Organic matter of technogenic soils and substrates on the dumps of sulfidic mine rock (carbonaceous shale) in Western Donets Basin

Data on the total carbon content and on the composition of humic substances extracted from the technogenic soils and substrates of dumped mine rocks are analyzed. It is shown that two types of humic substances are formed upon the oxidation of sulfidic rocks and their overgrowing with vegetation. The first type is represented by humic substances originating in the course of transformation of plant remains. The second type includes humic substances formed due to the oxidation of coal particles; these humic substances are characterized by a higher C_ha/C_fa ratio. The role of humic acids in decreasing the mobility of aluminum ions in the strongly acid mine substrate is experimentally confirmed.     

Transformation of corn plant residues in loamy and sandy substrates

The mineralization and humification dynamics of corn plant residues in loamy and sandy substrates have been studied under laboratory conditions. It has been shown that the dynamics are determined by the undulating development laws of the microbial community under constant temperature and moisture conditions. At the same time, the intensity and final results of the processes significantly differ depending on the composition and properties of the mineral substrate. The loss of C_org during the mineralization and the content of newly formed humic substances reached the maximum values a month after the beginning of the experiment. The mineralization is more intensive in sand at the early stages, and the humification is more active in loam throughout the incubation period. The loamy substrate has better protective properties compared to the sand; therefore, it favors the accumulation of significant amounts of fulvic acids (FAs), along with humic acids (HAs), and causes the relative fulvatization of the humic substances. It has been found using densimetric fractionation and Fourier IR spectroscopy that the different mineralogy of the fractions results in differences in the chemical composition of the formed mineral-organic compounds of newly formed humic substances, mainly due to carboxyl and nitrogen-containing groups. The similarity of the humification products in the heavy fractions of the loamy and sandy substrates has been revealed.     

腐殖物质对有机污染物的吸附行为及环境学意义

综述了近年来腐殖物质的研究进展,具体包含以下几个方面的内容:腐殖物质的分离、纯化、元素组成和结构特征及其环境意义。重点讨论了腐殖物质的环境学意义,阐述了腐殖物质主要是胡敏素在吸附疏水性有机污染物的过程中所起到的重要作用,其中包括可溶性腐殖物质的增溶作用和不溶性腐殖物质———胡敏素的吸附固定作用;且对吸附/解吸的机理及一些模型的建立进行了探讨。最后针对研究中面临的问题,提出了今后的重点研究方向。     

Composting And Humification

The development of humic substances in the course of four composting processes was monitored quantitatively, recording both relative and absolute contents. Relative data showed contrasting results if the humic substances (HS) were related to the dry matter (d.m.) or to volatile solids (VS). Humic substances were apparently formed because of a concentration effect due to organic matter degradation. If absolute contents were considered, a decrease in the humic substances was observed, above all in the early stages of the process, due, probably, to degradation of the organic material, such as proteins, carbohydrates and lipids, coextracted with the humic substances. Processing of the data in respect of humic substance content over 13 composting processes and one study on the degradation of plant residues in soils, confirmed that no net humic substances are formed during composting and that the humification should be interpreted merely as degradation of the organic matter associated with the humic substances, after uncovering what is known as the core of the humus. The concept of humification during the composting process therefore needs to be reviewed, bearing in mind that neither the method commonly used for humic substance extraction nor the relative results obtained enable it to be interpreted satisfactorily.     

Effects of mineral and monocarboxylic acids on the molecular association of dissolved humic substances

The conformational structure of dissolved humic substances is an important property that controls the reactivity of humus in the soil solution. High performance size-exclusion chromatography was used here to study the changes in molecular size of different humic substances brought about by addition of mineral (HCl) and monocarboxylic (formic, acetic, propionic, and butyric) acids. The CPMAS-NMR spectra showed that humic substances had varying chemical composition and that the ratio of hydrophilic to hydrophobic carbon (HI/HB) was greater for a humic acid from soil than for ones from oxidized coal and lignite. All humic substances showed a decrease in UV absorbance of chromatographic peaks when treated with either HCl or monocarboxylic acids. This was due to the hypochromic effect by which the absorptivity of associated molecules is decreased when they are separated. We attributed the molecular separation upon acid treatment to the formation of intermolecular hydrogen bonding that alters the original conformation stabilized mainly by weaker hydrophobic interactions. Addition of organic acids not only further decreased peak absorbances of humic acids but also caused their shift to larger elution volumes, indicating a larger conformational disruption than with HCl. The extent of the molecular size changes showed a relation to the number of carbons of monocarboxylic acids and to the HI/HB ratios of humic materials. The larger the carbon content of organic acids and the smaller the HI/HB ratio of humic materials, the larger was the decrease of the average molecular size of humic acids. These results suggest that dissolved humic substances associate predominantly by hydrophobic forces and that the apolar components of humic substances largely control their aggregation and reactivity in the environment.     

Systems of solutions,minerals, and humic substances in soils

The equilibrium composition of solutions, minerals, and humic substances of the humus-clay plasma from the humus horizon of a leached chernozem was calculated using the method of computerized physicochemical simulation based on Gibbs’ principle of minimum free energy in the equilibrium state of the system. It was shown that the plasma from the humus horizons of chernozems and soddy-deeply podzolic soil mainly consists of oxides, hydroxides, humic substances, kaolinite, and 2: 1 illite-smectite minerals. The stoichiometry of the humic substances corresponds to calcium-saturated humus acids with appreciable contents of iron and aluminum. The crystallochemical composition of the 2: 1 layered minerals classifies them among ferruginated mixed-layered illite-montmorillonites. Simulation at an increased concentration of carbon dioxide indicated the degradation of the humus-clay plasma in a leached chernozem under extensive soil use, which can be restored by application of potassium at rates 1-to ?1.5-fold its removal.     

Formation of humic acids during plant residue humification and their nature

The process of humic acid formation during humification of plant residues (clover leaves and roots as well as timothy roots) was studied. According to some characteristics (elementary composition, IR-spectra, the content of COOH-groups) the newly-formed humic acids may be defined as “young forms”. The comparison of the new forms with more mature soil humic acids revealed the following specific features of the latter: (a) a higher degree of aromatic nuclei condensation; (b) a higher content of carboxyl groups; and (c) a more uniform structure.The authors discuss some defects of the methods used for extraction of humic acids from fresh and slightly humified plant residues by alkaline solutions. An artificial formation of humus-like substances and their extraction as admixtures together with true humic acids are inevitable with these methods. This should be taken into account in studying and systematizing such forms of humic acids.     

A comparative study of elemental composition of water-soluble humic substances,humic acids,and fulvic acids extracted from sod-podzolic soils

Elemental analysis of water-soluble humic substances extracted from three sod-podzolic soils was carried out. Data on elemental composition were compared to those of humic and fulvic acids extracted from the same soils.     

钾肥和腐殖酸互作对烤烟有机钾盐指数的影响

以烤烟品种金神农1号为材料,采用钾肥与腐殖酸双因子大田试验,分析了不同钾肥和腐殖酸水平及其互作对烤烟干物质量、化学成分、香味物质及有机钾盐指数的影响。结果表明:在同一钾肥水平下增施腐殖酸及在同一腐殖酸水平下增施钾肥均可增加烤烟前期的总干物质和烘烤后烟叶的总香味物质量,改善烟叶化学成分,提高有机钾盐指数;钾肥和腐殖酸互作对烟叶还原糖、总氮、氮碱比、钾及有机钾盐指数均有显著的正效应,而对烤烟干物质量及其余化学成分指标的影响则未达到显著水平;较高水平的钾肥和腐殖酸配施相对于较低水平两者配施有利于改善烤烟品质,提高烟叶钾含量和有机钾盐指数。     

Computer modelling of partial specific volumes of humic substances

The determination of the structure of humic substances from peat soils and natural waters is a major problem in soil science. Humic substances are chemically heterogeneous and consist of molecules covering a wide distribution of molecular size. A quantity related to both molecular size and structure in the hydrated state is the volume of the humic molecules per unit mass or partial specific volume (ν₂). The partial specific volumes of humic substances have been estimated from atom and chemical group volume contributions for 17 proposed structures of fulvic and humic acids taken from the literature. The results show that the partial specific volume reflects the composition of humic substances, decreasing with increase in the carbon: hydrogen (C:H) molar ratio. The more oxidized the humic material the smaller is its partial specific volume. These trends agree with our experimental measurements of partial specific volumes for a range of humic materials (aquatic fulvics, aquatic and peat humics). The predicted values of partial specific volumes for the proposed structures, however, are overestimated by approximately 15% compared to the experimental values. There is little difference between values of ν₂ calculated from the detailed humic structures and those calculated from their empirical formulae; calculations of partial specific volumes using a random modelling approach leads to overestimation by approximately 37%. It seems that the estimates based on additivity of atom and chemical group volumes do not take into account an overall contraction of the structures because of hydrophobic interactions. In general terms the values of the partial specific volumes of humic substances suggest they are more compact molecules than globular proteins, and intrinsic viscometry studies suggest that aqueous salt solutions approach θ-solvent conditions for humic substances.     

Relations between organic carbon and methylmercury in humic rich surface waters from Svartberget catchment in northern Sweden

Monthly sampling of a mire outlet and two tributaries, one of them originating in the mire, on the Svartberget catchment in northern Sweden was performed during one year. The concentration of total organic carbon (TOC) in the three waters was fairly high (10–40 mg/l). Methylmercury (MeHg) was analysed in the original water sample (MeHg-whl) and in the humic fraction (MeHg-hum). The MeHg-hum increased with increasing concentration of humic substances (HS; measured as absorbance at 254 nm) in the water. A seasonal variation of the MeHg-hum/TOC ratio was superimposed on a negative relationship to the water flow, which indicates that the methylation is a slow process which results in a rapid drainage of the storage during periods of high flow. A minimum of the MeHg-whl/TOC ratio observed during the spring flood was followed by a slow increase during the rest of the year.     

Changes in the composition and properties of humic acids under the influence of microorganisms

By gel filtration on Sephadex G-50 and G-75, we investigated the changes in the composition and ratio of the molecular fractions of humic acids under the influence of native soil microbial complexes. The highest degree of decomposition of the initial humic acid was observed when ammonium nitrate was used as a source of additional energy in the mineral nutrient medium without a yeast extract. The appearance of a low molecular fraction of organic substances on chromatograms may be associated with the synthesis by bacteria of simple organic substances on the medium with humic acids as a single source of carbon.     

Dissolved organic matter in lysimetric water of mountain forest soils in the southern Sikhote Alin

The fractional composition of dissolved organic matter and the chemical nature of humic and fulvic acids were studied in lysimetric waters from forest soils of different altitudinal zones in the Sikhote Alin Range. The elemental composition, infrared absorption spectra, concentrations of acid functional groups, and pK spectra of humic and fulvic acids were determined. Fulvic acids predominated in the upper soil horizons, and fraction of nonspecific dissolved organic substances predominated in the lower mineral horizons. The portion of humic acids in the humus horizons markedly decreased from the low-mountain soils to the high-mountain soils; the nitrogen content of humic and fulvic acids decreased in the same direction. Three classes of carboxyl and phenolic groups were determined in pK-spectra of humic and fulvic acids. The soils of high-mountain zones had stronger acidic properties of humic and fulvic acids in comparison with the soils of low-mountain zones. The determined characteristics of the composition of dissolved organic matter and the trends of their changes contribute to our knowledge of pedogenetic processes in the altitudinal sequence of forest landscapes of the Sikhote Alin Range.     

Über Veränderungen im Humuskomplex bei der Degradation von Schwarzerden (Tschernosemen)

Dynamics of organic matter during the degradation of Chernozems In the course of pedogenesis especially the amount and the composition of soil organic matter changes. This is investigated in the presented paper at 6 different developmentstages of a Chernozem-degradation-sequence from Hildesheim region. The mechanisms of this process can be deduced from the ‘degradation products’, found in the different soils. Using several methods for extraction of organic substances by successively stronger reagents or conditions, different amounts of fulvic and humic acids were got. The findings give indications to the different stability of bondings between mineral and organic substances in the soils and their change during degradation. The ascending exhaustive fractionating method was found to be the best for obtaining and-simultaneously - separating completely the organic matter in distinct franctions and also to earn a humus-clay and a silica humic acid component. Using this method, 5 fractions of the humus complex at any of profile-horizons were got in greater amounts and quantitative as far as qualitative determined. It was found that the loss of organic matter is differently distributed to the single humus fractions in the profiles and in the horizon-zones. Therefore it is not sufficient to determine only the total C- and N-content. Comparing the increase or decrease of humic substances in the upper resp. lower zones of the profiles of the sequence, the degradation process can be pursued retrospectively.     

Analysis of the variable charge of two organic soils by means of the NICA-Donnan model

We have tested to see if the generic set of NICA‐Donnan model parameters, used to describe isolated humic substances, can also describe soil humic substances in situ. A potentiometric back‐titration technique was used to determine the variable surface charge of two organic peat soils at three different ionic strengths. The non‐ideal, competitive‐adsorption NICA‐Donnan model was used to simulate the surface charge, by assuming a bimodal distribution of H⁺ affinity on the soil solid phase. The model provided an excellent fit to the experimental data. The Donnan volume, V_D, varied slightly with ionic strength, although the variation was less than for humic substances in solution. The values obtained for the parameters that define the affinity distributions, the intrinsic proton binding constant (log K_i^int) and the heterogeneity of the site (m_i), were similar to those observed for isolated soil humic acids. The abundance of carboxylic groups in the whole soil represented 30% of the typical value for isolated soil humic acids. The composition of the organic matter of the whole soils, obtained by ¹³C CPMAS NMR, was comparable to the characteristic composition of soil humic acids.     

Elemental composition and structural features of humic substances in young podzols developed on sand quarry dumps

Data were analyzed on the elemental composition of humic and fulvic acids isolated from organic and mineral horizons of different-aged podzols developed on sand quarry dumps in Leningrad oblast. It was shown that the humic substances from the young podzols significantly differed from those isolated from the mature soils. The humic acids (HAs) of the young podzols composed a more homogeneous group of natural compounds compared to the fulvic acids (FAs). The HAs isolated from the organic, podzolic, and illuvial horizons of the embryopodzols significantly differed in their structure. The litter HAs were characterized by the minimum aromaticity and the maximum content of aliphatic components. The HAs from the illuvial horizons contained the maximum portion of aromatic components; a significant portion of carboxyls, ethers, polysaccharides, carbohydrates, and amino acids; and the minimum portion of aliphatic components. The HAs from the podzolic horizons occupied an intermediate position between the humic substances of the organic and illuvial horizons. It was shown that Mendeleev’s formula was more suitable than Aliev’s formula for calculating the calorific values of the HAs because of their structural features. Based on the particular features of the humic substances studied, they were classified as prohumic substances.     

Die Veränderung von Huminsäuren in alkalischer Lösung

The change of humic acids in alkaline solution Five natural humic acids were fragmented under the conditions of the conventional method of extraction of humic substances with sodium hydroxide. Fulvic acid, hymatomelanic acid and a water soluble fraction (at pH 2) could be isolated as fragmentation products. The three fractions were formed directly after the treatment with sodium hydroxide, their quantities depend on the concentration and time of treatment with sodium hydroxide and from the function of the system. The deviating, differentiating and reproducing formation of fragments is explained by partial reversible reactions. Therefore fulvic acid and hymatomelanic acid must be regarded as artefacts. existing during the procedure of isolation of humic substances at high pH-values. Therefore the conventional isolation of humic substances from soils should always be accompanied by experiments, which inform about the arteficial production of ‘fulvic acids’ and ‘hymatomelanic acids’ during the procedure of isolation.     

Effects of HCl–HF purification treatment on chemical composition and structure of humic acids

Sample preparation for the study of humic acids involves a purification treatment to remove both mineral and organic components extracted along with the humic substances. The effects of HCl–HF purification on the chemical composition and structure of humic acids were studied in samples from eight different composts. Only small increases in the concentrations of C, N and H and a decrease in O were found in purified humic acids when compared with the unpurified materials, no more than 10% of average concentration. Total and phenolic acidity increased in the purified materials, whereas carboxylic and carbonyl acidity showed no statistically significant differences as a result of the purification. Gel permeation chromatography showed that only minor changes occurred in molecular size distribution of the humic acids, and the infrared spectra showed no appreciable differences between the purified humic acids and the untreated materials. We conclude that the HCl–HF treatment successfully reduced the ash contents of the humic acids without modifying their chemical composition and structure significantly.     

Effect of long-term drainage on the content and composition of humus in soddy-podzolic soils and their particle-size fractions

Changes in the quantitative and qualitative characteristics of humic substances in soddy-podzolic soils and their particle-size fractions in the course of long-term drainage have been studied under the conditions of pronounced microrelief and different intensities of agrotechnical impacts. The transformation features of humic substances during the periods of specific impacts have been characterized.     

Water- and pyrophosphate-extractable humic substances fractions as a source of iron for Fe-deficient cucumber plants

The capacity of Fe-deficient cucumber plants to utilise water-extractable and pyrophosphate-extractable humic substances as a source of Fe was investigated. Plants were grown for 13 days in nutrient solution in the presence or absence of Fe and during the last 7 days water-extractable and pyrophosphate-extractable humic substances were added to the solution at a final concentration of 5 μg organic C ml^–1. The water-extractable humic fraction did not significantly modify leaf area and dry matter accumulation, leaf total Fe or chlorophyll content of cucumber plants adequately supplied with Fe. In contrast, pyrophosphate-extractable humic substances caused a slight but significant decrease of all the leaf parameters considered, with the exception of the chlorophyll content. Root Fe content of Fe-sufficient plants was decreased by more than 50% in the presence of each humified fraction. Addition of each humic fraction to Fe-deficient plants led to a partial disappearance of leaf chlorosis symptoms with a significant increase in chlorophyll and leaf Fe content. Fe content of roots was also significantly increased in Fe-deficient plants by the addition of humic substances to the nutrient solution. These results show that Fe-deficient cucumber plants can utilise Fe contained in the two fractions of humified organic matter. However, by calculating the amount of total Fe accumulated per plant in the presence of water-extractable or pyrophosphate-extractable humic substances, it could be seen that Fe contained in the water-extractable humic fraction was almost totally used by Fe-deficient cucumber plants, while that present in the pyrophosphate-extractable fraction could only be partially absorbed. The results strongly support a role of humified organic matter in Fe nutrition of plants and are discussed in terms of a possible interaction between soil humic substances and the biochemical mechanisms involved in the plant response to Fe deficiency. Received: 6 November 1996