ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 8, pp. 1070−1076. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © E.V. Maltseva, A.V. Savel’eva, A.A. Ivanov, N.V. Yudina, O.I. Lomovskii, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87,
No. 8, pp. 1085−1091.
ORGANIC SYNTHESIS AND INDUSTRIAL
Comparative Study of the Fragment Composition
of Humic Acids Isolated from Caustobioliths
and Soil by the Mechanochemical Method
E. V. Maltseva
, A. V. Savel’eva
, A. A. Ivanov
, N. V. Yudina
, and O. I. Lomovskii
Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences,
Akademicheskii pr. 3, Tomsk, 634021 Russia
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch,
Russian Academy of Sciences, ul. Ketateladze 18, Novosibirsk, 630128 Russia
Received August 28, 2014
Abstract—Fragment composition of humic acids isolated from solid caustobioliths of varied genesis and from
soil was subjected to a comparative analysis. It was found that the composition of these humic acids is affected by
the mechanochemical treatment conditions. It was shown that a mechanochemical treatment leads to a decrease
in the molecular mass of humic acids to a varied extent for all caustobioliths and to an increase in the content of
aromatic fragments in their structure and in the degree of their oxidation.
Properties of humic polyphenolic polymers primarily
depend on their molecular mass, structure, and presence
and content of functional groups. The mechanochemical
treatment is widely used to obtain humic preparations
from caustobioliths because of its being economical,
simple in technological implementation, and ecological
It has been believed previously that the chemical
activity of caustobioliths changes under a mechanical
treatment predominantly due to the dispersion, formation
of new pores and opening of inaccessible pores, and
increase in the external and internal surface area.
However, these phenomena are accompanied by changes
in physicochemical properties because of the rupture
of chemical bonds and decrease in the size of polymer
molecules, formation of soluble products and volatiles,
and oxidation by atmospheric oxygen. Data on changes
in the composition and properties of humic acids (HAs)
from peat and coals in the course of mechanochemical
transformations have been reported in the literature [1, 2].
The efﬁ ciency of humic preparations is improved and
a required function is enhanced by directed modiﬁ cation
via chemical (oxidative destruction, ozonation, amylation,
etc.) [3–5], thermal [6, 7], and physical  treatments.
The authors of [9, 10] have demonstrated the possibil-
ity of oxidation and activation of HAs in the course of
processing of solid caustobioliths via mechanical activa-
tion (MA). Oxidative-hydrolytic processes in peat lead
to destruction of polysaccharides and proteins and result
in that activated HAs enriched with oxygen-containing
functional groups and also melanoidins, pectins, and
amino acids pass to the liquid phase.
Determining the amount of functional groups by
methods based on differences in their chemical properties,
e.g., acidity of oxygen-containing functional groups, is
insufﬁ cient or characterizing important properties of
polyphenols, e.g., their capacity for chelation. Phenolic
groups in neighboring ortho-positions are involved in the
formation of chelate complexes, whereas structures with
phenolic groups in meta- and para-positions do not form
strong chelate complexes.
The information about the content of structural frag-
ments in organic compounds, necessary for prognosti-
cation of their properties, can be obtained by using the