Skip to main content
Log in

The photochemical generation of hydrogen peroxide in natural waters

  • Published:
Archives of Environmental Contamination and Toxicology Aims and scope Submit manuscript

Abstract

The photochemical formation of hydrogen peroxide in tryptophan solutions and natural waters was monitored by a sensitive spectrophotometric assay. Peroxide was characterized by ion exchange properties and mobility via thin-layer chromatography. Tryptophan photodecomposed in sunlight or near ultraviolet light (λ > 283 nm) with the formation of uncharacterized, acidic photoproducts and hydrogen peroxide; other oxidants (i.e. organic peroxides) were not detected in tryptophan photolysis mixtures. After brief exposure to sunlight, hydrogen peroxide in natural waters varied from below the detection limit (1.5μM) to 6.8μM; in highly eutrophic samples peroxide was formed in excess of 30μM. A humic acid soil extract, tyrosine, and several aromatic compounds including substituted phenols and anilines also generated stable photochemical oxidants suggesting that many compounds may serve as sources for hydrogen peroxide in natural waters.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Asquith, R. S., and D. E. Rivett: Studies on the photooxidation of tryptophan. Biochim. Biophys. Acta252, 111 (1971).

    Google Scholar 

  • Beer, R. J. S., T. Donavanik, and A. Robertson: Peroxides of tetrahydrocarbazole and related compounds. Part VI. Some indoleninyl hydroperoxides. J. Chem. Soc. 4139 (1954).

  • Bent, D. V., and E. Hayon: Excited state chemistry of aromatic amino acids and related peptides. III. Tryptophan. J. Am. Chem. Soc.97, 2612 (1975).

    Google Scholar 

  • Bonneau, R., R. Pottier, O. Bagno, and J. Joussot-Dubien: pH dependence of singlet oxygen production in aqueous solutions using thiazine dyes as photosensitizers. Photochem. Photobiol.21, 159 (1975).

    Google Scholar 

  • Crosby, D. G.: Experimental approaches to pesticide photo-decomposition. Residue Reviews25, 1 (1969).

    Google Scholar 

  • Draper, W. M., and D. G. Crosby: Hydrogen peroxide and hydroxyl radical: Intermediates in indirect photolysis reactions in water. J. Agric. Food Chem.29, 699 (1981a).

    Google Scholar 

  • —: Sensitive, enzyme-catalyzed, chromogenic reagent for hydrogen peroxide and other peroxygen compounds on TLC plates. J. Chromatogr.216, 413 (1981b).

    Google Scholar 

  • Draper, W. M., D. G. Crosby, and J. B. Bowers: Measurement of photochemical oxidants in agricultural field water. Proceedings of the 172nd National Meeting of the American Chemical Society, San Francisco, CA (1976).

  • Gjessing, E. T.: Humic substances in natural water: Methods for separation and characterization, In H. L. Golterman and R. S. Clymo (eds.): Chemical environment in the aquatic habitat. Amsterdam: Noord-Hollandsch Uitgevers Maatschappij (1967).

    Google Scholar 

  • Grossweiner, L. I., and H. Joschek: Optical generation of hydrated electrons from aromatic compounds, In R. F. Gould (ed.): Solvated electron. Washington, DC: American Chemical Society (1965).

    Google Scholar 

  • Hart, E. J., and M. Anbar: The hydrated electron. New York: Wiley-Interscience (1970).

    Google Scholar 

  • Larson, R. A., K. Smykowski, and L. L. Hunt: Occurrence and determination of organic oxidants in rivers and wastewaters. Chemosphere10, 1335 (1981).

    Google Scholar 

  • McCormick, J. P., J. R. Fischer, J. P. Pachlatko, and A. Eisenstark: Characterization of a cell-lethal product from the photooxidation of tryptophan; hydrogen peroxide. Science191, 468 (1976).

    Google Scholar 

  • McCormick, J. P., and T. Thomason: Near-ultraviolet photooxidation of tryptophan. Proof of formation of superoxide ion. J. Am. Chem. Soc.100, 312 (1978).

    Google Scholar 

  • Mill, T., D. G. Hendry, and H. Richardson: Free-radical oxidants in natural waters. Science207, 886 (1980).

    Google Scholar 

  • Mottola, H., B. Simpson, and G. Gorin: Absorptiometric determination of hydrogen peroxide in submicrogram amounts with leuco crystal violet and peroxidase as catalyst. Anal. Chem.42, 410 (1970).

    Google Scholar 

  • Richardson, A., and E. Fortey: Action of light on amyl alcohol. J. Chem. Soc.69, 1349 (1896).

    Google Scholar 

  • Ross, R., and D. G. Crosby: Characterization of photosensitizers in agricultural water. Proceedings of the 167th National Meeting of the American Chemical Society, Philadelphia, PA (1975).

  • Schnitzer, M., and S. U. Khan: Humic substances in the environment. New York: Marcel Dekker (1972).

    Google Scholar 

  • Sinel'nikov, V. E.: Hydrogen peroxide level in river water, and methods for detecting it. Gidrobiol. Zh.7, 1 (1971a).

    Google Scholar 

  • —: Experimental study of separate stages in the mechanism of oxidation of organic matter in waters by a chemiluminescent method. Akad. Nauk.20, 159 (1971b).

    Google Scholar 

  • Soderquist, C. J., J. B. Bowers, and D. G. Crosby: The dissipation of molinate in a rice field. J. Agric. Food. Chem.25, 940 (1977).

    Google Scholar 

  • Van Baalen, C. and J. E. Marler: Occurrence of hydrogen peroxide in sea water. Nature211, 951 (1966).

    Google Scholar 

  • Witkop, B., and J. B. Patrick: On the mechanism of oxidation. 1. A new type of peroxide rearrangement catalyzed by acid. J. Am. Chem. Soc.73, 713 (1951).

    Google Scholar 

  • Zepp, R. G., N. L. Wolfe, G. L. Baughman, and R. C. Hollis: Singlet oxygen in natural waters. Nature207, 421 (1977).

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Draper, W.M., Crosby, D.G. The photochemical generation of hydrogen peroxide in natural waters. Arch. Environ. Contam. Toxicol. 12, 121–126 (1983). https://doi.org/10.1007/BF01055010

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01055010

Keywords

Navigation