The effect of pH on the binding of heavy metal ions with humic substances and hymatomelanic acids of peats

E.D. Dmitrieva^*, K.V. Siundiukova^**, M.M. Leontieva^***, N.N. Glebov^****

Tula State University, Tula, 300012 Russia

E-mail: ^*dmitrieva_ed@rambler.ru, ^**kristina-syundyukova@yandex.ru, ^***senara07@gmail.com, ^****nikolay.glebov.94@mail.ru

Received February 7, 2017

Full text PDF

Abstract

The values of the dissociation constants (–COOH and –OH) of humic substances and hymatomelanic acids have been determined by the potentiometric titration method. It has been shown that hymatomelanic acids are enriched in phenolic groups compared with the original humic substances. The solubility of humic substances and hymatomelanic acids at various pH values is not influenced by their origin. The maximum concentration of humic substances in the absence of metal ions has been observed at pH 4–5. The reduction of pH inhibits dramatically the solubility of humic substances; complete subsidence of macromolecules of humic substances occurs at рН 3 ? 1. The content of humic substances and hymatomelanic acids in the presence of metal ions in the solution decreases due to the formation of humic substance – metal complexes. The maximum binding of metal cations with humic substances of black-alder fen peat and sphagnum transition peat has been found at рН 4–7 and 3.5–4, respectively. The binding of humic substances with lead ions takes place in the sludge phase due to the precipitation of insoluble lead humates, and the binding of humic substances with zinc ions takes place preferentially in the solution phase with the formation of soluble humates. Additional deprotonation of phenolic groups contained in hymatomelanic acids with the increasing of pH enhances their binding capacity in the solution phase in relation to zinc ions.

Keywords: humic substances, hymatomelanic acids, heavy metals, sorption, binding capacity, effect of pH

Acknowledgments. This study was supported by the project “Participant of the Youth Innovation and Research Competition” (UMNIK) no. 12167GU/2017.

Figure Captions

Fig. 1. Alkalimetric titration curves: a) humic substances of black-alder fen peat; b) hymatomelanic acids black-alder fen peat.

Fig. 2. Acidimetric titration curves: a) humic substances of black-alder fen peat; b) hymatomelanic acids.

Fig. 3. Henderson–Hasselbach graphs for hymatomelanic acids: a) alkalimetric titration; b) acidimetric titration.

Fig. 4. The content of humic substances in the solution in the absence and presence of metal ions: a) humic substances of black-alder fen peat; b) humic substancs of sphagnum transition peat.

Fig. 5. The content of hymatomelanic acids in the solution in the absence and presence of metal ions: a) humic substances of black-alder fen peat; b) humic substancs of sphagnum transition peat.

Fig. 6. Scheme showing the formation of intraspheric complexes with Zn(II) ions.

Fig. 7. Specific binding of Pb(II) with humic substances in the phase of solution a); precipitation (b).

Fig. 8. Specific binding of Zn(II) with humic substances in the phase of solution a); precipitation (b).

References

1. Orlov V.D. Humic substances in the biosphere. Soros. Obraz. Zh., 1997, no. 2, pp. 56–63. (In Russian)
2. Zavarzinа A.G. Interaction of humic acids of various origin with metal ions and mineral components of soil. Extended Abstract of Cand. Chem. Sci. Diss. Moscow, 2000. 23 p. (In Russian)
3. Popov A.I. Humic Substances: Properties, Structure, Formation. St. Petersburg, Izd. S.-Peterb. Univ., 2004. 248 p. (In Russian)
4. Gil'miyarova F.N., Agapov A.I. Avakumova N.P. Method of obtaining a preparation based on hymatomelanic acids of low-mineralized silt sulfide mud for physiotherapy. Patent RF no. 97106909, 1998. (In Russian)
5. Siundiukova K.V., Dmitrieva E.D., Goryacheva A.A., Muzafarov E.N. Sorption ability of humic substances from different origin peats of the Tula region in relation to Pb(II). Sorbts. Khromatogr. Protsessy, 2016, vol. 16, no. 6, pp. 788–796.
6. State Standard 27593-88. Soil. Terms and Definitions. Moscow, 1988. 11 p. (In Russian)
7. Zavarzinа A.G. Interaction of humic acids of various origin with metal ions and mineral components of soil. Cand. Chem. Sci. Diss. Moscow, 2000. 133 p. (In Russian)
8. Perminova I.V. Analysis, classification, and prediction of humic acid properties. Doct. Chem. Sci. Diss. Moscow, 2000. 359 p. (In Russian)
9. De Paolis F., Kukkonen J. Binding of organic pollutants to humic and fulvic acids: Influence of pH and the structure of humic material. Chemosphere, 1997, vol. 34, no. 8, pp. 1693–1704. doi: 10.1016/S0045-6535(97)00026-X.
10. Dmitrieva E., Efimova E., Siundiukova K., Perelomov L. Surface properties of humic acids from peat and sapropel of increasing transformation. Environ. Chem. Lett., 2015, vol. 13, no. 2, pp. 197–202. doi: 10.1007/s10311-015-0497-3.
11. Boikova O.I., Volkov E.M. The chemical and biological features of peat in Tula region. Izv. Tul. Gos. Univ., Estestv. Nauki, 2013, no. 3, pp. 253–264. (In Russian)
12. Platonov V.V., Dmitrieva E.D., Proskuryakov V.A., Sypchenko A.I., Hadarcev A.A. Biological Activity of Sapropel and Products Based on It. Available from VINITI. TGPU-St. Petersburg, 2003, no. 1262 V. 20 p. (In Russian)
13. Zavarzina A.G., Demin V.V. Acid-base properties of humic acids of different origin as seen from the potentiometric titration data. Eurasian Soil Sci., 1999, vol. 32, no. 10, pp. 1115–1122.
14. Nenakhov V.D., Kotov V.V., Stekol'nikov K.E., Selemenev V.F., Karpov S.I., Lukin A.N. Detection of different purity humic acids preparations by spectroscopy method. Sorbts. Khromatogr. Protsessy, 2009, vol. 9, no. 5, pp. 665–670. (In Russian)
15. Sokolova S.A., Tsyplakov S.E., Kotov V.V., D'yakonova O.V., Zyablov A.N. Determination of the concentration constants of stability of ion complexes of heavy metals with humus acids. Sorbts. Khromatogr. Protsessy, 2013, vol. 13, no. 2, pp. 162–172. (In Russian)
16. Nenakhov V.D., Kotov V.V., Stekol'nikov K.E., Electro-membrane clearing and acid-base properties of humic acids of leached chernozem. Sorbts. Khromatogr. Protsessy, 2009, vol. 9, no. 2, pp. 301–307. (In Russian)
17. Zolotov Yu.A. Fundamentals of Analytical Chemistry. Moscow, Vyssh. Shk., 1999. 351 p. (In Russian)
18. de Melo B.A.G., Motta F.L., Santana M.H.A. Humic acids: Structural properties and multiple functionalities for novel technological developments. Mater. Sci. Eng.: C, 2016, vol. 62. pp. 967–974. doi: 10.1016/j.msec.2015.12.001.
19. Wang S., Hu J., Li J., Dong Y. Influence of pH, soil humic/fulvic acid, ionic strength, foreign ions and addition sequences on adsorption of Pb (II) onto GMZ bentonite. J. Hazard. Mater., 2009, vol. 167, nos. 1–3, pp. 46–56. doi: 10.1016/j.jhazmat.2008.12.079.
20. Oltra R., Maurice V., Akid R., Marcus P. Local Probe Techniques for Corrosion Research. Woodhead Publ., 2014. 208 p.
21. Kayugin A.A. Distribution of cadmium in model systems containing kaolinite and humic acids. Cand. Chem. Sci. Diss. Tyumen, 2009. 151 p. (In Russian)

For citation: Dmitrieva E.D., Siundiukova K.V., Leontieva M.M., Glebov N.N. The effect of pH on the binding of heavy metal ions with humic substances and hymatomelanic acids of peats. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2017, vol. 159, no. 4, pp. 575–588. (In Russian)

The content is available under the license Creative Commons Attribution 4.0 License.