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About us
We are interdisciplinary research team engaged with the studies on humic substances. The team involves scientists and students from the Department of Chemistry and the Department of Soil Science of Lomonosov Moscow State University. The team leader is Dr. Irina V. Perminova – Senior Scientist of the Laboratory of Physical Organic Chemistry (Head – Professor Valery S. Petrosyan).
Thanks to multidisciplinarity of the team, our interests spread over from the traditionally "chemical" subjects – studies on structure and reactions of humic substances – to investigation of their detoxifying ability and biological activity. From the chemical point of view, the most fascinating feature of humic substances is the supramolecular nature of their molecular structure connected with the stochastic synthesis of humic macromolecules out of the plant and animal debris. On the other side, this very feature makes them very difficult to study, rendering direct application of the common analytical techniques for determination of their molecular parameters subject to artefacts.
Realising the problem, quantitative analysis of humic substances has become one of the major field of our activities. Up to date, the particular developments of our group in the field of analytical chemistry of humic substances are:
- an approach to determination of the elemental composition of HS on ash – and water – free basis which implies direct determination of the ash content and accounts for water content present in HS sample (in average 8%);
- determination of the molecular weight distribution of humic substances using size exclusion chromatographic (SEC) technique under conditions of suppression of non-size exclusion effects and justification of the use of polydextrans as the most adequate calibrants (Perminova et al., 1998, Perminova, 1999);
- 1H NMR determination of exchangeable and non-exchangeable protons (Kovalevskii et al., 1999);
- quantitative conditions of 13C NMR spectroscopy of humic substances (Kovalevskii et al., 2000).
The developments on the SEC-technique were conducted in close collaboration with Prof. Dr. F.H. Frimmel and his group – Drs. Abbt-Braun and S. Hesse from the Technical University of Karlsruhe (Germany). Due to long term co-operation with Dr. Norbert Hertkorn from the National Research Centre for Protection of Health and Environment (GSF, Munich, Germany) we got also deeply engaged with 2D NMR spectroscopy of humic substances (Hertkorn et al., 2000). The most recent developments in this field concern the comparative studies of partial structures of humic and fulvic acids (Hertkorn et al., 2001) and studies on the hydrolyzed and fractionated preparations of HS (Permin et al., in preparation).
Another important direction of our studies is development of the data treatment technique aimed at the numerical description of the structure of humic substances. In the framework of this direction, the program Geltreat was designed by A. Kudryavtsev which allows to calculate the numerical descriptors from the raw SEC-chromatographic and electrophoretic data to (Kudryavtsev et al., 2000). They are to be used for the purposes of classification of humic substances and predictive modelling of their properties (Perminova et al., 2000). Very interesting results on the numerical description of the protolytic properties of HS are recently obtained by Dr. Andrey Garmash from the Division of Analytical Chemistry and his graduate student E. Kunenkov who work in close co-operation with our group. We are continuing to work in this direction.
In addition to the quantitative analysis and structural studies of humic substances, another large field of our investigation is interaction of humic substances with different chemical compounds. Due to dual chemical nature of the molecular structure of humic substances consisting of the aromatic core highly substituted with functional groups and hydrophilic carbohydrate-protein periphery, they are able of almost any kind of chemical interaction - ionic, donor-acceptor, hydrophobic bonding. As a result, humic substances form complexes with heavy metals, bind both highly hydrophobic and functionalised organic compounds. In terms of environmental chemistry, humic substances may substantially influence the speciation of the major classes of harmful chemical substances - so called ecotoxicants. To evaluate an impact of humic substances on the behavior of the ecotoxicants in the natural environments, the quantitative estimates of their binding properties are in need. We have chosen to elaborate these estimates for three classes of ecotoxicats of substantially different chemical nature - heavy metals, herbicides and polycyclic aromatic hydrocarbons. For this purpose, for representative sets of humic materials of different origin and fractional composition, the binding constants were determined for Hg(II), atrazine and pyrene, fluoranthene and anthracene using corresponding analytical techniques (Ph.D. Thesises of Zhilin (1998), Kulikova (1999) and Gretchishcheva (2000), respectively). The determination of binding constants of PAH to humic substances was conducted with a use of laser fluorescence in collaboration with Prof. V.V. Fadeev and Dr. E.M. Filippova from the Department of Physics of Lomonosov MSU, Laboratory of Laser Spectroscopy. The corresponding studies for atrazine were conducted with a use of HPLC technique in collaboration with Prof. F-D Kupinke and G. Balcke from the UFZ (Leipzig, Germany).
To establish a link between the chemical binding of ecotoxicants to humic substances and its environmental impact, the detoxifying properties of the same sets of humic materials in relation to the target ecotoxicants were characterised. For quantitative estimation of the detoxifying properties, an approach was developed to calculate the detoxification constants from the reduction in toxicity of ecotoxicants in the presence of humic substances similar to the determination of the binding constants. Its detailed description can be found in (Perminova et al., 2001a). This approach was applied to all three classes of the ecotoxicants studied to produce the quantitative characteristics of the detoxifying properties of humic substances in terms of the detoxification constants (Perminova et al., 2001b, 2001c). The corresponding studies on herbicides were conducted by the present and former team members from the Soil Science Department (Kulikova N., Kholodov V., Lebedeva G., Anisimova M.). The toxicological studies on Hg(II) and PAH were conducted by the chemists (Zhilin D. and Gretchishcheva N., respectively) in close collaboration with Profs. D.N. Matorin and P.S. Venediktov from the Division of Biophysics, the Department of Biology of Lomonosov MSU.
The relatively new field of our research is interaction of humic substances with clay minerals and binding of herbicides to the humic-mineral complexes. This direction is introduced and led by Dr. N. Kulikova - a team member from the Department of Soil Science. The quantitative characterisation of herbicide binding to humic-mineral complexes is one of the key issues for adequate modelling of the herbicide migration in the soil profile.
The amount of the samples of humic substances isolated by the members of our group over seven years of work has reached about 100. This allowed us to obtain the representative data sets both on the structure and binding and detoxifying properties of humic substances, that is, to create the necessary prerequisites for the studies on classification and prognostic modelling of humic substances. We consider development of the "structure-activity" relationships for the detoxifying properties and biological activity of humic substances as an important step towards the practical application of humic substances.
The latter field - practical application of humic substances as natural detoxicants, microfertilizers and biologically active substances is gaining more and more importance in our recent research. The scope of the humic materials of interest includes:
- the traditionally produced humates - non-fractionated mixture of the coal or peat humic substances isolated from the raw materials using alkali extraction;
- fractionated humates obtained using different fractionation techniques;
- metal complexes of humates;
- chemically modified humates.
As the most promising prospective for our future research we see the close coupling of the fundamental and applied research in the field of deepening the knowledge on the structure and properties of humic substances and search for their new practical applications.
2001-2002 "Detoxification of contaminated soils using humic substances", Program "Integration".
2001-2003 "Use of one- and two-dimensional NMR methods for study of molecular structure of humic substances using analysis of their narrow fractions", Russian Foundation for Basic Research (RFBR), #01-03-32664.
2000-2002 "Interactions of humic substances with herbicides: binding, detoxification and relationship to the structure", Russian Foundation for Basic Research (RFBR), #00-04-48692.
1998-2001 "Humic and humic-like substances from natural and anthropogenic sources: structure, reactivity and detoxifying ability in relation to heavy metals and organic ecotoxicants", INTAS - 1129/97.
1998-1999 "Use of proton NMR for study of humic substances structure", Russian Foundation for Basic Research (RFBR), #98-03-33186а.
1997-2001 "Combined use of instrumental analytics, in particular, NMR-Spectroscopy and mathematical modelling for structure elucidation of humic substances", BMBF(Germany)/Russian Ministry for Science and Technology: bilateral cooperation with GSF (Neuherberg, Munich), RUS-143/97.
1996-1998 "Influence of humic substances on biological activity of ecotoxicants of different classes", Russian State Committee for High Education, #4-26.
1996-1998 "Study of protective properties of natural organic matter in soil-herbicide-plant", Russian Foundation for Basic Research (RFBR), #96-04-49838.
1993-1996 "Delopment of the complex approaches of the chemical-biological wastewater treatment", Ministry for Environment, # 8.1.3.28.
1994/1995 "Impact of humic acids on the biological activity of environmentally harmful chemicals: prediction from structural and physico-chemical properties of the humic acids", International Science Foundation (ISF) NBN000/NBN300.
- Leonid A. Karpyuk "Synthesis of alkoxisilylated humic derivatives and adsorption of them onto silicagel"
- Anton N. Kovalenko "Synthesis of quinone-enriched humic materials"
- Elena Yu. Belyaeva "Non-exclusive effects in size-exclusion chromatography analysis of humic substances"
- Erast V. Kunenkov "Classification of humic substances based on size-exclusion chromatography and high-resolution mass-spectroscopy", co-supervisor A.V. Garmash
- Larisa V. Vyborova "Synthesis of salycilate-enriched humic derivatives and investigation of their physiological activity"
Dr. Sc. Thesis
Perminova I.V. Dr. Sc. Thesis. 2000. "Analysis, classification and predictive modelling of properties
of humic substances."
Kulikova N.A. Dr. Sc. Thesis. 2008.
"Protective activity of humic substances towards plants in aquatic and soil media under abiotic stresses conditions".
Ph. D. Theses
- Danchenko N.N. 1997. Functional composition of humic acids: determination and relation to reactivity. Abstract, in Russian / Full text, in Russian
- Anisimova M. A. 1997. Detoxifying ability of soils and isolated from them humic acids to herbicides. Abstract, in Russian / Full text, in Russian
- Zhilin D.M. 1998. Reactivity and detoxifying properties of humic substances to Hg(II) and their interrelationship. Abstract, in Russian / Full text, in Russian
- Kovalevskii D.V. 1998. Investigation of the structure of humic substances with a use of 13C and 1H NMR spectroscopy. Abstract, in Russian / Full text, in Russian
- Kulikova N.A. 1999. Binding and detoxifying ability of soil humic substances to herbicide atrazine. Abstract, in Russian / Full text, in Russian
- Grechishcheva N.Yu. 2000. Chemical and toxicological aspects of interaction of humic substances with PAH. Abstract, in Russian / Full text, in Russian
- Kholodov V.A. 2003. Adsorption and toxicity of herbicide acetochlor in soils of different types. Abstract, in Russian / Full text, in Russian
- Saleem K.M.A. 2004. Usage of humic preparations for detoxification and biodegradation of oil pollution. Abstract, in Russian
- Karpiouk L.A. 2008. Alkoxysilylated derivatives of humic substances: synthesis, structure, sorption properties (Abstract, in Russian / Full text, in Russian)
- Ekaterina A. Ilyukhina "Synthesis of phenolic and quinoid enriched humic derivatives of different molecular sizes"
- Leonid A. Karpyuk "Synthesis of alkoxisilylated humic derivatives and adsorption of them onto silicagel"
- Elena Yu. Belyaeva "Non-exclusive effects in size-exclusion chromatography analysis of humic substances" Full text, in Russian
- Anton N. Kovalenko "Synthesis and characterization of humic substances enriched in quinoic moieties" Full text, in Russian
- Tatiana A. Sorkina "Interaction of humic substances and plutonium ions in different oxidation state" Full text, in Russian
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