., Dixon, J., Arnold, S., Liss, P., and Nightingale, P.: Methanol, acetaldehyde and acetone in the surface waters of the Atlantic Ocean, J. Geophys. Res., 118, 1–14, <a href="http://dx.doi.org/10.1002/jgrc.20322">https://doi.org/10.1002/jgrc.20322</a>, 2013. Bell, R. P., Rand, M. H., and Wynne-Jones, K. M. A.: Kinetics of the hydration of acetaldehyde, Trans. Faraday Soc., 52, 1093–1102, 1956. Bell, R. P. and Avans, P. G.: Kinetics of the dehydration of methylene glycol in aqueous solution. Proc. R. Sot. London, Ser. A, 291, 297–321, 1966. Bell, T. G., Poulton, A. J., and Malin, G.: Strong linkages between dimethylsulphoniopropionate (DMSP) and phytoplankton community physiology in a large subtropical and tropical Atlantic Ocean data set, Global Biogeochem. Cy., 24, GB3009, <a href="http://dx.doi.org/10.1029/2009GB003617">https://doi.org/10.1029/2009GB003617</a>, 2010. Benkelberg, H. J., Hamm, S., and Warneck, P.: Henry's low coefficients for aqueous solutions of acetone, acetaldehyde and acetonitrile, equilibrium constants for the addition-compounds of acetone and acetaldehyde with bisulfite, J. Atmos. Chem. 20, 17–34, 1995. Blomquist, B., Fairall, C. W., Huebert, B. J., Kieber, D., and Westby, G.: DMS sea-air transfer velocity: Direct measurements by eddy covariance and parameterization based on the NOAA/COARE gas transfer model, Geophys. Res. Lett., 33, L07601, <a href="http://dx.doi.org/10.1029/2006GL025735">https://doi.org/10.1029/2006GL025735</a>, 2006. Blomquist, B. W., Huebert, B. J., Fairall, C. W., and Faloona, I. C.: Determining the sea-air flux of dimethylsulfide by eddy correlation using mass spectrometry, Atmos. Meas. Tech., 3, 1–20, <a href="http://dx.doi.org/10.5194/amt-3-1-2010">https://doi.org/10.5194/amt-3-1-2010</a>, 2010. Carpenter, L. J., Archer, S. D., and Beale, R.: Ocean-atmosphere trace gas exchange, Chem. Soc. Rev., 41, 6473–6506, 2012. Carpenter, L. J., Lewis, A. C., Hopkins, J. R., Read, K. A., Longley, I. D., and Gallagher, M. W.: Uptake of methanol to the North Atlantic Ocean surface, Global Biogeochem. Cy., 18, GB4027, <a href="http://dx.doi.org/10.1029/2004GB002294">https://doi.org/10.1029/2004GB002294</a>, 2004. Dachs, J., Calleja, M. L., Duarte, C. M., del Vento, S., Turpin, B., Polidori, A., Herndl, G. J., and Agust\i , S.: High atmosphere-ocean exchange of organic carbon in the NE subtropical Atlantic, Geophys. Res. Lett., 32, L21807, <a href="http://dx.doi.org/10.1029/2005GL023799">https://doi.org/10.1029/2005GL023799</a>, 2005. Dixon, J. L, Beale, R., and Nightingale, P. D.: Production of methanol, acetaldehyde, and acetone in the Atlantic Ocean, Geophys. Res. Lett., 40, 1-6, https://doi.org/ 10.1002/grl.50922, 2013. Duce, R. A., Liss, P. S., Merrill, J. T., Atlas, E. L., Buat-Menard, P., Hicks, B. B., Miller, J. M., Prospero, J. M., Arimoto, R., Church, T. M., Ellis, W., Galloway, J. N., Hansen, L., Jickells, T. D., Knap, A. H., Reinhardt, K. H., Schneider, B., Soudine, A., Tokos, J. J., Tsunogai, S., Wollast, R., and Zhou, M.: The Atmospheric Input of Trace Species to the World Ocean, Global Biogeochem. Cy., 5, 193–259, 1991. Edson, J., Hinton, A., Prada, K., Hare, J., and Fairall, C.: Direct covariance flux estimates from mobile platforms at sea, J. Atmos. Ocean. Technol., 15, 547–562, 1998. Fairall, C. W., Bradley, E. F., Rogers, D. P., Edson, J. B., and Young, G. S.: Bulk parameterization of air-sea fluxes for Tropical Ocean-Global Atmosphere Coupled-Ocean Atmosphere Response Experiment, J. Geophys. Res., 101, 3747–3764, 1996. Fairall, C. W., Yang, M., Bariteau, L., Edson, J. B., Helmig, D., McGillis, W., Pezoa, S., Hare, J. E., Huebert, B., and Blomquist, B.: Implementation of the Coupled Ocean-Atmosphere Response Experiment flux algorithm with CO<sub>2</sub>, dimethyl sulfide, and O<sub>3</sub>, J. Geophys. Res., 116, C00F09, <a href="http://dx.doi.org/10.1029/2010JC006884">https://doi.org/10.1029/2010JC006884</a>, 2011. Fischer, E. V., Jacob, D. J., Millet, D. B., Yantosca, R. M., and Mao, J.: The role of the ocean in the global atmospheric budget of acetone, Geophys. Res. Lett., 39, L01807, <a href="http://dx.doi.org/10.1029/2011GL050086">https://doi.org/10.1029/2011GL050086</a>, 2012. Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., and Fall, R.: Natural emissions of non-methane volatile organic compounds; carbon monoxide, and oxides of nitrogen from North America, Atmos. Environ., 34, 2205–2230, 2000. Heald, C. L., Goldstein, A. H., Allan, J. D., Aiken, A. C., Apel, E., Atlas, E. L., Baker, A. K., Bates, T. S., Beyersdorf, A. J., Blake, D. R., Campos, T., Coe, H., Crounse, J. D., DeCarlo, P. F., de Gouw, J. A., Dunlea, E. J., Flocke, F. M., Fried, A., Goldan, P., Griffin, R. J., Herndon, S. C., Holloway, J. S., Holzinger, R., Jimenez, J. L., Junkermann, W., Kuster, W. C., Lewis, A. C., Meinardi, S., Millet, D. B., Onasch, T., Polidori, A., Quinn, P. K., Riemer, D. D., Roberts, J. M., Salcedo, D., Sive, B., Swanson, A. L., Talbot, R., Warneke, C., Weber, R. J., Weibring, P., Wennberg, P. O., Worsnop, D. R., Wittig, A. E., Zhang, R., Zheng, J., and Zheng, W.: Total observed organic carbon (TOOC) in the atmosphere: a synthesis of North American observations, Atmos. Chem. Phys., 8, 2007–2025, <a href="http://dx.doi.org/10.5194/acp-8-2007-2008">https://doi.org/10.5194/acp-8-2007-2008</a>, 2008. Heikes, B. G., Chang, W. N., Pilson, M. E. Q., Swift, E., Singh, H. B., Guenther, A., Jacob, D. J., Field, B. D., Fall, R., Riemer, D., and Brand, L.: Atmospheric methanol budget and ocean implication, Global Biogeochem. Cy., 16, 1133, <a href="http://dx.doi.org/10.1029/2002GB001895">https://doi.org/10.1029/2002GB001895</a>, 2002. Hicks, B, Wesely, M, Lindberg, S, Bromberg, S. Proceedings of the NAPAP Workshop on Dry Deposition, Harpers Ferry, W. Va., 25–27, p. 77, 1986. Hoover, T. E. and Berkshire, D. C.: Effects of hydration on carbon dioxide exchange across an air-water interface. J. Geophys. Res., 74, 456–464, 1969. Jacob, D. J., Field, B. D., Jin, E. M., Bey, I., Li, Q., Logan, J. A., Yantosca, R. M., and Singh H. B., Atmospheric budget of acetone, J. Geophys. Res., 107, 4100, <a href="http://dx.doi.org/10.1029/2001JD000694">https://doi.org/10.1029/2001JD000694</a>, 2002. Jacob, D. J., Field, B. D., Li, Q. B., Blake, D. R., de Gouw, J., Warneke, C., Hansel, A., Wisthaler, A., Singh, H. B., and Guenther, A.: Global budget of methanol: Constraints from atmospheric observations, J. Geophys. Res., 110, D08303, <a href="http://dx.doi.org/10.1029/2004JD005172">https://doi.org/10.1029/2004JD005172</a>, 2005. Johnson, M.: A numerical scheme to calculate temperature and salinity dependent air-water transfer velocities for any gas. Ocean Sci. 6, 913–932, <a href="http://dx.doi.org/10.5194/os-6-913-2010">https://doi.org/10.5194/os-6-913-2010</a>, 2010. Jardine, K., Harley, P., Karl, T., Guenther, A., Lerdau, M., and Mak, J. E.: Plant physiological and environmental controls over the exchange of acetaldehyde between forest canopies and the atmosphere, Biogeosciences, 5, 1559–1572, <a href="http://dx.doi.org/10.5194/bg-5-1559-2008">https://doi.org/10.5194/bg-5-1559-2008</a>, 2008. Kaimal, J., Wyngaard, J., Izumi, Y., and Coté, O.: Spectral characteristics of surface layer turbulence, Q. J. Roy. Meteorol. Soc., 98, 563–589, <a href="http://dx.doi.org/10.1002/qj.49709841707">https://doi.org/10.1002/qj.49709841707</a>, 1972. Kameyama, S., Tanimoto, H., Inomata, S., Tsunogai, U., Ooki, A., Takeda, S, Obata, H., Tsuda, A., and Uematsu, M.: High-resolution measurement of multiple volatile organic compounds dissolved in seawater using equilibrator inlet–proton transfer reaction-mass spectrometry (EI–PTR-MS). Mar. Chem., 122, 59–73, 2010. Karl, T., Guenther, A., Lindinger, C., Jordan, A., Fall, R., and Lindinger, W.: Eddy covariance measurements of oxygenated volatile organic compound fluxes from crop harvesting using a redesigned proton-transfer-reaction mass spectrometer, J. Geophys. Res., 106, 24157–24167, <a href="http://dx.doi.org/10.1029/2000JD000112">https://doi.org/10.1029/2000JD000112</a>, 2001. 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, <a href="http://dx.doi.org/10.1029/2004JD004738">https://doi.org/10.1029/2004JD004738</a>, 2004. Kieber, R. J., Zhou, X., and Mopper, K.: Formation of carbonyl compounds from UV-induced photodegradation of humic substances in natural waters: Fate of riverine carbon in the sea. Limnol. Oceanogr., 35: 1503–1515, 1990. Kurz, J. L. and Coburn, J. I.: The hydration of acetaldehyde. II. Transition-state characterization, J. Am. Chem. Soc., 89, 3524–3528, 1967. Lerot, C., Stavrakou, T., De Smedt, I., Mueller, J.-F., and Van Roozendael, M.: Glyoxal vertical columns from GOME-2 backscattered light measurements and comparisons with a global model, Atmos. Chem. Phys., 10, 12059–12072, <a href="http://dx.doi.org/10.5194/acp-10-12059-2010">https://doi.org/10.5194/acp-10-12059-2010</a>, 2010 Lewis, A. C., Hopkins, J. R., Carpenter, L. J., Stanton, J., Read, K. A., and Pilling, M. J.: Sources and sinks of acetone, methanol, and acetaldehyde in North Atlantic marine air, Atmos. Chem. Phys., 5, 1963–1974, <a href="http://dx.doi.org/10.5194/acp-5-1963-2005">https://doi.org/10.5194/acp-5-1963-2005</a>, 2005. Lindinger, W., Hansel A., and 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 Spectrom. Ion Proc., 173, 191–241, 1998. Liss, P. S. and Slater, P. G.: Flux of gases across the air-sea interface, Nature, 247, 181–184, <a href="http://dx.doi.org/10.1038/247181a0">https://doi.org/10.1038/247181a0</a>, 1974. Marandino, C. A., De Bruyn, W. J., Miller, S. D., Prather, M. J., and Saltzman, E. S.: Oceanic uptake and the global atmospheric acetone budget, Geophys. Res. Lett., 32, L15806, <a href="http://dx.doi.org/10.1029/2005GL023285">https://doi.org/10.1029/2005GL023285</a>, 2005. Millet, D. B., Jacob, D. J., Turquety, S., Hudman, R. C., Wu, S., Fried, A., Walega, J., Heikes, B. G., Blake, D. R., Singh, H. B., Anderson, B. E., and Clarke, A. D.: Formaldehyde distribution over North America: Implications for satellite retrievals of formaldehyde columns and isoprene emission, J. Geophys. Res., 111, D24S02, <a href="http://dx.doi.org/10.1029/2005JD006853">https://doi.org/10.1029/2005JD006853</a>, 2006. Millet, D. B., Jacob, D. J., Custer, T. G., de Gouw, J. A., Goldstein, A. H., Karl, T., Singh, H. B., Sive, B. C., Talbot, R. W., Warneke, C., and Williams, J.: New constraints on terrestrial and oceanic sources of atmospheric methanol, Atmos. Chem. Phys., 8, 6887–6905, <a href="http://dx.doi.org/10.5194/acp-8-6887-2008">https://doi.org/10.5194/acp-8-6887-2008</a>, 2008. Mopper, K. and Kieber, D. J.: Distribution and biological turnover of dissolved organic compounds in the water column of the Black Sea, Deep-Sea Res., 38, 1021–1047, 1991. Read K., Carpenter, L., Arnold, S., Beale, R., Nightingale, P., Hopkins, J., Lewis, A., Lee. J, Mendes, L., and Pickering S.: Multiannual Observations of Acetone, Methanol, and Acetaldehyde in Remote Tropical Atlantic Air: Implications for Atmospheric OVOC Budgets and Oxidative Capacity, Environ. Sci. Technol., 46, 11028–11039, 2012. Sander, R.: Compilation of Henry's Law constants for inorganic and organic species of potential importance in environmental chemistry (Version 3), <a href="http://www.henrys-law.org">http://www.henrys-law.org</a> (last access: 19 March 2014), 1999. Schecker, H. and Schultz, G.: Untersuchungen zur Hydrationskinetik von Formaldehyd in waessriger Loesung, Z. Phys. Chem., Neue Folge, 65, 221–224, 1969. Singh, H., Chen, Y., Tabazadeh, A., Fukui, Y., Bey, I., Yantosca, R., Jacob, D., Arnold, F., Wohlfrom, K., Atlas, E., Flocke, F., Blake, D., Blake, N., Heikes, B., Snow, J., Talbot, R., Gregory, G., Sachse, G., Vay, S., and Kondo, Y.: Distribution and fate of selected oxygenated organic species in the troposphere and lower stratosphere over the Atlantic, J. Geophys. Res., 105, 3795–3805, 2000. Singh, H. B., Salas, L. J., Chatfield, R. B., Czech, E., Fried, A., Walega, J., Evans, M. J., Field, B. D., Jacob, D. J., Blake, D., Heikes, B., Talbot, R., Sachse, G., Crawford, J. H., Avery, M. A., Sandholm, S., and Fuelberg, H.: Analysis of the atmospheric distribution, sources, and sinks of oxygenated volatile organic chemicals based on measurements over the Pacific during TRACE-P, J. Geophys. Res., 109, D15S07, <a href="http://dx.doi.org/10.1029/2003JD003883">https://doi.org/10.1029/2003JD003883</a>, 2004. Singh, H. B., Tabazadeh, A., Evans, M. J., Field, B. D., Jacob, D. J., Sachse, G., Crawford, J. H., Shetter, R., and Brune, W. H.: Oxygenated volatile organic chemicals in the oceans: Inferences and implications based on atmospheric observations and air-sea exchange models, Geophys. Res. Lett., 30, 1862, <a href="http://dx.doi.org/10.1029/2003GL017933">https://doi.org/10.1029/2003GL017933</a>, 2003. Sinreich, R., Coburn, S., Dix, B., and Volkamer, R.: Ship-based detection of glyoxal over the remote tropical Pacific Ocean, Atmos. Chem. Phys., 10, 11359–11371, <a href="http://dx.doi.org/10.5194/acp-10-11359-2010">https://doi.org/10.5194/acp-10-11359-2010</a>, 2010. Snider, J. and Dawson, G.: Tropospheric light alcohols, carbonyls, and acetonitrile: Concentrations in the southwestern United States and Henry's law data, J. Geophys. Res. 90, 3797–3805, 1985. 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, <a href="http://dx.doi.org/10.5194/acp-5-465-2005">https://doi.org/10.5194/acp-5-465-2005</a>, 2005. Stavrakou, T., Mueller, J.-F., De Smedt, I., Van Roozendael, M., Kanakidou, M., Vrekoussis, M., Wittrock, F., Richter, A., and Burrows, J. P.: The continental source of glyoxal es- timated by the synergistic use of spaceborne measurements and inverse modelling, Atmos. Chem. Phys., 9, 8431–8446, <a href="http://dx.doi.org/10.5194/acp-9-8431-2009">https://doi.org/10.5194/acp-9-8431-2009</a>, 2009. Taddei, S., Toscano, P., Gioli, B., Matese, A., Miglietta, F., Vaccari, F. P., Zaldei, A., Custer, T., and Williams, J.: Carbon dioxide and acetone air-sea fluxes over the Southern Atlantic, Environ. Sci. Technol., 43, 5218–5222, 2009. Tanimoto, H., Kameyama, S., Iwata, T., Inomata, S., and Omori, Y.: Measurement of air-sea exchange of dimethyl sulfide and acetone by PTR-MS coupled with gradient flux technique, Environ. Sci. Technol., 48, 526–533, <a href="http://dx.doi.org/10.1021/es4032562">https://doi.org/10.1021/es4032562</a>, 2014. Webb, E. D., Pearman, G. I., and Leuning, R.: Correction of flux measurements for density due to heat and water vapor transport, Q. J. Roy. Meteor. Soc., 106, 85–100, <a href="http://dx.doi.org/10.1002/qj.49710644707">https://doi.org/10.1002/qj.49710644707</a>, 1980. Williams, J., Holzinger, R., Gros, V., Xu, X., Atlas, E., and Wallace, D. W. R.: Measurements of organic species in air and seawater from the tropical Atlantic, Geophys. Res. Lett., 31, L23S06, <a href="http://dx.doi.org/10.1029/2004GL020012">https://doi.org/10.1029/2004GL020012</a>, 2004. Woolf, D. K.: Bubbles and their role in gas exchange, in The Sea Surface and Global Change, edited by: Duce, R. and Liss, P., Cambridge Univ. Press, New York, 173–205, <a href="http://dx.doi.org/10.1017/CBO9780511525025.007">https://doi.org/10.1017/CBO9780511525025.007</a>, 1997. Wróblewski, T., Ziemczonek, L. Alhasan, A. M., and Karwasz, G. P.: Ab initio and density functional theory calculations of proton affinities for volatile organic compounds, Eur. Phys. J. Spec. Top., 144, 191–195, <a href="http://dx.doi.org/10.1140/epjst/e2007-00126-7">https://doi.org/10.1140/epjst/e2007-00126-7</a>, 2007. Yang, M., Beale, R., Smyth, T., and Blomquist, B.: Measurements of OVOC fluxes by eddy covariance using a proton-transfer-reaction mass spectrometer – method development at a coastal site, Atmos. Chem. Phys., 13, 6165–6184, <a href="http://dx.doi.org/10.5194/acp-13-6165-2013">https://doi.org/10.5194/acp-13-6165-2013</a>, 2013a. Yang, M., Nightingale, P., Beale, R., Liss, P., Blomquist, B., and Fairall, C.: Atmospheric deposition of methanol over the Atlantic Ocean, P. Natl. Acad. Sci., <a href="http://dx.doi.org/10.1073/pnas.1317840110">https://doi.org/10.1073/pnas.1317840110</a>, 110, 20034–20039, 2013b. Zhao, J. and Zhang, R. Y.: Proton transfer reaction rate constants between hydronium ion (H<sub>3</sub>O(+)) and volatile organic compounds, Atmos. Environ., 38, 2177–2185, 2004. Zhou, X. and Mopper, K.: Apparent partition coefficients of 15 carbonyl compounds between air and seawater and between air and freshwater; implications for air-sea exchange, Environ. Sci. Technol., 24, 1864–1869, 1990. Zhou, X. and Mopper, K.: Photochemical production of low- molecular-weight carbonyl compounds in seawater and surface microlayer and their air-sea exchange, Mar. Chem., 56, 201–213, 1997.