Infrared spectroscopic investigations of humic substances and their metal complexes

A study has been made on the infrared spectra of lowland peats and purified humic, hymatomelanic and fulvic acids, as well as their acetylated derivatives and metal complexes. Extraction and purification may modify humic acids of untreated peats only to a small extent. Acetylation of fulvic and humic acids with acetic acid anhydride resulted mainly in the reaction of phenolic hydroxyl and quinone groups. Similarities of the spectra of the individual humic substances point to similar structures, differing only in the number of functional groups and the degree of aggregation. Metals are bound by humic substances mainly in metalcarboxylate bonds. The degree to which these bonds are ionic or covalent can be determined by the antisymmetric carboxylate stretching frequencies.     

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.     

Humus degradation under the influence of simulated ‘acid rain’

The purpose of these investigations was to describe changes occurring in soil under the influence of simulated ‘acid rains’. It was achieved by treating three kinds of soil with water solutions of pH: 2.0, 3.0, 4.0, 5.0, 6.0, 7.8 for two vegetation periods. Differences were found in the pH of soils reaching 2.5 values in the sorption complex. The content of H⁺ increased and the sum of bases considerably decreased. Significant changes in number of bacteria, fungi, macromycetes were found. In most acid solutions they decreased by 100% as compared with the reference surface. The processes of nitrification, cellulose decomposition and soil respiration were limited, whereas ammonification was stimulated. Under the influence of ‘acid rains’ the content of C and N remained unchanged, while the content both of fulvic and grey and brown humic acids was reduced. With the increase in soil acidity the content of hymatomelanic acids increased. So significant changes in the content of bitumen, humins, humic C and the Q_4/6 color quotient were observed under the influence of simulated ‘acid rains’.     

Effect of temperature on the fragmentation of humic acids in alkaline solutions

The fragmentation of one synthetic and four soil humic acids was studied in solutions of sodium hydroxide (pH 13) at different temperature between 0 and 90°C. The dissolved parts of the initial amounts of humic acids decreased to a minimum with the increase in temperature from 0 to 10°C. The fragmentation in this region was a function of both; temperature and concentration. At 15–20°C all of the initial amounts of humic acids were dissolved. The rate of fragmentation increased rapidly between 15 and 20°C and later slowed down between 20 and 40°C. This was due to the reaggregation of the particles of the produced hymatomelanic acids into particles of similar solubilities as those of the residual nonfragmented parts of the humic acids. This reaggregation took place probably through the formation of hydrophobic bonds. The fragmentation increased at temperatures above 40°C, and reached a maximum between 50 and 70°C depending on the type of the humic acid. The decline in fragmentation at temperatures higher than those corresponding to the maxima is most probably due to chemical reactions, in which the fragmentation products especially fulvic acids recombine together at about 60°C. Importance of these results in analytical methods of extraction and characterisation of humic acids is discussed.     

Ein Vergleich der Huminstoffsysteme einer Parabraunerde aus der Kölner Bucht und einer österreichischen Schwarzerde

A comparison of the humic systems from a Luvisol from the area of Köln and from an Austrian Chernozem Grey humic acids, brown humic acids and fulvic acids have been extracted from a Luvisol after removal of the “light fraction”. The humic fractions were investigated chromatographically using controlled pore glass with a pore diameter of 17,7 nm. Concentration of both coloured material and carbon were simultaneously recorded in the chromatograms. Specific extinctions at 400 nm were calculated and maximal values were taken as constants specific for “pure” humic substances. These were 349,6; 155,8 and 39,4 for “pure” grey humic acids, brown humic acids and fulvic acids, respectively, and were in part considerably below those determined earlier for an Austrian Chernozem. Using these constants “pure” humic substances could be distinguished numerically from accompanying non-humic substances. The ratio of “pure” humic to non-humic substances was approximately 2:1 for both soils. Within the “pure” humic substances Chernozem humus was dominated by grey humic acids amounting up to 52% whereas in the Luvisol brown humic acids had the same level.     

腐殖物质的某些物理化学性质

土壤腐殖物质的形状,与土壤物理性质和物理化学性质有密切关系.已经知道,线型分子对土壤颗粒的团聚化有着特别良好的作用^[1].腐殖物质是土壤中主要的有机物质.     

Nitrogen in humic and fulvic acid fractions from a volcanic soil under pine: recovery efficiency of two extractants

The nitrogen content of humic and fulvic acid fractions recovered in parallel with sodium hydroxide and a mixture of sodium hydroxide and sodium pyrophosphate from a volcanic soil under pine was determined. Despite minor differences for some horizons, the values found by the two methods were similar. Furthermore, the ratio between the N contents in the humic and fulvic acid fractions (Nh : Nf) was independent of the nature of the extractant. This fact and the facility of the determination suggest investigating if the Nh: Nf ratio can be used as indicator for the quality of soil organic matter.     

Humus composition of soils under forest, coffee and arable cultivation in hilly areas of south Sumatra, Indonesia

To understand the effect of land use changes on the composition of humus in tropical soils, samples from land under primary forest, secondary forest, coffee plantation, and arable crops were investigated at three sites in south Sumatra, Indonesia. Total carbon and total nitrogen contents were 1.7 to 4.3 times and 1.1 to 2.8 times greater in the topsoil under primary forest than under the other types of land use. Following change from primary forest to other uses, the proportion of humic acids in the organic matter of the topsoils decreased while that of the fulvic acid fraction increased. Within the range of land uses, differences in the yields of humic acids and fulvic acid fractions were, respectively, larger and smaller than those in total carbon content. The humic acids were classified into the low and middle classes in the degree of humification. Absorption due to the green fraction of humic acids, Pg, was detected in the UV‐visible spectra of almost all the humic acids. No relation was observed between the degree of humification of humic acids or the strength of Pg absorption in their spectra and land use change. The fulvic acid fractions were fractionated on insoluble polyvinylpyrrolidone (PVP) into the adsorbed fractions consisting of humic substances and the non‐adsorbed fractions consisting of non‐humic substances. A positive correlation between the amount of the fulvic acid fraction and the percentage of the PVP‐adsorbed fraction within it indicated that the variation in the amount of the fulvic acid fraction was attributable to acid‐soluble humic substances. The ionization difference spectra of solutions between pH 12 and pH 7 suggested that the chemical structures of the PVP‐adsorbed fulvic acids have been altered by land use change.     

Wechselwirkungen zwischen Boden-Huminstoffen und Metall-Ionen I. Isolierung und Charakterisierung der Boden-Huminstoffe

Interactions between soil humic substances and metal ions I. Isolation and characterization of the soil humic substances From two horizons of a podzol humic acids and fulvic acids were isolated by two different methods. The obtained samples were characterized by elemental analysis, the determination of the ash and moisture content, functional group analysis as well as FTIR-, ¹H-NMR-, and ¹³C-NMR-spectroscopic examinations. In spite of the different isolation methods humic and fulvic acids show great similarities. A higher oxidized state and a lower content of aromatic structural features are clearly observed in the fulvic acids in contrast to humic acids. Besides aromatic structural elements, distinct aliphatic sections were detected in the investigated samples, which showed a lower concentration in the less transformed fractions of the Ahe-horizon.     

Einfluß der Konzentration der Huminsäuren auf ihre Fragmentierung in Alkalilösungen

The influence of concentration of humic acids on their fragmentation in alkaline solutions The fragmentation of synthetic and other four natural humic acids with accending concentrations in sodium hydroxide solutions would be examined. It was found that the fragmentation decreases with increase of concentration of the humic acids. A critical concentration at 0,2% is needed for the begin of retard reactions and the micell formation. The fragmentation of humic acids with high fragmentation rate will be less influenced by change of the concentration than those whose fragmentation rate are low.     

Wechselwirkungen zwischen Boden-Huminstoffen und Metall-Ionen II. Untersuchung von Boden-Huminstoffen mit der Gel-Permeations-Chromatographie und der Dampfdruck-Osmometrie

Interaction between soil humic substances and metal ions. II. Investigation of soil humic substances by gel permeation chromatography and vapour pressure osmometry By gel permeation chromatography and vapour pressure osmometry average molar masses of soil fulvic and soil humic acids from two horizons of a podzol were determined. For the fulvic acids average molar masses of 9000 g/mol were obtained by the chromatographic method, while 5000 g/mol were obtained by the osmometric method. In contrast to these results for the humic acids values were measured which are 3 - 4 times larger when measured by gel permeation chromatography and 2 - 3 times smaller when measured by vapour pressure osmometry. The average molar masses found show that the applied methods of isolation and purification as well as the different determination methods with the experimental conditions attached to them have a considerable influence on the molecular size of the isolated humic substances.     

Speciation of iodine in soils

In order to analyze the behavior and phytoxicity of iodine in soil, the chemical forms of soil iodine must be identified. Therefore, a method for quantitative speciation of iodine in soil was proposed. Iodine extracted from soil samples with tetrametBPyIammonium hydroxide (TMAH) was separated into humic and fnalvic acid fractions at pH4 1.5 after the addition of ascorbic acid into the TMAH extract to reduce iodate into iodide. Since the iodide in the TMAH extract was recovered in the fdvic acid fraction by this procedure, iodine contained in the haamic acid fraction was considered to be organically bound. Podine in the fulvic acid fraction was separated into organic iodine bound to fnlvic acids and the total inorganic iodine. Furthermore, iodine soluble from soil in 0.1 mol L^-1 potassium chloride was assumed to correspond to the amount of total iodide in soil, and from the difference in the concentration of total inorganic iodine and soluble iodide, the amount of iodate was calculated. By the application of this method, iodine in soil was separated into four fractions: organic iodine bound to humic acids, organic iodine bound to fulvic acids, iodate, and iodide. This speciation method was applied to two soils. It was found that s Barge proportion of iodine in soil occurred in an organicalPy bound form.     

The process of manganese depositton in paddy soils

Abstract

The changes in quality and quantity of phenolic substances in the decaying process of rice straw in a soil were compared under moist and flooded conditions for 200 days. The amounts of phenolic substances divided into fractions of humic acid and fulvic acid, ether- and butanol-extractable and organic solvent-unextractable fractions, then the amounts of individual phenolic acids were determined. The following results were obtained.

1) Alkali-extractable total phenolics as well as individual phenolic acids decreased more rapidly under moist, than under flooded, conditions as rice straw decayed in the soil. The phenolics present were mainly attributable to the straw, not to the soil.

2) The decrease in the level of total phenolics in the early stage of the decaying process was mainly due to the decrease in ether-extractable phenolic compounds in the fulvic acid fraction, and in the later stage, was mainly due to the decrease in butanol-extractable phenolics in the humic acid fraction.

3) The amounts of butanol-extractable phenolics and organic solvent-unextractable phenolics were larger in humic acid than in fulvic acid. On the other hand, a larger amount of organic solvent-extractable phenolics, especially ether-extractable phenolics, was present in fulvic acid.

4) The degradation patterns and pathways of individual phenolic acids in the decaying process of rice straw in soil were found to be the lame as those of decaying straw without soil which were reported previously.

5) The level of phenolic substances in the humic acid was not greatly changed during the decaying process, but the phenolic substances in fulvic acid rapidly increased for 30 days and then rapidly decreased to a constant level.     

A COMPARISON OF THE POLYCARBOXYLIC ACIDS EXTRACTED BY WATER FROM AN AGRICULTURAL TOP SOIL WITH THOSE EXTRACTED BY ALKALI

Humic and fulvic acids were isolated from an agricultural soil by conventional means. The same soil was extracted with water and the organic matter freed of inorganic and low molecular weight substances. The usual chemical differences between humic acid and fulvic acid were confirmed and the water extract was shown to resemble fulvic acid quite closely. Further fractionation of the fulvic acid and water extract showed that the elemental composition, carboxyl and acidic hydroxyl contents, molecular weights, and infrared spectra of the purified polycarboxylic acids were virtually identical. Both promoted the same growth response in cultured isolated tomato roots. It is suggested that the qualitative similarity of fulvic acid to the polycarboxylic acid extracted by water justifies the use of the more easily isolated fulvic acid in physiological experiments on the direct effects on plants of soil organic matter.     

Chromatographische Unterscheidung von Huminstoffen und Nichthuminstoffen aus Schwarzerdehumus

Chromatographic distinction of humic and non humic substances in chernozem-humus Fulvic acids, brown humic acids and grey humic acids from a chernozem from the Austrian Marchfeld were analyzed chromatographically on controlled pore glass with pore diameters of 177 and 259 Å. Concentration of coloured material and concentration of carbon were recorded in the chromatogramms. Specific extinctions at 400 nm were calculated for unit of C and maximal values were taken as constants specific for “pure” humic substances. These were 445,6 ± 10,5,388,7 ± 19,3 and 128,9 ± 0,8 for “pure” grey humic acids, brown humic acids and fulvic acids, respectively. With the aid of these constants, “pure” humic substances could be distinguished from accompanying non humic substances. “Pure” humic substances amounted to 63%, non humic substances to 37% of extractable organic C. 53%, 22% and 25% of the carbon of “pure” humic substances were from grey humic acids, brown humic acids and fulvic acids, respectively.     

Effect of soil depth on acid properties of humic substances extracted from an ombrotrophic peat bog in northwest Spain

The most southerly ombrotrophic peat bogs in Europe are in Galicia (northwest Spain). The humic matter in them originates from chemical processes in anaerobic conditions. We studied the acid properties of fulvic acids and humic acids isolated from two peat horizons of an ombrotrophic peat bog by potentiometric titration. Solutions containing 25, 50 and 100 mg l⁻¹ of each humic substance were titrated at ionic strengths 0.005 m , 0.01 m and 0.1 m (with KNO₃ as the inert electrolyte). Charge curves were analysed with a Donnan model to determine the intrinsic proton binding parameters. The concentration of the humic substance affected the charge curves more significantly at pH exceeding 6, and tended to disappear at greater concentrations. The proton binding conditional constants decreased with increasing ionic strength, this effect being more significant in the carboxylic groups with less affinity for protons. The proton binding constant of the carboxyl groups in a fulvic acid was one order of magnitude less than the value for the corresponding humic acid, whereas for the phenolic groups the values for both fractions were similar. The total content of acid groups was approximately 2 mol kg⁻¹ greater in the fulvic fraction than in the humic fraction. Both humic fractions from the lower horizon contained more acid groups than those from the upper horizon, mainly because the content of carboxyl groups increases with soil depth. Therefore, the humic substances in the lower horizon of the peat will be more negatively charged, which will affect their solubility and the binding of metal ions.     

Sequential exhaustive extraction of a Mollisol soil, and characterizations of humic components, including humin, by solid and solution state NMR

A comprehensive sequential extraction procedure was applied to isolate soil organic components using aqueous solvents at different pH values, base plus urea (base‐urea), and finally dimethylsulfoxide (DMSO) plus concentrated H₂SO₄ (DMSO‐acid) for the humin‐enriched clay separates. The extracts from base‐urea and DMSO‐acid would be regarded as ‘humin’ in the classical definitions. The fractions isolated from aqueous base, base‐urea and DMSO‐acid were characterized by solid and solution state NMR spectroscopy. The base‐urea solvent system isolated ca. 10% (by mass) additional humic substances. The combined base‐urea and DMSO‐acid solvents isolated ca. 93% of total organic carbon from the humin‐enriched fine clay fraction (<2 μm). Characterization of the humic fractions by solid‐state NMR spectroscopy showed that oxidized char materials were concentrated in humic acids isolated at pH 7, and in the base‐urea extract. Lignin‐derived materials were in considerable abundance in the humic acids isolated at pH 12.6. Only very small amounts of char‐derived structures were contained in the fulvic acids and fulvic acids‐like material isolated from the base‐urea solvent. After extraction with base‐urea, the 0.5 m NaOH extract from the humin‐enriched clay was predominantly composed of aliphatic hydrocarbon groups, and with lesser amounts of aromatic carbon (probably including some char material), and carbohydrates and peptides. From the combination of solid and solution‐state NMR spectroscopy, it is clear that the major components of humin materials, from the DMSO‐acid solvent, after the exhaustive extraction sequence, were composed of microbial and plant derived components, mainly long‐chain aliphatic species (including fatty acids/ester, waxes, lipids and cuticular material), carbohydrate, peptides/proteins, lignin derivatives, lipoprotein and peptidoglycan (major structural components in bacteria cell walls). Black carbon or char materials were enriched in humic acids isolated at pH 7 and humic acids‐like material isolated in the base‐urea medium, indicating that urea can liberate char‐derived material hydrogen bonded or trapped within the humin matrix.     

The distribution of the stable carbon isotope (13C/12C) in fractions of soil organic matter

The carbon-isotopic composition of fulvic and humic acid from the A horizons of eight soil types, developed under a wide variety of climatological conditions, was measured. The fulvic acid is always enriched in ¹³C as compared with the humic acid from the same soil by a rather constant factor of 0.9?. The fulvic acids are isotopically closer to the plant source of the organic matter and thus represent an intermediate stage in the formation of humic substances. Depth sections of peat soil showed that carbon isotopes can be used to evaluate the dynamic nature of the fulvic-acid fraction. With depth, a transfer of carbon groups from polysaccharides to fulvic acid is seen. Based on isotopic evidence it is shown that in addition to formation of β-humus, part of the fulvic acid is condensed with depth to a stable humic fraction — humin.     

土壤中水溶性有机质的结构特征及其与富里酸、胡敏酸的比较

采用元素分析、1HNMR和FTIR研究了黄泥土中水溶性有机质组成及结构特征,并与富里酸、胡敏酸进行比较。结果表明:胡敏酸含有大量的芳香族不饱和物质,烷基链烃多,支链长;富里酸以含有大量的羧基为主要结构特征;水溶性有机质主要由碳水化合物组成,含有大量的羟基,芳香族不饱和物质少。