Skip to main content
Log in

Assessing redox properties of standard humic substances

  • Original Paper
  • Published:
International Journal of Environmental Science and Technology Aims and scope Submit manuscript

Abstract

Redox properties of humic substances (HS) control important biogeochemical processes. Thus, accurate estimation of redox properties of HS is essential. However, there is no general consensus regarding the best available measurement method of HS redox properties. In this study, we compared several common HS redox property measurement methods using anthraquinone-2,6-disulfonate (AQDS) as model compound, and standard Elliot soil humic acid (1S102H, ESHA), reference Pahokee peat (1R103H, PPHA), and Suwannee River natural organic matter (1R101N, SRNOM) as representative HS. We found that the H2/Pd reduction method followed by incubation with ferric citrate (FeCit) reagent was incomplete, and the H2/Pd reduction method followed by incubation with potassium ferricyanide (K3Fe(CN)6) was insensitive. Stannous chloride (SnCl2) reduction followed by titration of excess stannous (Sn2+) by potassium dichromate (K2Cr2O7) was found to be most accurate. These findings will help in future investigations on detailed characterizations of functional groups of HS responsible for oxidation/reduction reactions.

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.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  • Adhikari D, Poulson SR, Sumalia S, Dynes JJ, McBeth JM, Yang Y (2016) Asynchronous reductive release of iron and organic carbon from hematite-humic acid complexes. Chem Geol 430:13–20

    Article  CAS  Google Scholar 

  • Aeschbacher M, Sander M, Schwarzenbach RP (2010) Novel electrochemical approach to assess the redox properties of humic substances. Environ Sci Technol 44:87–93

    Article  CAS  Google Scholar 

  • Borch T, Kretzschmar R, Kappler A, Van Cappellen P, Ginder-Vogel M, Voegelin A, Campbell KM (2010) Biogeochemical redox processes and their impact on contaminant dynamics. Environ Sci Technol 44:15–23

    Article  CAS  Google Scholar 

  • Chen J, Gu B, Royer RA, Burgos WD (2003) The roles of natural organic matter in chemical and microbial reduction of ferric iron. Sci Total Environ 307:167–178

    Article  CAS  Google Scholar 

  • de Melo BAG, Motta FL, Santana MHA (2016) Humic acids: structural properties, and multiple functionalities for novel technological developments. Mater Sci Eng C 62:967–974

    Article  Google Scholar 

  • Diaz AN (1990) Absorption and emission spectroscopy and photochemistry of 1,10-anthraquinone derivatives: a review. J Photochem Photobiol A 53:141–167

    Article  Google Scholar 

  • Dunnivant FM, Schwarzenbach RP, Macalady DL (1992) Reduction of substituted nitrobenzenes in aqueous solutions containing natural organic matter. Environ Sci Technol 26:2133–2141

    Article  CAS  Google Scholar 

  • Gautrot JE, Hodge P, Cupertino D, Helliwell M (2007) 2, 6-Diaryl-9,10-anthraquinones as models for electron-accepting polymers. New J Chem 31:1585–1593

    Article  CAS  Google Scholar 

  • Hernandez-Monotoya V, Alvarez LH, Montes-Moran MA, Cervantes FJ (2012) Reduction of quinone and non-quinone redox functional groups in different humic acid samples by Geobacter sulfurreducens. Geoderma 183–184:25–31

    Article  Google Scholar 

  • Irving HMNH (1978) Recommendations on the usage of the terms ‘Equivalent’ and ‘Normal’. Pure and Appl Chem 50:325–338

    Article  Google Scholar 

  • Jiang J, Bauer I, Paul A, Kappler A (2009) Arsenic redox change by microbially and chemically formed semiquinone radicals and hydroquinones in a humic substance model quinone. Environ Sci Technol 43:3639–3645

    Article  CAS  Google Scholar 

  • Kappler A, Haderlein SB (2003) Natural organic matter as reductant for chlorinated aliphatic pollutants. Environ Sci Technol 37:2714–2719

    Article  CAS  Google Scholar 

  • Kappler A, Benz M, Schink B, Brune A (2004) Electron shuttling via humic acids in microbial iron(II) reduction in freshwater sediment. FEMS Microbiol Ecol 47:85–92

    Article  CAS  Google Scholar 

  • Klüpfel L, Pipenbrock A, Kappler A, Sander M (2014) Humic substances as fully regenerable electron acceptors in recurrently anoxic environments. Nat Geosci 7:195–2000

    Article  Google Scholar 

  • Lovley DR, Blunt-Harris EL (1999) Role of humic-bound iron as an electron transfer agent in dissimilatory Fe(III) reduction. Appl Environ Microbiol 65:4252–4254

    CAS  Google Scholar 

  • Macalady DL, Walton-Day K (2011) Redox chemistry and natural organic matter (NOM): geochemists’ dream, analytical chemists’ nightmare. In: Tratnyek PG, Grundl TJ, Haderlein SB (eds). American Chemical Society, Washington, pp 85–111

  • Matthiessen A (1995) Determining the redox capacity of humic substances as a function of pH. Vom Wasser 84:229–233

    CAS  Google Scholar 

  • Nevin KP, Lovley DR (2000) Potential for nonenzymatic reduction of Fe(III) via electron shuttling in subsurface sediments. Environ Sci Technol 34:2472–2478

    Article  CAS  Google Scholar 

  • Peretyazhko T, Sposito G (2006) Reducing capacity of terrestrial humic acids. Geoderma 137:140–146

    Article  CAS  Google Scholar 

  • Peters RH, Sumner HH (1953) Spectra of anthraquinone derivatives. J Chem Soc 2102–2110. doi:10.1039/JR9530002101

  • Pipenbrock A, Schröder C, Kappler A (2014) Elelctron transfer from humic substances to biogenic and abiogenic Fe(III) oxyhydroxy minerals. Environ Sci Technol 48:1656–1664

    Article  Google Scholar 

  • Rakshit S, Uchimiya M, Sposito G (2009) Iron(III) bioreduction in soil in the presence of added humic substances. Soil Sci Soc Am J 73:66–71

    Article  Google Scholar 

  • Ratasuk N, Nanny MA (2007) Characterization and quantification of reversible redox sites in humic substances. Environ Sci Technol 41:7844–7850

    Article  CAS  Google Scholar 

  • Schnitzer M, Riffaldi R (1972) The determination of quinone groups in humic substances. Soil Sci Soc Am Proc 36:772–777

    Article  Google Scholar 

  • Scott DT, McKnight DM, Blunt-Harris EL, Kolesar SE, Lovley DR (1998) Quinone moieties act as electron acceptors in the reduction of humic substances by humics-reducing microorganisms. Environ Sci Technol 32:2984–2989

    Article  CAS  Google Scholar 

  • Sposito G (2011) Electron shuttling by natural organic matter: twenty years after. In: Tratnyek PG, Grundl TJ, Haderlein SB (eds) American Chemical Society, Washington, pp 113–127

  • Stookey LL (1970) Ferrozine: a new spectrometric reagent for iron. Anal Chem 42:779–781

    Article  CAS  Google Scholar 

  • Vasilyevskaya NA, Glebko LI, Maximov OB (1971) Determination of quinoid groups in humic acids. Pochvovdenie 4:63–67 (in Russian)

    Google Scholar 

  • Visser SA (1964) Oxidation-reduction potentials and capillary activities of humic acids. Nature 204:581

    Article  CAS  Google Scholar 

  • Weber KA, Achenbatch LA, Coates JD (2006) Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction. Nat Rev Microbiol 4:752–763

    Article  CAS  Google Scholar 

  • Yang Z, Du M, Jiang J (2016) Reducing capacities and redox potentials of humic substances extracted from sewage sludge. Chemosphere 144:902–908

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This research was supported by the Evans-Allen Grant from USDA and NSF Grant DEB-0543558. The authors express gratitude to Professor Garrison Sposito at the University of California, Berkeley, for providing laboratory facilities to conduct experimental work for completing this manuscript. The authors also thank Mr. Andrew Yang for his help in the laboratory.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to S. Rakshit.

Additional information

Editorial responsibility: R. Datta.

Appendix

Appendix

See Figs. 9 and 10.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Rakshit, S., Sarkar, D. Assessing redox properties of standard humic substances. Int. J. Environ. Sci. Technol. 14, 1497–1504 (2017). https://doi.org/10.1007/s13762-017-1263-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13762-017-1263-9

Keywords

Navigation