References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-6-2439-2006

A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 2 – chloride solutions and mixed bromide/chloride solutions

Anastasio

¹ Matthew

B. M.

¹ ²

Atmospheric Science Program, Department of Land, Air & Water Resources, University of California, Davis, USA

now at: Hach Company, Loveland, Colorado, USA

29 06 2006

6 9 2439 2451

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.

This article is available from http://www.atmos-chem-phys.net/6/2439/2006/acp-6-2439-2006.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/6/2439/2006/acp-6-2439-2006.pdf

Although reactive halogen species (X*=X•, •X2-, X2 and HOX, where X=Br, Cl, or I) are important environmental oxidants, relatively little is known about their kinetics in condensed phases such as seawater and sea-salt particles. Here we describe a new technique to determine reactive chlorine and bromine species in aqueous solutions by using allyl alcohol (CH2=CHCH2OH) as a chemical probe. This probe is combined with competition kinetics in order to determine steady state concentrations of X*(aq). In some cases the technique also can be used to determine the rates of formation and lifetimes of X* in aqueous solution. In a companion paper we reported the results of our method development for aqueous solutions containing only bromide (Br-). In this paper, we discuss method development for solutions containing chloride (Cl-) alone, and for solutions containing both bromide and chloride.

References 1

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.

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.

Donati, A.: Spectroscopic and kinetic investigations of halogen-containing radicals in the tropospheric aqueous phase, Ph.D. Dissertation, University of Leipzig, 2002.

Ershov, B. G.: Kinetics, mechanism and intermediates of some radiation-induced reactions in aqueous solutions, Russian Chem. Rev., 73, 101–113, 2004.

Matthew, B. M.: Chemical probe technique for the detection of oxidized halogen species in aqueous solution, Ph.D. Dissertation, University of California – Davis, 2002.

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. and Anastasio, C.: A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 1 – Bromide solutions, Atmos. Chem. Phys., 6, 2423–2437, 2006.

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.

Newberg, J. T.: Measurements of inorganic ion composition, UV-visible absorption and hydroxyl radical kinetics in marine particles from the northeasetrn Pacific Ocean, M. S. Thesis, University of California – Davis, 2003.

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.

Zhou, X. and Mopper, K.: Determination of photochemically produced hydroxyl radicals in seawater and freshwater, Mar. Chem., 30, 71–88, 1990.