CONFORMATIONAL RESTRUCTURES OF SUPERSTRUCTURE OF HUMIC ACIDS OF CHERNOZEM TYPICAL IN DEPENDENCE BY SOIL TILLAGE

The physicochemical methods have been used to study the effect of soil tillage of typical black soil for the state of water and the restructuring of intermolecular bonds that determine the of the superstructure of humic acids (HA). It have been established that the HA of the virgin soil is more heterogeneous in composition, due to the presence of hydrophobic and hydrophilic domains, that is due to the equilibrium of the conjugated processes of accumulation and decomposition of soil organic matter (SOM), while tillage of typical black soil caused losses of SOM. It was found that plowing increases the content of fulvic acids and the amount of free water and hydroxyl and carboxyl groups of HA, due to the increase the biodegradation of SOM, which promotes the labile SOM and release of more nutrients. It have been established that plowing of typical black soil leads to conformational rearrangement of intermolecular interactions in the superstructure of HA by hydrophilic hydration. Polar structural elements coordinated by free water dipoles with accessible carboxyl groups. They stabilized the new conformation of HA mainly by hydrogen bonds. It has been shown that the 9-year use of No till leads to a decrease in free water, due to the greater availability of non-polar aromatic structures, and to the reduction of unavailable hydrophilic components, which causes the conformation of the superstructure of HA to stabilize mainly by hydrophobic forces, which causes the accumulation of a hard-to-degradable conservative SOM. Transmission electron microscopy (TEM) have been revealed the presence of smaller particles in the HA samples, in contrast to the sample of HA by No till, which is due to the difference in the molecular organization of their humic superstructures.

1. Skril’nik E. V., Perebikovs’ka O. S., Moskalenko V. P. Influence of systems of cultivation and fertilization on the humus state and nutrient content in chernozem typical. Agrokhіmіya і gruntoznavstvo: mіzhvіdomchii tematichnii naukovii zbіrnik = AgroСhemistry and Soil Science: a collected papers. Kharkiv, 2008, Iss. 68, pp. 90–94 (in Ukrainian).

2. Kravchenko Y., Rogovska N., Petrenko L., Zhang X., Song C., Chen Y. Quality and dynamics of soil organic matter in a typical chernozem of Ukraine under different long-term tillage systems. Canadian Journal of Soil Science, 2012, vol. 92, no. 3, pp. 429–438. DOI: 10.4141/cjss2010-053

3. Orlov D. S. Soil humus acids and general theory of humification. Мoscow, Moscow State University Publ., 1990. 325 p. (in Russian).

4. Wershaw R. L. Molecular aggregation of humic substances. Soil Science, 1999, vol. 164, no. 11, pp. 803–813. DOI: 10.1097/00010694-199911000-00004

5. Piccolo A. The supramolecular structure of humic substances. Soil Science, 2001, vol. 166, no. 11, pp. 810–832. DOI: 10.1097/00010694-200111000-00007

6. Piccolo A. The supramolecular structure of humic substances. A novel understanding of humus chemistry and application in soil science. Advances in Agronomy, 2002, vol. 75, pp. 57–134. DOI: 10.1016/S0065-2113(02)75003-7

7. Yonebayashi K., Hattori T. Surface active properties of soil humic acids. Science of the Total Environment, 1987, vol. 62, pp. 55–64. DOI: 10.1016/0048-9697(87)90481-5

8. Milanovskii E. Yu. Amphiphilous Components of Soil Humic Substances. Eurasian Soil Science, 2000, vol. 33, no. 6, pp. 617–625.

9. Nebbioso A., Piccolo A. Advances in Humeomic: enhanced structural identification of humic molecules after size fractionation of a soil humic acid. Analytica Chimica Acta, 2012, vol. 720, pp. 77–90. DOI: 10.1016/j.aca.2012.01.027

10. Nuzzo A., Sánchez A., Fontaine B., Piccolo A. Conformational changes of dissolved humic and fulvic superstructures with progressive iron complexation. Journal of Geochemical Exploration, 2013, vol. 129, pp. 1–5. DOI: 10.1016/j. gexplo.2013.01.010

11. Ovchinnikova M. F. Attributes and mechanism of the agrogenic transformation of humic substances in soddypodzolic soil. Agrokhimiya [Agrochemistry], 2012, no. 1, pp. 3–13 (in Russian).

12. Tsapko Yu. L. Discussion problems of humus nature. Gruntoznavstvo [Soil Science], 2015, vol. 16, no. 3–4, pp. 83–89 (in Ukrainian).

13. Ionenko V. I., Golovachev E. A., Sukacheva O. I., Kotlyarenko I. P., Beskrovnyi A. M. Phenomenology of functional structural models of natural humus and synthesized humic-like substances. Sibirskii vestnik sel’skhozyaistvennoi nauki [Siberian Herald of Agricultural Science], 1988, no. 5, pp. 91–104 (in Russian).

14. Aquino A. J. A., Tunega D., Pašalić H., Schaumann G. E., Haberhauer G., Gerzabek M. H., Lischka H. Molecular dynamics simulations of water molecule-bridges in polar domains of humic acids. Environmental Science and Technology, 2011, vol. 45, no. 19, pp. 8411–8419. DOI: 10.1021/es201831g

15. Cihlář Z., Vojtová L., Conte P., Nasir S., Kučerík J. Hydration and water holding properties of cross-linked lignite humic acids. Geoderma, 2014, vol. 230–231, pp. 151–160. DOI: 10.1016/j.geoderma.2014.04.018

16. Medvedev V. V. Zero soil cultivation in European countries. Kharkiv, EDENA Publ., 2010. 200 p. (in Ukrainian).

17. Shevchenko M. V. Efficiency of the minimum tillage technologies in growing grain crops in the left-bank forest-steppe. Kormi і kormovirobnitstvo [Feed and Feed Production], 2014, iss. 79, pp. 56–61 (in Ukrainian).

18. Soil quality. Sample selection: SSU 4287:2007 [Introduction of 2004–30–04]. Kiev, Gospotrebstandart Ukrainy, 2005. 9 p. (in Ukrainian).

19. Quality of soil. Methods of determination of organic matter: SSU 4289:2004 [Introduction of 2005–07–01]. Kiev, Gospotrebstandart Ukrainy, 2005. 14 p. (Natsіonal’nyi standart Ukrainy) (in Ukrainian).

20. Quality of soil. Determination of total nitrogen in the modification of the NSC IPA named after A. N. Sokolovsky: SSU 4726:2004 [Introduction of 2005–07–01]. Kiev, Gospotrebstandart Ukrainy, 2005. 14 p. (Natsіonal’nyi standart Ukrainy) (in Ukrainian).

21. Quality of soil. Methods for the determination of available (labile) organic matter: SSU 4732:2007 [Introduction of 2008–01–01]. Kiev, Gospotrebstandart Ukrainy, 2008. 12 p. (Natsіonal’nyi standart Ukrainy) (in Ukrainian).

22. Quality of soil. Determination of the group composition of humus by the method of Tyurin in the modification of Kononova and Belchikov: SSU 7855:2015 [Introduction of 2016–07–01]. Kiev, Gospotrebstandart Ukrainy, 2016. 9 p. (Natsіonal’nyi standart Ukrainy) (in Ukrainian).

23. Quality of soil. Methods for determination of total phosphorus and gross potassium in the modification of the NNC IPA named after A. N. Sokolovsky: SSU 4290:2004 [Introduction of 2005–07–01]. Kiev, Gospotrebstandart Ukrainy, 2005. 14 p. (Natsіonal’nyi standart Ukrainy) (in Ukrainian).

24. Orlov D. S., Grishina L. O. Practical course on the chemistry of humus. Моscow, Moscow State University Publ., 1981. 272 p. (in Russian).

25. Nikolov O. T., Zhilyakova T. A. Measurement of the complex dielectric permittivity of liquid dielectrics with large losses. Zhurnal fizicheskoi khimii = Russian Journal of Physical Chemistry A, 1991, vol. 65, no. 5, pp. 1417–1420 (in Russian).

26. Osterman L. A. Chromatography of proteins and nucleic acids. Моscow, Nauka Publ., 1985. 536 p. (in Russian).

27. Popіrnу M. A., Nіkolov O. T., Skril’nik E. V. Effect of soil treatment intensity on the composition, physical and chemical properties of the second fraction of humic acids extracted from typical chernozem. Bіofіzichnii vіsnik = Biophysical Bulletin, 2016, vol. 1, no. 35, pp. 34–45 (in Ukrainian).

28. Bakhshiev N. G. Introduction to molecular spectroscopy. 2nd ed. Leningrad, Leningrad State University Publ., 1987. 216 p. (in Russian).

29. Gorbatsevich S. K. Spectroscopy of intermolecular interactions. Nonlinear effects. Minsk, Belarusian State University Publ., 2002. 149 p. (in Russian).

30. Kudeyarova A. Yu. Application of basic chemical concepts to understanding the formation and transformation mechanisms of humic substances: A revue of publications and own experimental data. Eurasian Soil Science, 2007, vol. 40, no. 9, pp. 934–948. DOI: 10.1134/s1064229307090037

31. Stevenson F. J., Gosh K. M. Infrared spectra of humic acid and related substances. Geochimica et Cosmochimica Acta, 1971, vol. 35, no. 5, pp. 471–483. DOI: 10.1016/0016-7037(71)90044-5

32. Piccolo A., Stevenson F. J. Infrared spectra of Cu2+, Pb2+ and Ca2+ complexes of coil humic substances. Geoderma, 1982, no. 27, vol. 27, no 3, pp. 195–208. DOI: 10.1016/0016-7061(82)90030-1

33. Baalousha M., Motelica-Heino M., Galaup S., Le Coustumer P. Supramolecular structure of humic acids by TEM with improved sample preparation and staining. Microscopy Research and Technique, 2005, vol. 66, no. 6, pp. 299–306. DOI: 10.1002/jemt.20173