Skip to main content

Role of Humic Substances in the Complexation and Detoxification of Heavy Metals: Case Study of the Dnieper Reservoirs

  • Conference paper
Use of Humic Substances to Remediate Polluted Environments: From Theory to Practice

Part of the book series: NATO Science Series ((NAIV,volume 52))

Abstract

Results of long-term investigations of the heavy metal content and speciation in the Dnieper water bodies (Ukraine) are presented. The particular importance was given to the study of dissolved organic matter (DOM) composition, to binding affinity of metals such as Fe, Mn, Cu, Zn, Pb, Cr, and Cd for DOM, and to molecular weight distribution and chemical nature of metal-DOM complexes. The chemiluminescence and anodic stripping voltammetry in combination with membrane filtration, gel permeation chromatography, and ion-exchange chromatography were used for this purpose. It is shown that complexation with natural organic ligands plays the major role in the fate of HM in fresh water systems. The prevailing fraction of dissolved metals is found to present as complexes with humic substances, mainly, with fulvic acids. For the evaluation of the stability of aquatic ecosystems to the toxic action of HM, the potential complexing ability of DOM was investigated. The results on copper toxicity are presented obtained in long-term experiments with distilled and tap waters as well as with the natural water from the Kanev reservoir containing additives of copper ions and humic acids (HA). The toxic effect of free Cu2+ ions is determined using biotests with Daphnia magna. It was established that a decrease in integral water toxicity correlated with a reduction in free Cu2+ concentration in water medium. Hence, Cu2+ ions present in aquatic media in the form of non-toxic complexes with organic ligands. The maximal decrease in toxicity was observed in natural water where the complexation occurred with participation of both DOM and added HA.

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

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 259.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 329.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 329.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Similar content being viewed by others

5. References

  1. Alberts, J.A., Giesy, J.P. and Evans, D.M. (1984) Distribution of dissolved organic carbon and metal-binding capacity among ultra-filterable fractions isolated from selected surface waters of the southeastern United States, Environ. Geol. 8(2), 91–101.

    Google Scholar 

  2. Appelblad, P.K., Baxter, D.C. and Thunberg, J.O. (1999) Determination of metal-humic complexes, free metal ions and total concentrations in natural waters, J. Environ. Monit. 1(3), 211–217.

    Article  CAS  Google Scholar 

  3. Belzile, N., Joly, H.A. and Li, H. (1997) Characterization of humic substances extracted from Canadian lake sediments, Can. J. Chem. 75(1), 14–27.

    Article  CAS  Google Scholar 

  4. Burba, P., Shkinev, V. and Spivakov, B. Ya. (1995) On-line fractionation and characterization of aquatic humic substances by means of sequential-stage ultrafiltration, Fresenius' J. Anal. Chem. 351, 74–82.

    Article  CAS  Google Scholar 

  5. Burba, P., Van den Bergh, J. and Klockow, D. (2001) On-site characterization of humic-rich hydrocolloids and their metal loading by means of mobile size-fractionation and exchange techniques, Fresenius' J. Anal. Chem. 371, 660–669.

    Article  CAS  Google Scholar 

  6. Campanella, L., Pyrzyñska, K. and Trojanowicz, M. (1996) Chemical speciation by flow-injection analysis. A review, Talanta 43, 825–838.

    Article  CAS  Google Scholar 

  7. Campbell, J.H. and Evans, R.D. (1987) Inorganic and organic ligands binding of lead and cadmium and resultant implications for bioavailability, Sci. Total Environ. 62, 219–227.

    Article  CAS  Google Scholar 

  8. Debeyko, E.V., Ryabov, A.K. and Nabivanets, B.I. (1973) Direct photometric determination of dissolved proteins in natural waters, Gidrobiologicheskiy Zhurnal (Hydrobiol. J.) 9(6), 109–113 (in Russian).

    Google Scholar 

  9. Denisova, A.I., Timchenko, V.M., Nakhshyna, Ye.P., Ryabov, A.K. and Novikov, B.I. (1989) Gidrologiya i gidrokhimiya Dnepra i yego vodokhranilishch (Hydrology and Hydrochemistry of the Dnieper and Its Reservoirs), Naukova Dumka Publishers, Kiev (in Russian).

    Google Scholar 

  10. Esteves da Silva, J.C.G., Machado, A.A.S.C., Oliveira, C.J.S. and Pinto, M.S.S.D.S. (1998) Fluorescence quenching of anthropogenic fulvic acids by Cu (II), Fe (III) and UO2 2+, Talanta 45, 1155–1165.

    Article  Google Scholar 

  11. Flemming, C.A. and Trevors, J.T. (1989) Copper toxicity and chemistry in the environment: a review, Water, Air, Soil Pollut. 44, 143–158.

    Article  CAS  Google Scholar 

  12. Förstner, U. and Wittman, G.T.W. (1983) Metal Pollution in the Aquatic Environment, 2nd ed., Springer-Verlag, New York.

    Google Scholar 

  13. Frimmel, F.H., Immerz, A. and Niedermann, H. (1983) Heavy metal interaction with aquatic humus, Intern. J. Environ. Anal. Chem. 14(2), 105–11.

    CAS  Google Scholar 

  14. Goyer, R.A. (1991) Toxic effects of metals, in M.O. Amdur, J. Doull and C.D. Klaassen (eds.), Toxicology: The Basic Science of Poisons, Pergamon Press, New York, pp. 623–860.

    Google Scholar 

  15. Imai, A., Fukushima, T., Matsushige, K. and Kim, Y. H. (2001) Fractionation and characterization of dissolved organic matter in a shallow eutrophic lake, its inflowing rivers, and other organic matter sources, Wat. Res. 35(17), 4019–4028.

    Article  CAS  Google Scholar 

  16. Itoh, A., Kimata, C., Miwa, H, Sawatari, H. and Haraguchi, H. (1996) Speciation of trace metals in pond water as studied by liquid chromatography/inductively coupled plasma mass spectrometry, Bull. Chem. Soc. Jpn. 69, 3469–3473.

    CAS  Google Scholar 

  17. Ivanova, E., Pershina, I.V., Polenova, T.V. and Chemyak, C.M. (1986) Fluorescence method of determination of fulvic acids in sea water, Zhurnal Analiticheskoy Khimii (J. Anal. Chem) 41(7), 1256–1259 (in Russian).

    CAS  Google Scholar 

  18. Khangarot, B.S., Ray, P.K. and Chandra, H. (1987) Preventive effects of amino acids on the toxicity of copper to Daphnia magna, Water, Air, Soil Pollut. 32, 379–387.

    Article  CAS  Google Scholar 

  19. Linnik, P.N. (1999) Heavy metals in the surface waters of the Ukraine: Content and migration forms, Gidrobiologicheskiy Zhurnal (Hydrobiol. J.) 35(1), 22–42 (inRussian).

    CAS  Google Scholar 

  20. Linnik, P.N. and Iskra, I.V. (1994) Application of anodic stripping voltammetry to the investigation of the physicochemical state of cadmium in surface water in the Ukraine, Microchem. J. 50, 184–190.

    Article  CAS  Google Scholar 

  21. Linnik, P.N. and Nabivanets, B.I. (1986) Migrating Forms of Metals in Fresh Surface Waters, Gidrometeoizdat Publishers, Leningrad (in Russian).

    Google Scholar 

  22. Linnik, P.N. and Nabivanets, Yu.B. (1988) Application of anodic stripping voltammetry to the determination free and bound in complexes ions of zinc and lead in natural waters, Gidrobiologicheskiy Zhurnal (Hydrobiol. J.) 24(1), 68–71 (inRussian).

    CAS  Google Scholar 

  23. Linnik, P.N., Nabivanets, Yu.B., Iskra, I.V. and Chubar, N.I. (1994) Complexing ability of dissolved organic matter and the buffering capacity of aquatic ecosystems, Gidrobiologicheskiy Zhurnal (Hydrobiol. J.) 30(5), 87–99 (in Russian).

    Google Scholar 

  24. Luoma, S.N. (1983) Bioavailability of trace metals to aquatic organisms — a review, Sci. Total Environ. 28, 1–22.

    CAS  Google Scholar 

  25. Mandal, R., Sekaly, A.L.R., Murimboh, J., Hassan, N.M., Chakrabarti, C.L., Back, M.H., Gregoire, D.C. and Schroeder, W.H. (1999) Effect of the competition of copper and cobalt on the liability of Ni (II)-organic ligand complexes. Part I. In model solutions containing Ni (I) and a well-characterized fulvic acid, Anal. Chim. Acta 395, 309–322.

    Article  CAS  Google Scholar 

  26. Mandal, R., Sekaly, A.L.R., Murimboh, J., Hassan, N.M., Chakrabarti, C.L., Back, M.H., Gregoire, D.C. and Schroeder, W.H. (1999) Effect of the competition of copper and cobalt on the liability of Ni (II)-organic ligand complexes, Part II: In freshwaters (Rideau River surface waters), Anal. Chim. Acta 395, 323–334.

    Article  CAS  Google Scholar 

  27. Moore, J.W. and Ramamoorthy, S. (1987) Heavy Metals in Natural Waters, Mir Publishers, Moscow (Russian ed.).

    Google Scholar 

  28. Nabivanets, B.I., Linnik, P.N. and Kalabina, L.V. (1981) Catalytic Methods for Natural Water Analysis, Naukova Dumka Publishers, Kiev (in Russian).

    Google Scholar 

  29. Nifant'eva, T.I., Shkinev, V.M., Spivakov, B. Ya. and Burba, P. (1999) Membrane filtration studies of aquatic humic substances and their metal species: a concise overview. Part 2. Evaluation of conditional stability constants by using ultrafiltration, Talanta 48, 257–267.

    Article  Google Scholar 

  30. Nomizu, T., Sanji, M. and Mizuike, A. (1988) Removal of iron for the spectrophotometric determination of humic substances in fresh waters, Anal. Chim. Acta 211(1–2), 293–297.

    Article  CAS  Google Scholar 

  31. Perminova I.V. (2000) Analysis, Classification and Prediction of Properties of Humic Substances, Dr. Sci. Thesis. (in Chemistry), Lomonosov Moscow State University, Moscow, Russia (in Russian).

    Google Scholar 

  32. Peters, A.J., Hamilton-Taylor, J. and Tipping, E. (2001) Americium binding to humic acid, Environ. Sci. Technol. 35, 3495–3500.

    Article  CAS  Google Scholar 

  33. Popovich, G.M. (1990) Sorption concentration and spectrophotometric determination of humic and fulvic acids in waters, Abstract of Ph.D. Thesis, Kiev (in Russian).

    Google Scholar 

  34. Salomons, W. and Förstner, U. (1984) Metals in the Hydrocycle, Springer-Verlag, Berlin.

    Google Scholar 

  35. Sedláček, J., Gjessing E. and Rambaek, J.P. (1987) Isotope exchange between inorganic iron and iron naturally completed by aquatic humus, Sci. Total Environ. 62, 275–279.

    Article  Google Scholar 

  36. Sekaly, A.L.R., Mandal, R., Hassan, N.M., Murimboh, J., Chakrabarti, C.L., Back, M.H., Gregoire, D.C. and Schroeder, W.H. (1999) Effect of metal/fulvic acid mole ratios on the binding of Ni (II), Pb (II), Cu (II), Cd (II), and Al (III) by two well-characterized fulvic acids in aqueous model solutions, Anal. Chim. Acta 402, 211–221.

    Article  CAS  Google Scholar 

  37. Semenov, A.D. (Ed.) (1977) Manual on the Chemical Analyses of Surface Waters of Land, Gidrometeoizdat Publishers, Leningrad (in Russian).

    Google Scholar 

  38. Sirotkina, I.S., Varshal, G.M., Lur'ye, Yu.Yu. and Stepanova, N.P. (1974) Application of cellulose sorbents and sephadexes in systematic analysis of natural water organic substances, Zhurnal Analiticheskoy Khimii (J. Anal. Chem.) 29(8), 1626–1633 (in Russian).

    CAS  Google Scholar 

  39. Steinberg, C.E.W., Haitzer, M., Brueggemann, R., Perminova, I.V., Yashchenko, N. Yu. and Petrosyan, V.S. (2000) Towards a quantitative structure activity relationship (QSAR) of dissolved humic substances as detoxifying agents in freshwaters, Int. Rev. Hydrobiol. 85(2–3), 253–266.

    Article  CAS  Google Scholar 

  40. Town, R.M. and Filella, M. (2000) A comprehensive systematic compilation of complexation parameters reported for trace metals in natural waters, Aquat. Sci. 62, 252–295.

    Article  Google Scholar 

  41. Tseeb, Ya. Ya. and Maistrenko, Yu. G. (eds.) (1972) Kiev Reservoir: Hydrochemistry, Biology, Productivity, Naukova Dumka Publishers, Kiev (in Russian).

    Google Scholar 

  42. Van den Bergh, J., Jakubowski, B. and Burba, P. (2001) Investigations on the conditional kinetic and thermodynamic stability of aquatic humic substance—metal complexes by means of EDTA exchange, ultrafiltration and atomic spectrometry, Talanta 55, 587–593.

    Article  Google Scholar 

  43. Varshal, G.M. (1977) On the state of mineral components in surface waters, in M.M. Senyavin (Ed.), Methods of Analysis of Natural Waters and Effluent: Problems of Analytical Chemistry, Vol. 5, Nauka Publishers, Moscow, 94–107 (in Russian).

    Google Scholar 

  44. Zhilin, D.M. and Perminova, I.V. (2000) Approach to assessment of the buffer capacity of an aquatic ecosystem on the example of Hg (II), Priroda (Nature) 11, 43–50 (in Russian).

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2005 Springer

About this paper

Cite this paper

Linnik, P., Vasilchuk, T. (2005). Role of Humic Substances in the Complexation and Detoxification of Heavy Metals: Case Study of the Dnieper Reservoirs. In: Perminova, I.V., Hatfield, K., Hertkorn, N. (eds) Use of Humic Substances to Remediate Polluted Environments: From Theory to Practice. NATO Science Series, vol 52. Springer, Dordrecht. https://doi.org/10.1007/1-4020-3252-8_6

Download citation

Publish with us

Policies and ethics