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.     

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.     

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.     

Sorption and desorption of cobalt by soils and soil components

The sorption of Co by individual soil components was studied at solution Co concentrations that were within the range found in natural soil solutions. Soil-derived oxide materials sorbed by far the greatest amounts of Co although substantial amounts were also sorbed by organic materials (humic and fulvic acids). Clay minerals and non-pedogenic iron and manganese oxides sorbed relatively little Co. It is considered that clay minerals are unlikely to have a significant influence on the sorption of Co by whole soils. Cobalt sorbed by soil oxide material was not readily desorbed back into solution and, in addition, rapidly became non-isotopically exchangeable with solution Co. In contrast, Co was relatively easily desorbed from humic acid and a large proportion of the Co sorbed by humic acid remained isotopically exchangeable. Cobalt sorbed by montmorillonite was more easily desorbed than that sorbed by soil oxide but less easily than that sorbed by humic acid. Cobalt sorption isotherms for whole soils at low site coverage were essentially linear and the gradients of isotherms increased with pH. A comparison of isotherm gradients for whole soils and individual soil components supported the suggestion that Co sorption in whole soils is largely controlled by soil oxide materials.     

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.     

MOLECULAR WEIGHT DISTRIBUTION OF SOIL ORGANIC MATTER AS AFFECTED BY ACID PRE-TREATMENT AND FRACTIONATION INTO HUMIC AND FULVIC ACIDS

Effects of acid pre-treatment and fractionation on the molecular weight distribution of OIM Na₄P₂O₇ organic matter extracts were investigated in a chronosequence of weakly weathered soils developed on aeolian sand in New Zealand. Acid pre-treatment of soils with OIM HCl followed by OIM HCI:03M HF was found to enhance the polydispersion in the nominal molecular weights of the extracts. The same treatment resulted in significant increases in yield and reduction in ash content. However, prolonged standing of extracts in the acids led to acid-induced polymerization, resulting in a predominance of organic matter in the higher nominal molecular weight ranges. Fractionation of organic matter extracts by acid precipitation into humic and fulvic acids did not separate them according to molecular weight as commonly believed. Instead, fulvic acids from most soils were found to have similar nominal molecular weight distributions to those of their humic acid counterparts. A large proportion of soil fulvic acid compounds was in the > 100 000 nominal molecular weight 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.     

Chemical studies on soil humic acids

Seventeen samples of soil humic acids, two fractions of soil fulvic acid sample, and several related compounds such as lignin, tannin, flavonoid and artificial humic substances were decomposed in conc. KOH solution at 180°C. Succinic acid, glutaric acid, phloroglucin, p-hydroxybenzoic acid, vanillic acid, protocatechuic acid, 3,4-dihydroxy-5-methoxybenzoic acid, and gallic acid were detected in the degradation products of humic acids. The amounts of these degradation products were discussed in relation to the degree of humification or the sources of the humic acid samples. Succinic acid also resulted from glucose, polymaleic acid, and the humic acid and humin prepared from glucose, but glutaric acid resulted only from glucose humic acid and glucose humin but not from glucose and polymaleic acid. Succinic acid and glutaric acid were supposed to result from the same structural portions in humic acids because of the very significant positive linear correlation between their amounts. p-Hydroxybenzoic, vanillic, protocatechuic, and 3,4-dihydroxy-S-methoxybenzoic acids were presumed to result mainly from lignin structure in humic acids. Soil humic acids yielded small amounts of gallic acid although the yields by hydrolysable tannins were in large amounts. The yields of above-mentioned degradation products from humic acids decreased with increasing degree of humification. Phloroglucin resulting from ftavonoids including condensed tannins were also found in the degradation products of humic substances. Its yield showed no linear correlation with RF value of humic acid, and is presumed to be rather related to the vegetation at the sites of soil sampling.     

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.     

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.     

Macromolecule‐P associations and inositol phosphates in some chilean volcanic soils of temperate regions

Abstract

Total organic P, humic and fulvic acid‐P associations and inositol phosphates in nine volcanic soils of southern Chile were determined. The concentration of organic P (Po) ranged from 654 to 1942 ppm accounting for 49% to 64% of total soil P. Phosphorus associated to humic (HA‐P) and fulvic acids (FA‐P) accounted for 51–68% and 32–49% of Po, respectively. Inositol penta‐ and hexaphosphates represented 42% to 67% of Po suggesting that significant amounts are associated with both humic and fulvic acids. Po content was significantly correlated to organic C, total soil P and HA‐P. HA‐P and FA‐P fractions obtained from the most representative soil were examined by dyalisis and gel filtration. While approximately 96% of HA‐P presented a molecular weight higher than 100,000 daltons, 53% of FA‐P had a molecular weight under 12,000 daltons. It is suggested that these more labile organic P forms would be more easily mineralized, thus increasing the available P pool.     

ANALYSIS OF THE POTENTIOMETRIC TITRATION OF NATURAL AND SYNTHETIC POLYCARBOXYLATES

Potentiomctric titrations of a variety of natural and synthetic poly-COOH's varying in molecular weight and COOH density gave pKm values varying from 3.5 to 5.2. The pattern of carboxylic acid group dissociation is discussed in terms of purely electrostatic assumptions and of COOH group clustering. Synthetic polymaleic acid showed many of the characteristics of both fulvic and humic acids, and therefore seems to be a reasonable representation of an average, hypothetical soil organic matter polycarboxylic acid.     

PROCESSES OF HUMUS FORMATION AND TRANSFORMATION IN SOILS OF THE CANADIAN GREAT PLAINS

A study of the A horizons of cultivated soils from Saskatchewan, Canada showed that the organic carbon contents were in the sequence semi-arid Dark Brown soils (1.7 per cent), < Black soils (2.55–2.8 per cent), < sub-humid Dark Gray soils (4.5 per cent). The relative proportions of humic acids and the ratios of humic acid: fulvic acid increased in a similar sequence. There were accompanying increases in extinction values at 280 nm, and in levels of nonhydrolyzable nitrogen suggesting more extensive polycondensation of humic materials. These observations are discussed in terms of a working hypothesis for humus formation and transformations, that gives particular emphasis to the soil environment and to interactions between organic and inorganic components.     

水稻土的腐殖质组成

土壤的有机质状况与成土条件之间有着紧密的联系。借助于腐殖质形成分析法,ТюРин确定了腐殖质形成过程的地带性规律。他指出,不同发生学土类,其腐殖质形成有着明显的不同^[1]。Кононова把土壤腐殖质看作为一个高分子物质体系,她证明成土条件对腐殖质的影响,不仅表现在分祖形成方面,而且也表现在胡敏酸的本性方面^[2]。另一方面,一些工作表明,有机厦状况的不同又将对土壤形成过程和土壤性质产生不同的影响^[3]。因此,研究土壤的腐殖质状况,不仅有助于对土壤性质的了解,而且可为成土过程,从而为土壤分类提供有益的资料。     

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.     

Analysis of total inositol phosphates in municipal solid waste compost-treated soils by two extraction methods

 Humic substances are the most dynamic component of agricultural soils. In this study, humic substances were extracted from soils based on standard acid/base solubility and by gel filtration using Sephadex G25. Organic P is a component of humic substances, and inositol phosphates are considered to have high prominence in organic P. The objectives of the study were to determine the effects of municipal solid waste (MSW) compost on the amount of inositol phosphates (IP) present in soils, and compare methods of extracting humic substances from soils. Total IP (IP_T) in soil extracts was determined following separation using a AG-1× 8 anion exchange resin, acid digestion and ICAP analysis for P. The percentage of IP (%IP) of the total P in the soil was also determined by colorimetric analysis. The soils were part of an experiment to study the effects of three rates of MSW compost and fertilizers on three crops grown in a Pugwash sandy loam (Humo-Ferric Podzol). The data were compared using ANOVA atP≤0.05; extraction methods, fractions [humic/fulvic, high/low molecular (MW)], and five treatments (three different rates of compost, fertilizer, and untreated soil) were compared. The gel filtration method extracted significantly more IP_T and %IP than the solubility method. In the solubility method, humic and fulvic acids contained the same amounts of IP_T and %IP, while the high MW fraction always contained more IP_T and %IP than the low MW fraction in the gel filtration method. Fulvic acids and the low MW fraction contained similar amounts of IP_T and %IP. There were differences in %IP between compost-treated soils and the non-compost-treated soils, although there were no differences in IP_T due to rate of compost addition. Received: 20 October 1999     

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.     

Studies of aluminium complexation to humic and fulvic acids using a method for the determination of quickly reacting aluminium

We have recently presented a method for the determination of quickly reacting aluminium in natural waters based on kinetic discrimination in a flow system. This method has been further validated using both an isolated fulvic acid and natural humus-rich waters. Different reaction times were used, further clarifying the response of aluminium complexed with humic and fulvic acids. Equilibrium dialysis was also used as a reference method for comparison. With the reaction time used normally, 2.3 s, aluminium complexed with humic or fulvic acids was shown not to be measured with our method. These results suggest that our method may be used for studies of the complexation of aluminium with humic and fulvic acids. We have compared results from a series of solutions with varying concentrations of fulvic acids with calculations based on two different models obtained from complexation studies performed by potentiometric titrations and by equilibrium dialysis. The results show fair agreement and suggest that our method can be used for such studies. This approach is more sensitive and rapid than potentiometric titrations, enabling studies of humus interactions with aluminium at concentrations similar to those found in natural waters.     

Incorporation of nitrogen from urea fertilizer into soil organic matter in rice paddy and cassava upland fields in Indonesia

Incorporation of newly-immobilized N into major soil organic matter fractions during a cropping period under paddy and upland cropping systems in the tropics was investigated in Jawa paddy fields with and without fish cultivation and a Sumatra cassava field in Indonesia. ¹⁵N-labelled urea (¹⁵N urea) was applied as basal fertilizer, and the soil samples were collected after harvest. The percentage of distribution of the residual N in soil from ¹⁵N urea into the humic acids, fulvic acid fraction, and humin were 13.1–13.9, 19.0–20.5, and 53.4–54.3%, respectively, for the Jawa paddy soils, and 14.9, 27.4, and 52.4%, respectively, for the Sumatra cassava soil. These values were comparable to the reported ones for other climatic zones. The percentage of distribution of ¹⁵N urea-derived N into humic acids was larger than that of total N into the same fraction in all the soils. The distribution into the fulvic acid fraction was also larger for ¹⁵N urea-derived N than for total N in the Jawa soils. Humic and non-humic substances in the fulvic acid fraction were separated using insoluble polyvinylpyrrolidone (PVP) into the adsorbed and non-adsorbed fractions, respectively. Less than 5% of the ¹⁵N urea-derived N in fulvic acid fraction was detected in the PVP-adsorbed fraction (generic fulvic acids). The proportion of non-hydrolyzable N remained after boiling with 6 M HCl in the ¹⁵N urea-derived N was 9.4–13.5%, 17.3–26.7%, and 8.4–16.6% for the humic acids, generic fulvic acids, and humin, respectively. The significantly low resistance to acid hydrolysis suggested that the ¹⁵N urea-derived N was less stable than the total N in soil regardless of the fractions of humus.     

Micronutrient extraction in calcareous soils treated with humic concentrates

The use of humic concentrates in drip irrigation cultures in Spain has increased recently. Several companies offer different products to the farmers. It is suggested that such products are useful in improving the structure of the substrates, in increasing CEC of soils, in mobilizing micronutrients towards the roots and in acting as biological hormones. In our work, we have studied the effect of 11 different humic concentrates on extraction of iron and other micronutrients in the soil. Two substrates were used, a calcareous soil and a mixed substrate called “soil standard” since it has been made with components similar to those of a soil, but with standard materials. These soils were incubated with 11 different commercial humic concentrates. After the interaction, soils were extracted by the AB‐DTPA method. The results show that, in general, all commercial products increased extraction of micronutrients, but large amounts of humic concentrates were needed to increase them significantly. These quantities were greater than those reached in the bulk soil with the doses proposed by the distributors. However the amounts of humic substances used in this experiment can be reached in microsites near the droppers in a drip irrigation system. Although all humic concentrates increased micronutrients extraction, differences were noted on the efficiency of the different products. Humic rather than fulvic acids were responsible for this increase in extraction.