Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
7
3
2007
10.5194/acpd-7-6329-2007
http://www.atmos-chem-phys-discuss.net/7/6329/2007/
http://www.atmos-chem-phys-discuss.net/7/6329/2007/acpd-7-6329-2007.html
http://www.atmos-chem-phys-discuss.net/7/6329/2007/acpd-7-6329-2007.pdf
6329
6356
2007-05-11
Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site
C. Arsene
carsene@uaic.ro
A. Bougiatioti
M. Kanakidou
B. Bonsang
N. Mihalopoulos
Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, Greece
Inorganic and Analytical Chemistry Department, Faculty of Chemistry, Al.I Cuza University of Iasi, Romania
Laboratoire des Sciences du Climat et de l'Environnement, CNRS/CEA, France
In situ continuous hourly measurements of C<sub>2</sub>-C<sub>8</sub> non-methane hydrocarbons
(NMHC<sub><i>S</i></sub>) have been performed from March to October 2006 at two coastal
locations on the island of Crete, in the Eastern Mediterranean. Well defined
diurnal variations were observed for several short lived NMHC<sub><i>S</i></sub>
(including ethene, propene, n-butane, n-pentane, n-hexane,
2-methyl-pentane). The daytime concentration of hydroxyl (OH) radicals
estimated from these experimental data varied from 1.3×10<sup>6</sup> to
~4.0×10<sup>6</sup> radical cm<sup>−3</sup>, in good agreement with
box-model simulations. In addition the relative variability of various
hydrocarbon pairs (at least 7) was used to derive the tropospheric levels of
Cl atoms. The Cl atom concentration has been estimated to range between
0.6×10<sup>4</sup> and 4.7×10<sup>4</sup> atom cm<sup>−3</sup>, in good
agreement with gaseous hydrochloric acid (HCl) observations in the area.
Such levels of Cl atoms can be of considerable importance for the oxidation
capacity of the troposphere on a regional scale.
Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, 2006.
Bardouki, H., Berresheim, H., Sciare, J., Vrekoussis, M., Kouvarakis, G., Oikonomou, C, Schneider, J., and Mihalopoulos, N.: Gaseous (DMS, DMSO, SO<sub>2</sub>, H<sub>2</sub>SO<sub>4</sub>, MSA) and particulate (MS$^-$ and SO$_4^2-)$ sulphur compounds during the MINOS campaign, Atmos. Chem. Phys., 3, 1871–1886, 2003.
Berresheim, H., Plass-Dulmer, C., Elste, T., Mihalopoulos, N., and Rohrer, F.: OH in the coastal boundary layer of Crete during MINOS, measurements and relationship with ozone photolysis, Atmos. Chem. Phys., 3, 639–649, 2003.
Bonsang, B., Kanakidou, M., and Lambert, G.: Non methane hydrocarbons chemistry in the atmosphere of an equatorial forest: a case of indirect photochemical production of OH radicals, Geophys. Res. Lett., 88, 1250–1253, 1987.
Bonsang, B. and Kanakidou, M.: Non-methane hydrocarbon variability during the FIELDVOC'94 campaign in Portugal, Chemosphere – Global Change Science, 3, 259–273, 2001.
Collins, W. J., Derwent, R. G., Johnson, C. E., and Stevenson, D. S.: The oxidation of organic compounds in the troposphere and their global warming potentials, Climatic Change, 52, 53–479, 2002.
Crutzen, P.: Photochemical reactions initiated by and influencing ozone in unpolluted tropospheric air, Tellus, 26, 47–57, 1974.
Derwent, R. G., Carslaw, N., Simmonds, P. G., Bassford, M., O'Doherty, S., Ryall, D. B., Pilling, M. J., Lewis, A. C., and McQuaid, J. B.: Hydroxyl radical concentrations estimated from measurements of trichloroethylene during the EASE/ACSOE campaign at Mace Head, Ireland, during July 1996, J. Atmos. Chem., 34, 185–205, 1999.
Derwent, R. G., Jenkin, M. E., Saunders, S. M., Pilling, M. J., Simmonds, P. G., Passant, N. R., Dollard, G. J., Dumitrean, P., and Kent, F.: Photochemical ozone formation in north west Europe and its control, Atmos. Environ., 37, 1983–1991, 2003.
Economou, C. and Mihalopoulos, N.: Formaldehyde in the rainwater in the eastern Mediterranean: occurrence, deposition and contribution to organic carbon budget, Atmos. Environ., 36, 1337–1347, 2002.
Gerasopoulos, E., Kouvarakis, G., Vrekoussis, M., Kanakidou, M., and Mihalopoulos, N.: Ozone variability in the marine boundary layer of the eastern Mediterranean based on 7-year observations, J. Geophys. Res., 110, 1–12, 2005.
Gros, V., Williams, J., Van Aardenne, J. A., Salisbury, G., Hofmann, R., Lawrence, M. G., Von Kuhlmann, R., Lelieveld, J., Krol, M., Berresheim, H., Lobert, J. M., and Atlas, E.: Origin of anthropogenic hydrocarbons and halocarbons measured in the summertime European outflow (on Crete 2001), Atmos. Chem. Phys., 3, 1223–1235, 2003.
Hopkins, J. R., Jones, I. D., Lewis, A. C., McQuid, J. B., and Seakins, P. W.: Non-methane hydrocarbons in the Arctic boundary layer, Atmos. Environ., 36, 3217–3229, 2002.
Jenkin, M. J., Saunders, S. M., Derwent, R. G., and Pilling, M.: Development of a reduced speciated VOC degradation mechanism for use in ozone models, Atmos. Environ., 36, 4725–4737, 2002.
Jobson, B. T., Niki, H., Yokouchi, Y., Bottenheim, J., Hopper, F., and Leaitch, R.: Measurements of C<sub>2</sub>-C$_6$ hydrocarbons during the polar sunrise (1992) experiment. Evidence for Cl atom and Br atom chemistry, J. Geophys. Res., 99, 25 355–25 368, 1994.
Kanakidou, M., Bonsang, B., and Lambert, G.: Light hydrocarbons vertical profiles and fluxes in a French rural area, Atmos. Environ., 23, 921–927, 1989.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J.P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E.G., and Wilson, J.: Organic aerosol and global climate modelling: A review, Atmos. Chem. Phys., 5, 1053–1123, 2005.
Kocak, M., Kubilay, N., and Mihalopoulos, N.: Ionic composition of lower tropospheric aerosols at a northeastern Mediterranean site: Implications regarding sources and long-range transport, Atmos. Environ., 38, 2067–2077, 2004.
Kouvarakis, G., Tsigaridis, K., Kanakidou M., and Mihalopoulos, N.: Temporal variations of surface regional background ozone over Crete island in the southeast Mediterranean, J. Geophys. Res., 105, 4399–4407, 2000.
Kouvarakis, G., Doukelis, Y., Mihalopoulos, N., Rapsomanakis, S., Sciare, J., and Blumthaler, M.: Chemical, physical, and optical characterization of aerosols during PAUR II experiment, J. Geophys. Res., 107, 8141, doi:10.1029/2000JD000291, 2002.
Kouyoumdjian, H. and Saliba, N. A.: Mass concentration and ion composition of coarse and fine particles in an urban area in Beirut: effect of calcium carbonate on the absorption of nitric and sulfuric acids and the depletion of chloride, Atmos. Chem. Phys., 6, 1865–1877, 2006.
Lelieveld, J., Berresheim, H., Borrmann, S., Crutzen, P. J., Dentener, F. J., Fischer, H., Feichter, J., Flatau, P. J., Heland, J., Holzinger, R., Korrmann, R., Lawrence, M. G., Levin, Z., Markowicz, K. M., Mihalopoulos N., Minikin, A., Ramanathan, V., De Reus, M., Roelofs, G. J., Scheeren, H. A., Sciare, J., Schlager, H., Schultz, M., Siegmund, P., Steil, B., Stephanou, E. G., Stier, P., Traub, M., Warneke, C., Williams, J., and Ziereis, H.: Global air pollution crossroads over the Mediterranean, Science, 298, 794–799, 2002.
Liakakou, E., Vrekoussis, M., Bonsang, B., Donousis, Ch., Kanakidou, M., and Mihalopoulos, N.: Isoprene above the Eastern Mediterranean: Seasonal variation and contribution to the oxidation capacity of the atmosphere, Atmos. Environ., 41, 1002–1010, 2007.
Liakakou, E.: Factors controlling the variability of NMHC$_S$ above the Eastern Mediterranean, PhD Thesis, University of Crete, 2007.
Logan, J.A., Prather, M. J., Wofsy, S. C., and McElroy M. B.: Tropospheric chemistry: A global perspective, J. Geophys. Res., 86, 7210–7254, 1981.
Metzger, S., Mihalopoulos, N., and Lelieveld, J.: Importance of mineral cations and organics in gas-aerosol partitioning of reactive nitrogen compounds: case study based on MINOS results, Atmos. Chem. Phys., 6, 2549–2567, 2006.
Mihalopoulos, N., Stephanou, E., Kanakidou, M., Pilitsidis, S., and Bousquet, P.: Tropospheric aerosol ionic composition in the eastern Mediterranean region, Tellus, 49B, 314–326, 1997.
Moschonas, N. and Glavas, S.: Non-methane hydrocarbons at a high-altitude rural site in the Mediterranean (Greece), Atmos. Environ., 34, 973–984, 2000.
Poisson, N., Kanakidou, M., Bonsang, B., Behmann, T., Burrows, J. P., Fischer, H., Golz, C., Harder, H., Lewis, A., Moortgat, G. K., Nunes, T., Pio, C. A., Platt, U., Sauer, F., Schuster, G., Seakins, P., Senzig, J., Seuwen, R., Trapp, D., Volz-Thomas, A., Zenker, T., and Zitzelberger, R.: The impact of natural non-methane hydrocarbon oxidation on the free radical and ozone budgets above a eucalyptus forest, Chemosphere – Global Change Science, 3, 353–366, 2001.
Putaud, J. P., Raes, F., Van Dingenen, R., Bruggemann, E., Facchini, M. C., Decesari, F., Fuzzi, S., Gehrig, R., Uglin, C. H., Laj, P., Lorbeer, G., Maenhaut, W., Mihalopoulos, N., Muller, K., Rodriguez, S. Q. S., Schneider, J., Spindler, G., ten Brink, H., Torseth, K., and Wiedensohler, A.: A European aerosol phenomenology. 2: chemical characteristics of particulate matter at kerbside, urban, rural and background sites in Europe, Atmos. Environ., 38, 2579–2595, 2004.
Pszenny, A. A. P., Maldanova, H., Keene, W. C., Sander, R., Maben, J. R., Martinez, M., Crutzen, P.J., Perner, D., and Prinn, R. G.: Halogen cycling and aerosol pH in the Hawaiian boundary layer, Atmos. Chem. Phys., 6, 2549–2567, 2006.
Ramacher, B, Rudolph, J., and Koppmann, R.: Hydrocarbon measurements during tropospheric ozone depletion events, Evidence for halogen atom chemistry, J. Geophys. Res., 104, 3633–3653, 1999.
Read, K. A., Lewis, A. C., Salmon, R. A., Jones, A., and Bauguitte, S.: OH and halogen atom influence on the variability of non-methane hydrocarbons in the Antarctic Boundary Layer, Tellus, 22–38, 59, 2007.
Rudolph, J., Koppmann, R., and Plass-Dulmer, C.: The budgets of ethane and tetrachloroethene: Is there evidence for an impact of reactions with chlorine atoms in the troposphere?, Atmos. Environ., 30, 1887–1894, 1996.
Rudolph, J., Ramacher, B., Plass-Dulmer, C., Muller, K. P., and Koppmann, R.: The indirect determination of chlorine atom concentration in the troposphere from changes in the patterns of non-methane hydrocarbons, Tellus, 49, 592–601, 1997.
Sander, R. and Crutzen, P. J.: Model study indicating halogen activation and ozone destruction in polluted air masses transported to the sea, J. Geophys. Res., 101, 9121–9138, 1996.
Singh, H. B., Gregory, G. L., Anderson, B., Browell, E., Sachse, G. W., Davis, D. D., Crawford, J., Bradshaw, J. D., Talbot, R., Blake, D.R., Thornton, D., Newell, R., and Merill, J.: Low ozone in the marine boundary layer of the tropical Pacific ocean: Photochemical loss, chlorine atoms, and entrainment, J. Geophys. Res., 101, 1907–1917, 1996.
Tsigaridis, K. and Kanakidou, M.: Importance of volatile organic compounds photochemistry over a forested area in central Greece, Atmos. Environ., 36, 3137–3146, 2002.
Vogt, R., Crutzen, P. J., and Sander, R.: A mechanism for halogen release from sea-salt aerosol in the remote marine boundary layer, Nature, 383, 327–330, 1996.
Vrekoussis, M., Kanakidou, M., Mihalopoulos, N., Crutzen, P. J., Perner, D., Berresheim, H., and Baboukas, E.: Role of NO<sub>3</sub> radicals in oxidation processes in the eastern Mediterranean troposphere during the MINOS campaign, Atmos. Chem. Phys., 4, 169–182, 2004.
Vrekousis, M., Liakakou, E., Mihalopoulos, N., Kanakidou, M., Crutzen, P.J., and Lelieveld, J.: Formation of HNO<sub>3</sub> and NO$_3^-$ in the anthropogenically-influenced eastern Mediterranean marine boundary layer, Geophys. Res. Lett.,~33,~L05811, doi:10.1029/2005GL025069, 2006.
Wingenter, O. W., Kubo, M. K., Blake, N. J., Smith, T. W., Blake, D. R., and Rowland, F. S.: Hydrocarbon and halocarbon measurements as photochemical and dynamical indicators of atmospheric hydroxyl, atomic chlorine, and vertical mixing obtained during Lagrangian flights, J. Geophys. Res., 101, 4331–4340, 1996.