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.     

Chemical and physical characteristics of humic and fulvic acids extracted from soils of the Mediterranean region

Humic and fulvic acids were extracted from two soils from Israel and from four soils from southern Italy. Following purification, the humic substances were characterized by elementary and functional group analyses, spectrophotometric and spectroscopic methods, thermal analysis and by scanning electron microscopy.The analytical characteristics of the humic and fulvic acids extracted from the Israeli and Italian soils were generally similar to those of humic materials originating from soils formed under widely differing geographic and pedologic conditions. There were some differences in the content and composition of inorganics in the fulvic acids which were reflected in functional group analyses, IR and ESR spectra, DTA curves and SEM micrographs.     

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.     

Paramagnetic Properties of Humic Substances in Taiga and Tundra Soils of the European Northeast of Russia

The study of paramagnetic activity of humic substances in taiga and tundra soils of the Komi Republic and the assessment of the influence of soil hydromorphism on concentrations of free radicals in the structure of humic acids (HAs) and fulvic acids (FAs) have been performed. The concentration of free radicals in HA specimens was up to 11 times higher than that in FA specimens due to a higher content of aromatic and other condensed structures in HA molecules. This fact attests to the high capacity of HAs to polymerization and complexation reactions with participation of radicals. The average value of g-factor is higher for FA specimens than for HA specimens, which attests to a greater electron density shift of unpaired electron to oxygen atom in the structure of FAs because of its spin-orbital interaction with oxygen-containing functional groups, the concentrations of which are significantly higher in FAs than in HAs. An increase in the concentration of free radicals in the molecular structure of HAs is observed in taiga soils with an increase in the degree of their hydromorphism (from automorphic to semihydromorphic soils), which is related to the biohydrothermal conditions of humus formation in bog-podzolic soils with retarded biochemical processes and low degree of plant litter humification. As a result, HAs with the high content of free radicals in their structure are formed. An opposite situation is observed for HAs in tundra soils with a decrease in the content of unpaired electrons under conditions of the increased hydromorphism. The difference in the character of changes in the paramagnetic activity of HAs in taiga and tundra soils with different degrees of hydromorphism may be related to different natures of plant residues participating in humification processes. A tendency for a decrease in the paramagnetic activity in both HAs and FAs from the south to the north is observed, which may be related to a general decrease in the content of poly-conjugated systems in the structure of humic substances in tundra soils.     

Molecular composition of humic substances in tundra soils (13C-NMR spectroscopic study)

Functional groups and molecular fragments of humic substances (HSs) from cryohydromorphic peat gley tundra and surface-gley tundra soils have been identified by ¹³C-NMR spectroscopy. The analysis of HS preparations has shown that the molecules of humic acids (HAs) are enriched with aromatic fragments compared to fulvic acids (FAs). Aliphatic chains, carbohydrate- and amino acid-type structures prevail in the carbon skeleton of the FAs. An integrated parameter of the HS hydrophobicity has been proposed. The parameter represents the total portion of unoxidized carbon atoms and allows indirectly assessing the amphiphilic properties of HSs.     

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.     

几种胡敏酸和富里酸分子结构模型的三维可视化与特性研究

针对已提出的几种胡敏酸和富里酸的二维分子结构模型,应用HyperChem软件转换为三维结构并进行几何优化,计算了这些三维模型的能量以及定量构效关系(QSAR)参数。结果表明:几种模型在三维结构和特性上都各不相同,这为从空间角度更直观地认识腐殖物质的分子结构提供了可能性。     

Chemical structure of humic acids in biosolids-amended soils as revealed by NMR spectroscopy

We used NMR spectroscopy to characterize humid acids extracted from soils that had received long-term application of 2 levels of biosolids to evaluate the soil organic matter (SOM) stability in biosolids-amended soils. The study also quantified fulvic acids (FAs), humic acids (HAs) and Fe/Al oxides. The soils were collected in 2004 from 7 fields, in Fulton County, southwestern Illinois, which received biosolids at a cumulative rate of 0 (control), 554 (low biosolids) and 1,066 (high biosolids) Mg ha⁻¹. The application of biosolids increased both FA and HA contents, but biosolids-amended soil and control soil did not differ in FA/HA ratio. Biosolids application had no effect on water-soluble organic carbon content. Biosolids application increased the presence of Fe/Al in the SOM complex and lowered its C/Fe and C/Al ratios. ¹³C NMR spectra showed increased alkyl C and decreased aromatic C content in soil HAs with the application of biosolids, and the extent of such changes was higher with high than low biosolids treatment. Under biosolids application, the soil HAs’ C structure shifts from O-alkyl-dominant to alkyl-dominant. Biosolids application does not decrease SOM stability but rather increases the stability of soil humic substances.     

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.     

Chemical and spectroscopic characterization of Humic acids from a soil toposequence in venezuela

Abstract

An investigation was conducted on physico‐chemical properties of humic acids (HAs) in Venezuelan soils. The HAs were extracted by the NaOH method from a Banco‐Bajio‐Estero soil toposequence (local names for soils located at high, intermediate and low topographic levels), in the Venezuelan plains (Mantecal, Apure State). The extracted HAs were analyzed for elemental composition and characterized by fluorescence, Fourier transform infrared (FT‐IR) and electron spin resonance (ESR) spectroscopies. The results showed that free radical concentration of HAs increased from soils at the highest to soils at the lowest topographic position. High carbon (C), nitrogen (N), and carboxyl group contents, E₄/E₆ ratio, aliphatic character and concentration of free radicals, and low oxygen (O) and phenolic hydroxyl group contents and total acidity were typical of HA from soils at the lower relief position. The FT‐IR spectra indicated that the HA from the soil at the lowest topographic position tended to have a slightly higher content of carboxyl groups than the HAs from soils at higher topographic levels. The observed fluorescence was attributed to the presence of condensed aromatic moieties and/or conjugated unsaturated systems of various complexity in the HA macromolecules.     

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.     

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.     

土壤腐殖质分组研究

采用Pallo法对两种耕地土壤腐殖质进行分组,初步研究了各组分的数量和结构特征。结果表明:焦磷酸钠提取的胡敏酸(HAp)是胡敏酸(HA)的主要组分;游离富里酸(FAf)是富里酸(FA)的主要组分;胡敏素(HM)的主要组分为非溶解性胡敏素(ISHM),而溶解性胡敏素(SHM)含量较低。通常随土层深度增加,HA、HM各组分的绝对数量和相对数量都下降;FA各组分的绝对数量也下降,而相对数量增加;HA/FA比值下降。一般来看,焦磷酸钠提取的富里酸(FAp)、氢氧化钠提取的富里酸(FAs)比相应的HAp、氢氧化钠提取的胡敏酸(HAs)的分子结构简单,铁结合胡敏素(HMi)比粘粒结合胡敏素(HMc)的分子结构简单;随土层深度增加,HAp、HAs的分子结构变简单,而HMi、HMc的分子结构变复杂。     

Characterization of humic substances derived from swine manure-based compost and correlation of their characteristics with reactivities with heavy metals

Various composts contain a significant amount of humic substances including humic acid (HA) and fulvic acids (FAs). The FA fraction in soils is considered to be sensitive to agronomic and environmental factors. In this study, three fractions of humic substances, HA (MW > 1000 Da), FA (MW > 1000 Da), and FA (MW < 1000 Da) were extracted from swine manure-based compost and characterized, and then, their reactivities were correlated with heavy metals. Compositions of the three fractions of humic substances were characterized by elemental and total acidity analyses and electron spin resonance (ESR), Fourier transform infrared (FTIR), and 13C nuclear magnetic resonance with cross-polarization and magic-angle spinning spectroscopic techniques. Elemental analyses indicated that HA has higher contents of C, H, N, and S than those of FAs. However, FA (MW > 1000) and especially FA (MW < 1000) have higher contents of O than that of HA (MW > 1000). The g values of the ESR spectra of the three fractions showed that the organic free radical characteristics and the widths of the spectra and free radical concentrations of the three fractions are significantly different. The FTIR spectra indicated that HA (MW > 1000) is abundant in C=C bonds while FA (MW > 1000), especially FA (MW < 1000), are abundant in C=O bonds. In addition, 13C NMR spectra indicate that carboxyl contents of FA (MW > 1000), especially FA (MW < 1000), are higher than that of HA (MW > 1000). The sequence of the reactivity in terms of acidic functional groups was FA (MW < 1000) > FA (MW > 1000) > HA (MW > 1000). Elemental and functional group compositions of the three fractions significantly correlated with reported reactivities with heavy metals. The application of swine manure-based compost containing HA and FAs fractions to soil and associated environments may thus significantly affect the concerned reactions with organic and inorganic compounds including pollutants.     

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.     

Cultivation-Induced Effects on the Organic Matter in Degraded Southern African Soils

We studied quantitative and qualitative changes in soil organic matter (SOM) due to different land uses (reference woodland versus cultivated) on six soils from Tanzania (Mkindo and Mafiga), Zimbabwe (Domboshawa and Chickwaka), and South Africa (Hertzog and Guquka). Structural characteristics of the humic acids (HAs) were measured by Curie-point pyrolysis–gas chromatography/mass spectrometry (P_y–GC/MS) and solid-state ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy. Significant changes in concentration and composition of SOM were observed between land uses. Losses of organic carbon after cultivation ranged from 35% to 50%. Virgin soils showed large proportions of colloidal humus fractions: humic acids (HAs) and fulvic acids (FAs) but negligible amounts of not-yet decomposed organic residues. The change in land use produced a contrasting effect on the composition of the HAs: a noteworthy “alkyl enhancement” in Mkindo soil and “alkyl depletion” in Chikwaka and to a lesser extent in Domwoshawa. The remaining soils displayed only minor alterations.     

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.     

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.     

Phosphorus in humus acids

The distribution of phosphorus among humus acid groups in different soil types was studied. It was shown that the binding of P with acid-soluble and-insoluble organic components is determined by the acid-base status of soils, which controls the predominant interaction of P with Fe and Al or with Ca and Mg, and the solubility of the resulting organic phosphates in acid and alkali. The major part of P is associated with the group of humic acids (HAs) in the acid soils and with fulvic acids (FAs) in the neutral and calcareous soils. During the fractionation of organic matter from acid soils, the amount of P redistributed from the HA to the FA group can increase with an increasing acid or alkaline impact on the soil, which breaks the bonds of the phosphorus-bearing organic components with metals.