Environmental Chemistry Letters

, Volume 9, Issue 3, pp 447–451 | Cite as

Photoreactivity of humic substances: relationship between fluorescence and singlet oxygen production

  • Christian Coelho
  • Ghislain Guyot
  • Alexandra ter Halle
  • Luciano Cavani
  • Claudio Ciavatta
  • Claire Richard
Original Paper

Abstract

Humic substances are natural compounds abundantly present in the environment. They play a significant role in the natural attenuation of pollution in surface water due to their capacity to generate reactive species upon solar light excitation. Finding physico chemical parameters related to this property would be of a great help in the prediction studies of the organic pollutants fate. In this work, we investigated relationships between the ability of the humic substances to produce singlet oxygen and their fluorescence properties. For this, a series of sixteen humic acids, fulvic acids, and water-extractable organic matter from soils were studied. The steady-state singlet oxygen concentrations in the irradiated humic substances solutions were measured by monitoring the loss of furfuryl alcohol added as a singlet oxygen scavenger. The emission spectra of the sixteen samples were also recorded. Values of the steady-state singlet oxygen concentrations and the emission intensities showed significant variations among the humic samples and a parallel increase. Thus, here we demonstrate that the rate of singlet oxygen production and the emission intensity of the humic samples are correlated, the best correlation being obtained for emission wavelengths between 500 and 580 nm. This correlation which was never reported until now can be used to estimate the singlet oxygen-production capacity of the humic substances based on their fluorescent properties.

Keywords

Correlation Humic acids Fulvic acids Irradiation Fluorescence Singlet oxygen 

References

  1. Al Housari F, Vione D, Chiron S, Barbati S (2010) Reactive photoinduced species in estuarine waters. Characterization of hydroxyl radical, singlet oxygen and dissolved organic matter triplet state in natural oxidation processes. Photochem Photobiol Sci 9:78–86CrossRefGoogle Scholar
  2. Boyle ES, Guerriero N, Thiallet A, Del Vecchio R, Blough NV (2009) Optical properties of humic substances and CDOM: relation to structure. Environ Sci Technol 43:2262–2268CrossRefGoogle Scholar
  3. Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms, and hydroxyl radicals in aqueous solution. J Phys Chem Ref Data 17:513–886Google Scholar
  4. Cavani L, Halladja S, Ter Halle A, Guyot G, Corrado G, Ciavatta C, Boulkamh A, Richard C (2009) Relationship between photosensitizing and emission properties of peat humic acid fractions obtained by tangential ultrafiltration. Environ Sci Technol 43:4348–4354CrossRefGoogle Scholar
  5. Cory RM, Cotner JB, McNeill K (2009) Quantifying interactions between singlet oxygen and aquatic fulvic acids. Environ Sci Technol 43:718–723CrossRefGoogle Scholar
  6. Frimmel FH, Bauer H, Putzien J, Murasecco P, Braun AM (1987) Laser flash photolysis of dissolved aquatic humic material and the sensitized production of singlet oxygen. Environ Sci Technol 21:541–545CrossRefGoogle Scholar
  7. Haag WR, Hoigné J (1986) Singlet oxygen in surface waters. 3. Photochemical formation and steady-state concentrations in various types of waters. Environ Sci Technol 20:341–348CrossRefGoogle Scholar
  8. Halladja S, Ter Halle A, Aguer JP, Boulkamh A, Richard C (2007) Inhibition of humic substances mediated photooxygenation of furfuryl alcohol by 2, 4, 6-trimethylphenol. Evidence for reactivity of the phenol with humic triplet excited states. Environ Sci Technol 41:6066–6073CrossRefGoogle Scholar
  9. Hessler DP, Frimmel FH, Oliveros E, Braun AM (1996) Quenching of singlet oxygen by humic substances. J Photochem Photobiol B Biol 36:55–60CrossRefGoogle Scholar
  10. Latch DE, McNeill K (2006) Microheterogeneity of singlet oxygen distributions in irradiated humic acid solutions. Science 311:1743–1747CrossRefGoogle Scholar
  11. Paul A, Hackbarth S, Vogt RD, Räder B, Burnison BK, Steinberg CEW (2004) Photogeneration of singlet oxygen by humic substances: Comparison of humic substances of aquatic and terrestrial origin. Photochem Photobiol Sci 3:273–280CrossRefGoogle Scholar
  12. Rodgers MAJ, Snowden PT (1982) Lifetime of O2(1Δg) in liquid water as determined by time-resolved infrared luminescence measurements. J Am Chem Soc 104:5541–5543CrossRefGoogle Scholar
  13. Senesi N, Miano TM, Provenzano MR, Brunetti G (1991) Characterization, differentiation, and classification of humic substances by fluorescence spectroscopy. Soil Sci 152:259–271CrossRefGoogle Scholar
  14. Stevenson FJ (1994) Humus chemistry, 2nd edn. Wiley, New YorkGoogle Scholar
  15. Trubetskaya O, Trubetskoj O, Guyot G, Andreux F, Richard C (2002) Fluorescence of soil humic acids and their fractions obtained by tandem size exclusion chromatography-polyacrylamide gel electrophoresis. Org Geochem 33:213–220CrossRefGoogle Scholar
  16. Zepp RG, Schlotzhauer PF, Sink RM (1985) Photosensitized transformations involving electronic energy transfer in natural waters: Role of humic substances. Environ Sci Technol 19:74–81CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Christian Coelho
    • 1
  • Ghislain Guyot
    • 1
  • Alexandra ter Halle
    • 1
    • 2
  • Luciano Cavani
    • 3
  • Claudio Ciavatta
    • 3
  • Claire Richard
    • 1
    • 2
  1. 1.Laboratoire de Photochimie Moléculaire et Macromoléculaire (LPMM)Clermont Université, Université Blaise PascalClermont-FerrandFrance
  2. 2.UMR 6505, LPMMCNRSAubièreFrance
  3. 3.Dipartimento di Scienze e Tecnologie AgroambientaliAlma Mater Studiorum-Università di BolognaBolognaItaly

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