Chemical and physical characteristics of humic substances extracted from greek soils varying in classification order and natural drainage

Abstract

Humic and fulvic acids were extracted from the surface horizons of Alfisols, Vertisols, and Entisols with good and impeded natural drainage. These profiles are located in the temperate subhumid zone. The extracted humic substances were characterized by elementary and functional group analyses, IR‐spectroscopy, differential thermal analysis (DTA) and electron spin resonance spectroscopy (ESR). Some differences in the humic substances seem to be associated with differences in the natural drainage of the soils. When data from samples of the same soil order are compared, indicate that humic (HAs) and fulvic acids (FAs) extracted from soils with impeded drainage, have higher contents of carbon and spin concentration, but less total acidity and fewer carboxylic groups (COOH), than the respective humic substances extracted from well drained soils. The IR‐spectra of the HAs extracted from soils with impeded drainage showed more aliphatic groups than those of the well drained soils. No essential differences, which could be related to the drainage conditions of the studied soils, were observed in the IR‐spectra of FAs. DTA‐diagrams shows that the thermal stability of the HAs and the FAs are related to their carbon and ash contents. Iron was the dominant element in the ash of the humic acids, aluminum and silicon were the most abundant elements in the ash of the fulvic acids.     

The chemistry of humic and fulvic acids extracted from argentine soils—I. Analytical characteristics

Five humic and three fulvic acids were extracted from Argentine Chestnut, Brunizem, Solod and Solonetz soils and analysed by electrometric, spectroscopic and spectrometric methods. There were great similarities in elementary analysis, functional group content, absorption characteristics in the visible region and in the IR, and in the ESR measurements between the humic acids and, similarly, between the fulvic acids. There were distinct differences between the humic and fulvic acids in C, H, N and O content, distribution of oxygen in functional groups, E₄/E₆ ratios and free radical content.     

CHEMICAL DEGRADATION OF HUMIC AND FULVIC ACIDS EXTRACTED FROM MEDITERRANEAN SOILS

Humic and fulvic acids were extracted from two Israeli and tour Italian soils and oxidized with alkaline permanganate solution after methylation. Following oxidation, the degradation products were separated by solvent extraction and chromatographic methods and identified by gas chromatography-mass spectrometry. Major oxidation products were aliphatic, phenolic and benzenecarboxylic acids. In toto, 33 oxidation products were identified. These were essentially the same compounds as those produced by the permanganate oxidation of methylated humic and fulvic acids extracted from soils formed under widely differing climatic and geologic conditions, except that yields of phenolic acids from Mediterranean humic and fulvic acids were lower than those produced under similar conditions from humic materials extracted from other soils. The information provided by chemical degradation suggests that humic and fulvic acids from widely differing soils have similar chemical structures.     

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.     

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.     

The chemistry of humic and fulvic acids extracted from argentine soils—II. Permanganate oxidation of methylated humic and fulvic acids

Five humic and three fulvic acids, extracted from Argentine soils, were methylated and oxidized with KMnO* solution. The oxidation products were extracted into ethyl acetate, remethylated, separated by preparative gas chromatography and identified by comparing their mass and micro-IR spectra with those of authentic specimens.The major oxidation products from the humic acids were benzenetetra, -penta-, and -tricarboxylic and hydroxybenepentacarboxylic acid. The major compounds isolated from the fulvic acid oxidation products were aside from benzenecarboxylic and phenolic acids, substantial amounts of ethyl-benzylsulfonate and N-methyl-benzylsulfonamide, one complex aromatic ester and two anhydrides. The origin of the S-containing compounds is uncertain; they could be impurities. Weight ratios of benzenecarboxylic to phenolic acids averaged 5·8 for humic acids but only 0·9 for fulvic acids, suggesting an enrichment in phenolic structures in the fulvic acids. Possible structural arrangements for humic and fulvic acids are discussed.     

Paramagnetic properties of humus acids of podzolic and bog-podzolic soils

The contents of free radicals in preparations of humic and fulvic acids extracted from virgin and plowed podzolic, surface gleyic podzolic, and peaty podzolic-gleyic soils were determined. The concentration of paramagnetic centers in the humic acids was 1.5–2 times higher than that in the fulvic acids. The agricultural use decreases the paramagnetic activity of the humus compounds and promotes the accumulation of biothermodynamically stable organic compounds in the plow horizons.     

A comparative study of molecular weight distribution of water-soluble humic substances,humic acids,and fulvic acids extracted from sod-podzolic soils

The alteration of organic matter from three sod-podzolic soils in the course of the extraction of water-soluble humic substances was studied by means of size-exclusion chromatography using a combined UV-DOC detector. A comparison of water-soluble humic substances with humic and fulvic acids extracted from the same soils was carried out.     

Humic and fulvic acids as indicators of soil and water pollution

Humic substances are the major organic components of soil and sediments, but little is known on how they are affected by environmental and industrial pollution. To find out whether such effects could be recognized, a number of analytical characteristics were compared of humic and fulvic acids extracted from unpolluted and polluted soils and sediments. The main differences were that, per unit weight, polluted humic and fulvic acids contained more N, S and H but fewer CO₂H groups, and were more aliphatic than unpolluted samples. Unusually high N and S contents of humic materials appear to be the most valid indicators of pollution. Humic acids are preferred to fulvic acids as indicators of pollution because the former are more readily separated and purified.     

The distribution of nitrogen in some highly organic tropical volcanic soils

The qualitative and quantitative distribution of N-compounds in 10 tropical soils, and in a number of humic materials extracted from representative samples thereof, was determined after 6 N HCl hydrolysis.Eighty to 98% of the total N in the soils and humic materials was hydrolysable by 6n HCl. Slightly less than one half the hydrolysable N in the soils and humic fractions consisted of amino acids. Well-drained soils and fulvic acids extracted from them contained unusually high concentrations of the acidic amino acids, aspartic and glutamic acids. Between 80 and 95% of the amino acids in the soils was accounted for in the humic materials + NaOH-insoluble organic residues. NH⁺₄-N released by acid hydrolysis was generally higher for the soil samples than for the humic materials. Amino sugar-N constituted relatively small proportions of the total N in the soils and humic fractions.Our data suggest that large quantities of amorphous allophanic materials coupled with relatively high enzymic activity are responsible for the observed accumulation of acidic amino acids in the well-drained tropical volcanic soils.     

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.     

POLYCARBOXVLIC ACIDS EXTRACTED BY WATER AND BY ALKALI FROM AGRICULATURAL TOP SOILS OF DIFFERENT DRAINAGE STATUS

Water-ex tractable poly carboxy lie acids and alkali-extractable humic acids and fulvic acids, were isolated from agricultural top-soils of two soil associations. Samples from four soil series from each association were selected with drainage status varying from well-drained to very poorly-drained. The amounts of atkali-extractable humic acid and water-ex tractable polycarboxylic acids were highest in the very poorly-drained soils whilst the amounts of alkali-extractable fulvic acid were generally similar in all the soils, although the fulvic acid accounted for a lower proportion of the total organic matter in the poorly-drained soils. Oxalate-extractable aluminium decreased with increased drainage impedance, whilst no such trend was observed for oxalate-extractable iron. It is suggested that the fulvic acid-like polycarboxylic acids are removed from the soil solution by adsorption onto sesquioxides; so that the lower content of aluminium oxides in the very poorly-drained soils results in depressed levels of fulvic acid and increased concentrations of water-extractable polycarboxylic acids.     

Acid properties of fulvic and humic acids isolated from two acid forest soils under different vegetation cover and soil depth

We studied the acid‐base properties of 16 fulvic acids and 16 humic acids isolated from the surface (3–15 cm) and subsurface (> 45 cm) horizons of two types of acid forest soils, derived respectively from amphibolite and granite rocks, under five different types of vegetation. The observed differences between the contents of humic substances in the two types of soils were related to the degree of Al‐saturation of the soil organic matter, as indicated by the molar ratio between pyrophosphate extractable Al and C. Humic fractions were characterized in terms of elemental composition, and CPMAS ¹³C NMR spectrometry. The contents of carboxylic and phenolic groups were estimated by potentiometric titrations conducted in 0.1 m KNO₃ in a nitrogen atmosphere. The fulvic acids contained more carboxylic groups but less phenolic groups than the humic acids: the ratio of phenolic to carboxylic groups in the humic acids was 0.48 ± 0.10 and in the fulvic acids 0.23 ± 0.05. The mean values of the protonation constants of each of the humic substance fractions can be used as generic parameters for describing the proton binding properties. The fulvic acids isolated from the subsurface horizon of the soil contained between 2.6 and 23% more carboxylic groups, and the humic acids between 8 and 43% more carboxylic groups than those isolated from the surface horizon of the same soil.     

Effect of cultivated plants on physico‐chemical characteristics of humic substances of soils amended by sewage sludge

Abstract

Humic substances were extracted from raw sewage sludge samples as well as an alluvial slightly alkaline soil [Typic Xerofluvent (So)], a clay loam soil [Calcixerollic Xerochrept (M)] and the corresponding field plots amended with different rates of sewage sludge and cultivated with corn and cotton respectively, in a two‐year field experiment. These substances have been characterized by chemical and spectroscopic methods. The chemical analyses showed that humic acids (HAs) and fulvic acids (FAs), were effected by the cultivated plant. Humic substances extracted from field plots with cotton showed higher carbon, but less nitrogen (N), total acidity and carboxylic groups content, as compared with those under corn. Generally HAs and FAs extracted from the fields plots amended with sewage sludge had higher N content, lower values of total acidity, carboxylic groups and carbon contents than those from the unamended soils. The FT‐IR spectra of humic (HAs) and fulvic (FAs) acids extracted from sewage sludge indicated the presence of high percentage of aliphatic carbon, polysaccharides and proteinaceous materials. The spectra of the humic matter in the field plots showed less aliphatic but increased amide stretch in comparison with the sludge. The absorption due to C=O in carboxylic groups of the FAs was not pronounced, though the presence of polysaccharides and protein decomposition products was clearly indicated.     

Effect of continuous compost application on humus composition and nitrogen fertility of soils in a field subjected to double cropping

We investigated the effect of continuous compost application on humus composition and N fertility of soils in a field subjected to double cropping (paddy rice and barley) for 25 years. Soil samples were collected from three different plots: (a) No-NF, fertilizer containing P and K but no N; (b) F, fertilizer containing N, P, and K; and (c) F+C, fertilizer plus compost. The amounts of total humus, extracted humus, and humic and fulvic acids increased in the order No-NF<F≪F+C. The amounts of humic and fulvic acids were 2.7 and 1.7 times larger in the F+C plot than in the F plot, respectively. The degree of humification of the humic acids decreased in the order No-NF<F<F+C. The absorption curves and ¹³C-NMR spectra (TOSS method) of the humic acids indicated the presence of lignin-like structure, and its degree was the strongest in the F+C plot. The ¹³C-NMR spectra showed distinct differences in the distribution of carbon species between humic and fulvic acids. In humic acids, the content of aromatic-C, ranging from 37 to 44%, was the highest among carbon species. In fulvic acids, the content of O-alkyl-C, ranging from 45 to 51%, was the highest. The amounts of phosphate buffer-extractable N (PEON) and total N (TN) increased in the order No-NF<F<F+C. The amounts of PEON and TN were 1.2 and 1.7 times larger in the F+C plot than in the F plot, respectively. Present and previous findings indicated that continuous compost application could improve various properties of soils in a field subjected to long-term double cropping.     

不同年代的埃特纳火山土壤上用甘油萃取有机质的特性

We characterized humic acids (HAs) and glycerol-extractable organic fractions (GEOFs) extracted from four Andisols, taken from comparable soil-climate conditions on the east side of Mount Etna. The soils were formed on old lava (about 9 000 years ago), old tephra (about 8 700 years ago), recent lava (about 2 600 years ago) and recent tephra (about 3 600 years ago). A part of the organic matter of the soils, deprived of HAs and fulvic acids (FAs), was isolated by glycerol extraction. The GEOF can not be extracted with alkaline solutions, probably because it is closely bound to the mineral component of the soil. The characterization of the extracted organic fraction was carried out using elementary and functional group analysis and Fourier transform infrared (FT-IR) spectroscopy. About 20 extractions were necessary to extract the HA and FA from the older soils and about 10 extractions to extract them from the younger soils. Data showed that the GEOFs had a greater ash content and a smaller N content, as well as a greater presence of aliphatic compounds and carboxylic groups as compared to the HA extracted from the same soil. The GEOFs extracted from younger soils also had a lower yield, ash and COOH-group content, and were more aliphatic than the GEOF extracted from older soils. Finally, the GEOFs were more closely bound to the amorphous component of the soil (‘short-range’ minerals) and consequently less subject to biodegradation.     

The persulfate oxidation of fulvic acids

Persulfate oxidation of two fulvic acids from different soils was accomplished. This is a new mild chemical degradative method which differentiates between fulvic acids isolated from soils developed under widely differing environments. A fulvic acid isolated from an Humic Haplorthod gives as major oxidation products phenolic acids, whereas a fulvic acid from an Andic Hapludult yields benzenecarboxylic acids as most abundant compounds. The possibility to differentiate between fulvic acids from different soils, as chemical degradation with persulfate does, offers interesting prospects to the characterization of humic materials.     

The humus state of the soils of locally hydromorphic landscapes in the lower reaches of the don river

The humus state of rainfed chernozems affected by local waterlogging was studied. The total humus content in the hydromorphic chernozems increases, as well as the content of fulvic acids, whereas the content of nonhydrolyzable residue (humin) decreases. A significant increase in the portions of the third fractions of humic and fulvic acids is observed. The role of the fine silt and clay fractions in the binding of humic substances increases in the lower horizons of locally hydromorphic soils. The increase in the content of fulvic acids (fulvatization) is mainly due to their predominance in the clay fraction. The latter is specified by the significant narrowing of the C_ha-to-C_fa ratio, the lower content of the nonhydrolyzable residue, and the increased content of the clay-bound (3rd fraction) fulvic and humic acids. The composition of the humus in the fine silt fraction of the studied soils is characterized by an increased amount of humic acids of the second fraction with a decrease in the relative content of fulvic acids.     

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.