Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 6 9 2006 10.5194/acp-6-2423-2006 http://www.atmos-chem-phys.net/6/2423/2006/ http://www.atmos-chem-phys.net/6/2423/2006/acp-6-2423-2006.html http://www.atmos-chem-phys.net/6/2423/2006/acp-6-2423-2006.pdf 2423 2437 2006-06-29 A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 1 – bromide solutions B. M. Matthew C. Anastasio canastasio@ucdavis.edu Atmospheric Science Program, Department of Land, Air & Water Resources, University of California, Davis, USA now at: Hach Company, Loveland, Colorado, USA Reactive halogen species (X*=X•, •X₂^-, X₂ and HOX, where X=Br, Cl, or I) in seawater, sea-salt particles, and snowpacks play important roles in the chemistry of the marine boundary layer. Despite this, relatively little is known about the steady-state concentrations or kinetics of reactive halogens in these environmental samples. In part this is because there are few instruments or techniques that can be used to characterize aqueous reactive halogens. To better understand this chemistry, we have developed a chemical probe technique that can detect and quantify aqueous reactive bromine and chlorine species (Br*(aq) and Cl*(aq)). This technique is based on the reactions of short-lived X*(aq) species with allyl alcohol (CH₂=CHCH₂OH) to form stable 3-halo-1,2-propanediols that are analyzed by gas chromatography. Using this technique in conjunction with competition kinetics allows determination of the steady state concentrations of the aqueous reactive halogens and, in some cases, the rates of formation and lifetimes of X* in aqueous solutions. We report here the results of the method development for aqueous solutions containing only bromide (Br^-). Anastasio, C., Faust, B. C., and Allen, J. M.: Aqueous phase photochemical formation of hydrogen peroxide in authentic cloud waters, J. Geophys. Res., 99, 8231–8248, 1994. Anastasio, C. and Matthew, B. M.: A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 2 – Chloride solutions and mixed bromide/chloride solutions, Atmos. Chem. Phys., 6, 2439–2451, 2006. Anastasio, C. and McGregor, K. G.: Chemistry of fog waters in California's Central Valley: 1. In situ photoformation of hydroxyl radical and singlet molecular oxygen, Atmos. Environ., 35, 1079–1089, 2001. Arakaki, T., Anastasio, C., Shu, P. G., and Faust, B. C.: Aqueous-phase photoproduction of hydrogen peroxide in authentic cloud waters – wavelength dependence, and the effects of filtration and freeze-thaw cycles, Atmos. Environ., 29, 1697–1703, 1995. Arakaki, T. and Faust, B. C.: Sources, sinks, and mechanisms of hydroxyl radical ($^.$OH) photoproduction and consumption in authentic acidic continental cloud waters from Whiteface Mountain, New York: The role of the Fe(r) (r=II,III) photochemical cycle, J. Geophys. Res., 103, 3487–3504, 1998. Barrie, L. A., Bottenheim, J., Schnell, R. C., Crutzen, P. J., and Rasmussen, R. A.: Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere, Nature, 334, 138–141, 1988. Bottenheim, J., Fuentes, J. D., Tarasick, D. W., and Anlauf, K. G.: Ozone in the Arctic lower troposphere during winter and spring 2000 (ALERT2000), Atmos. Environ., 36, 2535–2544, 2002. Braun, W., Herron, J. T., and Kahaner, D. K.: Acuchem: A computer program for modeling complex chemical reaction systems, Int. J. Chem. Kin., 20, 51–62, 1988. Chu, L. and Anastasio, C.: Formation of hydroxyl radical from the photolysis of frozen hydrogen peroxide, J. Phys. Chem. A, 109, 6264–6271, 2005. Ebinghaus, R., Kock, H. H., Temme, C., Einax, J. W., Lowe, A. G., Richter, A., Burrows, J. P., and Schroeder, W. H.: Antarctic springtime depletion of atmospheric mercury, Environ. Sci. Technol., 36, 1238–1244, 2002. Faust, B. C. and Allen, J. M.: Aqueous-phase photochemical formation of hydroxyl radical in authentic cloudwaters and fogwaters, Environ. Sci. Technol., 27, 1221–1224, 1993. Foster, K. L., Plastridge, R. A., Bottenheim, J. W., Shepson, P. B., Finlayson-Pitts, B. J., and Spicer, C. W.: The role of Br$_2$ and BrCl in surface ozone destruction at polar sunrise, Science, 291, 471–474, 2001. Galbally, I. E., Bentley, S. T., and Meyer, C. P.: Mid-latitude marine boundary-layer ozone destruction at visible sunrise observed at Cape Grim, Tasmania, 41 degrees south, Geophys. Res. Lett., 27, 3841–3844, 2000. Gratzel, M. and Halmann, M.: Photosensitized oxidation of bromide in Dead Sea water, Mar. Chem., 29, 169–182, 1990. Hebestreit, K., Stutz, J., Rosen, D., Matveiv, V., Peleg, M., Luria, M., and Platt, U.: DOAS measurements of tropospheric bromine oxide in mid-latitudes, Science, 283, 55–57, 1999. Jobson, B. T., Niki, H., Yokouchi, Y., Bottenheim, J., Hopper, F., and Leaitch, R.: Measurements of C$_2$-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. Keene, W. C. and Savoie, D. L.: Correction to "The pH of deliquesced sea-salt aerosol in polluted marine air" (vol. 26, p. 1315, 1999), Geophys. Res. Lett., 26, 1315–1316, 1999. Lindberg, S. E., Brooks, S., Lin, C. J., Scott, K. J., Landis, M. S., Stevens, R. K., Goodsite, M., and Richter, A.: Dynamic oxidation of gaseous mercury in the Arctic troposphere at polar sunrise, Environ. Sci. Technol., 36, 1245–1256, 2002. March, J.: Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, Wiley, New York, 1992. Matthew, B. M. and Anastasio, C.: Determination of halogenated mono-alcohols and diols in water by gas chromatography with electron-capture detection, J. Chromatogr. A, 866, 65–77, 2000. Matthew, B. M., George, I., and Anastasio, C.: Hydroperoxyl radical (HO$_2)$ oxidizes dibromide radical anion (Br$_2$-) to bromine (Br$_2)$ in aqueous solutions: Implications for the formation of Br$_2$ in the marine boundary layer, Geophys. Res. Lett., 30, 2297–2301, 2003. McConnell, J. C., Henderson, G. S., Barrie, L., Bottenheim, J., Niki, H., Langford, C. H., and Templeton, E. M. J.: Photochemical bromine production implicated in Arctic boundary-layer ozone depletion, Nature, 355, 150–152, 1992. Michalowski, B., Francisco, J. S., Li, S., Barrie, L. A., Bottenheim, J. W., and Shepson, P. B.: A computer model study of multiphase chemistry in the Arctic boundary layer during polar sunrise, J. Geophys. Res., 105, 15 131–15 145, 2000. Miller, W. L. and Kester, D. R.: Hydrogen peroxide measurement in seawater by p-hydroxyphenylacetic acid dimerization, Anal. Chem., 60, 2711–2715, 1988. Moore, R. M. and Zafiriou, O. C.: Photochemical production of methyl-iodide in seawater, J. Geophys. Res.-Atmos., 99, 16 415–16 420, 1994. Nagao, I., Matsumoto, K., and Tanaka, H.: Sunrise ozone destruction found in the sub-tropical marine boundary layer, Geophys. Res. Lett., 26, 3377–3380, 1999. Richter, A., Wittrock, F., Eisinger, M., and Burrows, J. P.: GOME observations of tropospheric BrO in northern hemispheric spring and summer 1997, Geophys. Res. Lett., 25, 2683–2686, 1998. 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. Stutz, J., Ackermann, R., Fast, J. D., and Barrie, L. A.: Atmospheric reactive chlorine and bromine at the Great Salt Lake, Utah, Geophys. Res. Lett., 29, 181–184, 2002. Swanson, A. L., Blake, N. J., Dibb, J. E., Albert, M. R., Blake, D. R., and Rowland, F. S.: Photochemically induced production of CH$_3$Br, CH$_3$I, C$_2$H$_5$I, ethene, and propene within surface snow at Summit, Greenland, Atmos. Environ., 36, 2671–2682, 2002. Vogt, R., Sander, R., and Crutzen, P. J.: A mechanism for halogen release form sea-salt aerosol in the remote marine boundary layer, Nature, 383, 327–330, 1996. von Glasow, R., Sander, R., Bott, A., and Crutzen, P.: Modeling halogen chemistry in the marine boundary layer. 1. Cloud-free MBL, J. Geophys. Res., 107, 4341, doi:10.109/2001JD000942, 2002a. von Glasow, R., Sander, R., Bott, A., and Crutzen, P.: Modeling halogen chemistry in the marine boundary layer: 2. Interactions with sulfur and cloud-covered MBL, J. Geophys. Res., 107, 4323, doi:10.1029/2001JD000943, 2002b. Zafiriou, O. C., True, M. B., and Hayon, E.: Consequences of OH radical reaction in sea water: Formation and decay of Br$_2^-$ ion radical, in: Photochemistry of Environmental Aquatic Systems, edited by: Zika, R. G. and Cooper, W. J., American Chemical Society, Washington D.C., 89–105, 1987. Zepp, R. G., Faust, B. C., and Hoigné, J.: Hydroxyl radical formation in aqueous reactions (pH 3–8) of Iron(II) with hydrogen peroxide: The photo-Fenton reaction, Environ. Sci. Technol., 26, 313–319, 1992. Zhou, X. and Mopper, K.: Determination of photochemically produced hydroxyl radicals in seawater and freshwater, Mar. Chem., 30, 71–88, 1990.