References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-9-17125-2009

Coastal measurements of short-lived reactive iodocarbons and bromocarbons at Roscoff, Brittany during the RHaMBLe campaign

Jones

C. E.

¹ Hornsby

K. E.

¹ Dunk

R. M.

¹ ³ Leigh

R. J.

² Carpenter

L. J.

Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK

Department of Physics and Astronomy, University of Leicester, Leicester, LE1 7RH, UK

now at: Crichton Carbon Centre, Crichton University Campus, Dumfries, DG1 4ZL, UK

14 08 2009

9 4 17125 17155

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.

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Atmospheric concentrations of the volatile reactive iodocarbons C2H5I, 1-C3H7I, 2-C3H7I, CH2ICl, CH2IBr, CH2I2 and bromocarbons CH2Br2 and CHBr3 were determined by GC/MS analysis of marine boundary layer air at Roscoff, Brittany on the northwest coast of France during September 2006. Comparison with other coastal studies suggests that emissions of these trace gases are strongly influenced by site topography, seaweed populations and distribution, as well as tide height. Concentrations of the very short-lived dihalomethanes CH2IBr and CH2I2 in particular showed evidence of tidal dependence, with higher concentrations observed at low tide during maximum exposure of seaweed beds. We also present a limited number of halocarbon concentrations in surface seawater and estimate sea-air fluxes based on simultaneous water and air measurements of these gases. CH2Br2 and CHBr3 were strongly correlated both in air and in seawater, with CH2Br2/CHBr3 ratios of 0.19 in air and 0.06 in water. The combined midday I atom flux from the photolabile diahlomethanes CH2I2, CH2IBr and CH2ICl of ~5×103 molecules cm−3 s−1 is several orders of magnitude lower than the estimated I atom flux from I2 based on coinciding measurements at the same site, which indicates that at Roscoff the major I atom precursor was I2 rather than reactive iodocarbons.

References 1

Barnes, B.: Coast and shore, a nature guide. The Crowood Press, Marlborough, UK, 1986.

Bilde, M., Wallington, T. J., Ferronato, C., Orlando, J. J., Tyndall, G. S., Estupinan, E., and Haberkorn, S.: Atmospheric chemistry of CH2BrCl, CHBrCl2, CHBr2Cl, CF3CHBrCl, and CBr2Cl2, J. Phys. Chem. A, 102, 1976–1986, 1998.

Bloss, W. J., Lee, J. D., Johnson, G. P., Sommariva, R., Heard, D. E., Saiz-Lopez, A., Plane, J. M. C., McFiggans, G., Coe, H., Flynn, M., Williams, P., Rickard, A. R., and Fleming, Z. L.: Impact of halogen monoxide chemistry upon boundary layer OH and HO2 concentrations at a coastal site, Geophys. Res. Lett., 32(6), L06814, doi:10.1029/2004GL022084, 2005.

Butler, J. H., King, D. B., Lobert, J. M., Montzka, S. A., Yvon-Lewis, S. A., Hall, B. D., Warwick, N. J., Mondeel, D. J., Aydin, M., and Elkins, J. W.: Oceanic distributions and emissions of short-lived halocarbons, Global Biogeochem. Cy., 21(1), GB1023, doi:10.1029/2006GB002732, 2007.

Carpenter, L. J., Sturges, W. T., Penkett, S. A., Liss, P. S., Alicke, B., Hebestreit, K., and Platt, U.: Short-lived alkyl iodides and bromides at Mace Head, Ireland: Links to biogenic sources and halogen oxide production, J. Geophys. Res.-Atmos., 104, 1679–1689, 1999.

Carpenter, L. J., Malin, G., Liss, P. S., and Kupper, F. C.: Novel biogenic iodine-containing trihalomethanes and other short-lived halocarbons in the coastal East Atlantic, Global Biogeochem. Cy., 14(4), 1191–1204, 2000.

Carpenter, L. J. and Liss, P. S.: On temperate sources of bromoform and other reactive organic bromine gases, J. Geophys. Res.-Atmos., 105(D16), 20539–20547, 2000.

Carpenter, L. J., Liss, P. S., and Penkett, S. A.: Marine organohalogens in the atmosphere over the Atlantic and Southern Oceans, J. Geophys. Res.-Atmos., 108(D9), 4256, doi:10.1029/2002JD002769, 2003.

Carpenter, L. J.: Iodine in the Marine Boundary Layer, Chem. Rev., 103(12), 4953–4962, 2003.

Carpenter, L. J., Jones, C. E., Dunk, R. M., Hornsby, K. E., and Woeltjen, J.: Air-sea fluxes of biogenic bromine from the tropical and North Atlantic Ocean, Atmos. Chem. Phys., 9, 1805–1816, 2009.

Hornsby, K. E., Flynn, M. J., Dorsey, J. R., Gallagher, M. W., Chance, R., Jones, C. E., and Carpenter, L. J.: A Relaxed Eddy Accumulation (REA)-GC/MS system for the determination of halocarbon fluxes, Atmos. Meas. Tech. Discuss., 2, 951–980, 2009.

Jones, C. E. and Carpenter, L. J.: Solar photolysis of CH2I2, CH2ICI, and CH2IBr in water, saltwater, and seawater, Environ. Sci. Technol., 39(16), 6130–6137, doi:10.1021/es050563g, 2005.

Khalil, M. A. and Rasmussen, R. A.: Atmospheric chloroform, Atmos. Environ., 33(7), 1151–1158, 1999.

Klick, S.: Seasonal variations of biogenic and anthropogenic halocarbons in seawater from a coastal site, Limnol. Oceanogr., 37(7), 1579–1585, 1992.

Küpper, F. C., Schweigert, N., Gall, E. A., Legendre, J. M., Vilter, H., and Kloareg, B: Iodine uptake in Laminariales involves extracellular, haloperoxidase-mediated oxidation of iodide, Planta, 207(2), 163–171, 1998.

Küpper, F. C., Carpenter, L. J., McFiggans, G. B., Palmer, C. J., Waite, T. J., Boneberg, E. M., Woitsch, S., Weiller, M., Abela, R., Grolimund, D., Potin, P., Butler, A., Luther, G. W., Kroneck, P. M. H., Meyer-Klaucke, W., and Feiters, M. C.: Iodide accumulation provides kelp with an inorganic antioxidant impacting atmospheric chemistry, P. Natl. Acad. Sci. USA, 105(19), 6954–6958, doi:10.1073/pnas.0709959105, 2008.

Laturnus, F.: Volatile halocarbons released from Arctic macroalgae, Mar. Chem., 55, 359–366, 1996.

Mahajan, A. S., Oetjen, H., Saiz-Lopez, A., Lee, J. D., McFiggans, G. B., and Plane, J. M. C.: Reactive iodine species in a semi-polluted environment, Geophys. Res. Lett., doi:2009GL038018, in press, 2009.

Martino, M., Liss, P. S., and Plane, J. M. C.: The photolysis of dihalomethanes in surface seawater, Environ. Sci. Technol., 39(18), 7097–7101, doi:10.1021/es058022e, 2005.

McFiggans, G., Coe, H., Burgess, R., Allan, J., Cubison, M., Alfarra, M. R., Saunders, R., Saiz-Lopez, A., Plane, J. M. C., Wevill, D., Carpenter, L., Rickard, A. R., and Monks, P. S.: Direct evidence for coastal iodine particles from Laminaria macroalgae – linkage to emissions of molecular iodine, Atmos. Chem. Phys., 4, 701–713, 2004.

McFiggans, G., Flynn, M., Gallagher, M., Longley, I., Whitehead, J., Furneaux, K., Heard, D. E., Mahajan, A., Oetjen, H., Plane, J. M. C., Whalley, L., Ball, S. M., Hollingsworth, A., Kramer, L., Leigh, R., Monks, P. S., Carpenter, L. J., Dunk, R. M., Hornsby, K. E., Jones, C. E., Lee, J. D., Benton, A., Jones, R. L., Langridge, J., Shillings, A., Potin, P., Leblanc, C., Beams, J., Orr-Ewing, A., and Wada, R.: Reactive Halogens in the Marine Boundary Layer (RHaMBLe): overview of measurements in the Roscoff coastal study, in preparation, 2009.

Moore, R. M., Geen, C. E., and Tait, V. K.: Determination of Henry law constants for a suite of naturally-occurring halogenated methanes in seawater, Chemosphere, 30(6), 1183–1191, 1995.

Moore, R. M. and Groszko, W.: Methyl iodide distribution in the ocean and fluxes to the atmosphere, J. Geophys. Res., 104, 11163–11171, 1999.

Nielsen, J. E. and Douglass, A. R.: Simulation of bromoform's contribution to stratospheric bromine, J. Geophys. Res.-Atmos., 106(D8), 8089–8100, 2001.

Nightingale, P. D., Malin, G., Law, C. S., Watson, A. J., Liss, P. S., Liddicoat, M. I., Boutin, J., and Upstill-Goddard, R. C.: In situ evaluation of air-sea gas exchange parameterizations using novel conservative and volatile tracers, Global Biogeochem. Cy., 14(1), 373–387, 2000.

Palmer, C. J., Anders, T. L., Carpenter, L. J., Kupper, F. C., and McFiggans, G. B.: Iodine and halocarbon response of Laminaria digitata to oxidative stress and links to atmospheric new particle production, Environ. Chem., 2(4), 282–290, doi:10.1071/EN05078, 2005.

Pedersen, M., Collen, J., Abrahamsson, K., and Ekdahl, A.: Production of halocarbons from seaweeds: An oxidative stress reaction?, Sci. Mar., 60, 257–263, 1996.

Peters, C., Pechtl, S., Stutz, J., Hebestreit, K., Hönninger, G., Heumann, K. G., Schwarz, A., Winterlik, J., and Platt, U.: Reactive and organic halogen species in three different European coastal environments, Atmos. Chem. Phys., 5, 3357–3375, 2005.

Pfeilsticker, K., Sturges, W. T., Bosch, H., Camy-Peyret, C., Chipperfield, M. P., Engel, A., Fitzenberger, R., Muller, M., Payan, S., and Sinnhuber, B. M.: Lower stratospheric organic and inorganic bromine budget for the Arctic winter 1998/99, Geophys. Res. Lett., 27(20), 3305–3308, 2000.

Pirjola, L., O'Dowd, C. D., and Kumala, M.: A model prediction of the yield of cloud condensation nuclei from coastal nucleation events, J. Geophys. Res.-Atmos., 107(D15), 8098, doi:10.1029/2000JD000213, 2002.

Pirjola, L., O'Dowd, C. D., Yoon, Y. J., and Sellegri, K.: Modelling iodine particle formation and growth from seaweed in a chamber, Environ. Chem., 2(4), 271–281, doi:10.1071/EN05075, 2005.

Quack, B. and Wallace, D. W. R.: Air-sea flux of bromoform: Controls, rates, and implications, Global Biogeochem. Cy., 7(1), 1023, doi:10.1029/2002GB001890, 2003.

Read, K. A., Mahajan, A. S., Carpenter, L. J., Evans, M. J., Faria, B. V. E., Heard, D. E., Hopkins, J. R., Lee, J. D., Moller, S. J., Lewis, A. C., Mendes, L., McQuaid, J. B., Oetjen, H., Saiz-Lopez, A., Pilling, M. J., and Plane, J. M. C.: Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean, Nature, 453, 7199, 1232–1235, doi:10.1038/nature07035, 2008.

Saiz-Lopez, A. and Plane, J. M. C.: Novel iodine chemistry in the marine boundary layer, Geophys. Res. Lett., 31(4), L04112, doi:10.1029/2003GL019215, 2004.

Saiz-Lopez, A., Shillito, J. A., Coe, H., and Plane, J. M. C.: Measurements and modelling of I2, IO, OIO, BrO and NO3 in the mid-latitude marine boundary layer, Atmos. Chem. Phys., 6, 1513–1528, 2006.

Schall, C. and Heumann, K. G.: GC determination of volatile organoiodine and organobromine compounds in Arctic seawater and air samples, Fresenius, J. Anal. Chem., 346, 717–722, 1993.

Sturges, W. T., Oram, D. E., Carpenter, L. J., Penkett, S. A., and Engel, A.: Bromoform as a source of stratospheric bromine, Geophys. Res. Lett., 27(14), 2081–2084, 2000.

Theiler, R., Cook, J. C., Hager, L. P., and Siuda, J. F.: Halohydrocarbon synthesis by bromoperoxidase, Science, 202, 1094–1096, 1978.

Wever, R., Tromp, M. G. M., Krenn, B. E., Marjani, A., and Van Tol, M.: Brominating activity of the seaweed Ascophyllum nodosum: Impact on the biosphere, Environ. Sci. Technol., 25(3), 446–449, 1991.

Wevill, D. J. and Carpenter, L. J.: Automated measurement and calibration of reactive volatile halogenated organic compounds in the atmosphere, The Analyst, 129(7), 634–638, doi:10.1039/b403550j, 2004.

Wuosmaa, A. M. and Hager, L. P.: Methyl chloride transferase: A carbocation route for biosynthesis of halometabolites, Science, 249, 160–162, 1990.

Vogt, R., Sander, R., von Glasow, R., and Crutzen, P. J.: Iodine chemistry and its role in halogen activation and ozone loss in the marine boundary layer: A model study, J. Atmos. Chem., 32(3), 375–395, 1999.

Yonge, C. M.: The Sea Shore, The Fontana New Naturalist, Collins, London/Glasgow, UK, 1949.

Zhang, D. Q., Zhong, J. X., and Qiu, L. X.: Kinetics of the reaction of hydroxyl radicals with CH2Br2 and its implications in the atmosphere, J. Atmos. Chem., 27, 209–215, 1997.

Zhou, Y., Mao, H., Russo, R. S., Blake, D. R., Wingenter, O. W., Haase, K. B., Ambrose, J., Varner, R. K., Talbot, R., and Sive, B. C.: Bromoform and dibromomethane measurements in the seacoast region of New Hampshire 2002–2004, J. Geophys. Res., 113, D08305, doi:10.1029/2007JD009103, 2008.