Chemical characteristics of humic acids from five soils in Kenya

Humic acids (HAs) isolated from five soils (Luvisols, with 460–600 mm rainfall, Nitosols and Ferralsol, with 1060–1950 mm rainfall) from different ecological regions of Kenya were characterized by ¹³C NMR and IR spectroscopy, elemental analyses and optical measurements. The data suggest that excessive rainfall in sub-humid regions may lower the molecular weights of the HAs as well as their aromaticities. Concentrations of aliphatic components, including aminoacids and carbohydrates, in the HAs from the sub-humid regions were higher (40–42 wt/wt %) than those in the HAs isolated from soils of the semi-arid regions (29–32 wt/wt %). Chemical characteristics of the soils from the sub-humid regions of Kenya resembled those of the HAs from temperate regions but differed from those of HAs originating from arid regions. Annual rainfall and vegetation appeared to affect the composition of HAs but effects of elevation and temperature were less clear.     

Chemical and spectroscopic characteristics of humic acids in marshes from the Iberian Peninsula

Purpose

To characterise soil humic acids (HAs) extracted from Spanish marshes formed under different vegetation types (Spartina maritima (GSp), Juncus maritimus (GJc), Phragmites australis (GPh), and Scirpus maritimus (VSc)), soil depths (0–20, 20–40 and 40–60 cm), physiographic position (low and high marshes), wetland types (salt marshes and lagoons) and environmental conditions (Atlantic and Mediterranean coast).

Material and methods

Soil samples were collected in five Spanish marshes, three on the Galicia province and two on the Valencia province. Humic acids were extracted and their elemental composition, semiquinone-type free radical (SFR) content, FTIR and CPMAS ¹³C NMR spectra determined. Total carbon (TC), total nitrogen (TN), total sulphur (TS), CaCO₃ content, and field pH and Eh (mV) in the marsh soils sampled were also measured.

Results and discussion

The field pH and Eh values were typical of coastal areas submitted to periodic inundations and the highest TC, TN and TS contents were found in the soil of lagoon marshes as an effect of physiographic position and wetland type. The HAs, in general, were highly aliphatic and exhibited a low SFR content, which suggests a low humification degree of the SOM formed in the studied areas. This is a result of the anaerobic decomposition to which SOM is submitted and the high input of plant-derived organic matter (OM) by vegetation. However, among the studied sites low salt marsh and subsurface layer of the high salt marsh showed higher SFR content, simpler FTIR spectra, higher lignin degradation and lower O-alkyl C/alkyl C ratio than the lagoon marshes, thus suggesting the presence of a more humificated SOM in these sites.

Conclusions

From the different factors analysed, only physiographic position (low versus high salt marshes) and wetland type (marshes versus lagoons) caused variations in the HAs characteristics, because as the studied soils are under anaerobic conditions, they control the exportation of plant-derived OM and the allochthonous OM contribution in the studied areas.     

Fate of humic acids isolated from natural humic substances

Composition of humic acids (HA) is a function of plant-derived inputs, degradation processes regulated by microorganisms, organo-mineral interactions and age. Characterization of different origin humic substances is important for evaluation of their contribution to stabile and labile carbon pool in the environment. The relative abundance of chemical components in HA isolated from soils, compost, commercial lignohumates, alginite, acadiane and lignite was studied with aim to quantify content of important biomarkers such as amino acid, lipids and polyphenols. HA were considered as a heterogeneous complex and high concentration of peptides, polyphenols and lipids was determined in acadian-HA to compare with soil-HA. Compost-HA contained much more amino acids to compare with soil-HA samples. Alginite-HA and lignite-HA were similar in biomarkers content to soil-HA. Fourier transform infrared spectroscopy confirmed that chemical composition and functional groups content differs with the origin, humification degree and the age of studied samples. Soil-HA are typically composed of a variety of ?OH, COOH?, C–O, C–H₂, (aliphatic and aromatic) groups, quinines, lignin fragments, polysaccharide, monosaccharide and proteins fragments, which are linked together by ?O?, ?NH?, ?H=, >C=O, metal ions and –S? groups. ¹³C NMR spectroscopy showed that aromatic carbon content was the highest in lignite-HA and soil-HA.     

Molecular characteristics of humic acids extracted from compost at increasing maturity stages

The molecular composition of humic acids (HA) extracted from compost at increasing maturity stages was determined by off-line TMAH-thermochemolysis-GC-MS, in combination with solid-state nuclear magnetic resonance (NMR) and infrared (IR) spectroscopies. While spectroscopy measurements followed the bulk changes, thermochemolysis provided a detailed molecular variation of HA composition. Both thermochemolysis and spectroscopy indicated that polysaccharides, alkyl, cyclic, and aromatic compounds were the predominant components of HA, the stable fraction of compost. NMR dipolar dephasing (DD) experiments confirmed that HA extracts contained lignin in lower amount than its oxidized degradation products. The progressive compost maturity was reflected in HA extracts by a decrease of carbohydrate content and a selective preservation of hydrophobic alkyl molecules, such as medium- and long-chain fatty acids, aliphatic alcohols, linear hydrocarbons, and plant polyester derivatives, like long-chain alkyl dicarboxylic acids, and ω-hydroxyacids. Spectroscopy results showed a concomitant entrapment in HA of biolabile compounds, such as peptidic moieties. The wide range of identified lipid components and plant biomarkers may represent useful tools to trace origin, quality, and transformation of amended compost in soil ecosystems.     

Comparison of humic acids derived from city refuse with more developed humic acids

Abstract

The humic acids (HA) from composted and uncomposted city refuse (CR) were characterized by degradative (oxidation with persulphate and permanganate) and non-degradative techniques (FT-IR and ¹³C-NMR) in order to analyze the effect of the composting process on these HA. They were also compared with commercial HA extracted from leonardite. The carboxyl and carbonyl group content of the HA from CR increased slightly during composting. Since the HA from the composted CR showed a lower N and H content, the FT-IR spectra showed a lower intensity in the bands corresponding to peptides and carbohydrates. Differences were revealed when the HA from both CR were compared with those from leonardite which showed a much lower N and H content and a less aliphatic character. The percentage of degraded products by persulphate was higher for the HA from uncomposted CR. For the HA from both CR the major components among the oxidation products were dicarboxylic acids and normal fatty acids. In the leonardite HA, the major components consisted of benzene polycarboxylic acids. ¹³C-NMR revealed an attenuation of the aliphatic character of the HA from CR with composting.     

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.     

风化煤腐殖酸对氮、磷、钾的吸附和解吸特性

研究了风化煤腐殖酸在不同pH值条件下对氮、磷、钾的吸附和解吸特性。结果表明,1)在pH.4～8条件下,随着氮、磷、钾初始处理浓度的增加,腐殖酸对其吸附量和解吸量均呈上升趋势,但解吸率均呈下降趋势;2)在不同pH值的介质溶液中,腐殖酸对氮、磷、钾的吸附和解吸特性不尽相同,其中,在碱性条件下,腐殖酸对氮的吸附和解吸作用较强,在酸性条件下,腐殖酸对磷的吸附和解吸作用较强,而腐殖酸对钾的的吸附和解吸作用在中性条件下更易发生;3)腐殖酸对氮、磷、钾的等温吸附可用Linear、Langmuir和Freundlich三个吸附方程来拟合,相关性达显著或极显著水平,但以Freundlich方程为最优。     

Bound amino acids in humic acids from arable cropping systems

We investigated the varying concentrations of bound amino acids in humic acids (HA) extracted from soils under both crop rotation and continuous cropping of rye. The experiment was created in 1957. Since then, winter rye had been grown continuously and also the sequence of the 7 yr rotation had been started: potato, spring barley, alfalfa, alfalfa, oil seed rape, winter rye, and winter rye. Soils were fertilized with NPK and manure. Continuous cropping of rye increased total acidity of soils and the contents of carboxylic and phenolic groups in HA. The total amounts of the bound amino acids in HA from soils under crop rotation were higher than from continuous cropping of rye. Fertilization with NPK increased the contents of bound amino acids more than manure. Neutral amino acids dominated in all samples of HA, and basic amino acids had the lowest concentrations. In both types of cultivation, glutamic acids, glycine, alanine, valine, and lysine dominated. The proline contents in HA from continuous rye cropping were higher than in HA from soils under crop rotation. The concentrations of β‐alanine and lysine were higher in HA from crop rotation indicating a higher microbial biomass since these compounds are typical constituents of bacteria cell walls.     

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.     

Fluorescent properties of low-molecular-weight fractions from chernozem humic acids

The polyacrylamide gel electrophoresis of chernozem humic acids (HAs) followed by ultraviolet detection (λ = 312 nm) has revealed a new highly fluorescent fraction that has the highest electrophoretic mobility and the lowest nominal molecular weight (NMW). The preparative isolation of the fraction has been performed using the multiple microfiltration of the same HA sample in a 7 M carbamide solution on a membrane with a nominal pore size of 5 kDa. Thirty ultrafiltrates with NMW < 5 kDa and different fluorescence maximums in the region of 475–505 nm have been prepared, as well as a nonfluorescent concentrate with NMW > 5 kDa. Fluorescence maximums at and below 490 nm have been noted only in the first four ultrafiltrates. All the ultrafiltrates have been combined into the fraction with NMW < 5 kDa, which has been successively passed through membranes of 3 and 1 kDa. Solutions of subfractions F 3–5 kDa, F 1–3 kDa, and F < 1 kDa with fluorescence maximums at 505, 488, and 465 nm, respectively, have been prepared. The F < 1 kDa subfraction with the lowest NMW had the highest fluorescence intensity. The distribution of the fluorescence maximums in the ultrafiltrates has indicated the presence of at least two groups of fluorophores and has confirmed the supramolecular organization of the extracted soil HAs.     

Determination of DTNB-reactive sulphhydryl groups in soil humic acids: their enrichment in humic acids from volcanic acid soils

Thirteen acid soils were collected from typical volcanic regions in Japan (S content: 0.9–4.1, mean = 2.2g kg^?1; pH (H₂O): 2.81–3.93, mean = 3.33), as well as nine reference soils (S: 0.6–1.7, mean= 1.1 gkg^?1; pH(H₂O): 4.10–4.74, mean = 4.47). Humic acids were extracted from the soils separately with 0.1 M NaOH and precipitated by acidification (pH = 2, HCl). After purification, the humic acids were subjected to colorimetric analysis using a DTNB reagent [5,5′-dithiobis(2–nitrobenzoic acid] for the active -SH group. Since humic acids have significant absorption at 4I2 nm, the coloured compound (5–mercapto-2–nitrobenzoic acid) was separated from the humic acids by ultrafiltration or solvent extraction prior to the colorimetric measurement. Humic acids also caused discoloration of the coloured compound when they coexisted in the reaction solutions. Thus, the reproducible determination of -SH was accomplished by employing a standard addition technique (-SH standard: cysteine). Although -SH contents obtained by the ultrafiltration method were considerably higher than those by the solvent-extraction method, probably due to the denaturation of humic acids by the higher buffer concentration used in the ultrafiltration method, they correlated well with each other. The humic acids from acid soils contained apparently higher concentrations of -SH (120–510, mean = 270mg S kg^?1 by the ultrafiltration method; 8–110, mean = 38mg S kg^?1 by the solvent-extraction method) compared to those from reference soils [20–260, mean = 90mg S kg^?1 by the former; not detectable (<5)-34, mean = 11 mg S kg^?1 by the latter]. This -SH enrichment in the humic acids from acid soils may result from the degradation and subsequent humification of S-rich debris of plants and micro-organisms and/or direct incorporation of volcanic acid gas (H₂S) into the humic acids.     

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.     

Chemical characteristics and influences of two fractions of Chinese lignite humic acids on urease

Soil urease is crucial for the nitrogen cycle and its association with humic acids (HAs) is a fundamental requirement for its stability. In this work, the chemical characteristic of two HA fractions (HA1, ≥50 kDa; HA2, 10–50 kDa) extracted from lignite was evaluated, and their effects on the activity and stability of Jack Bean urease were also studied. HA1 and HA2 exhibited different structural properties in the micro-FT-IR and ¹³C NMR spectra and influences on urease stability during 12 days of incubation: HA1 stabilized the urease activity. After 12 days, the residual activity of urease, at pH 6.0, 7.0 and 8.0, was 2.1, 2.6 and 3.9 times higher in the treatment of HA1-urease than in the free urease, respectively. With pH values increasing, the stability of free urease decreased and that of HA1-urease increased, which indicated that HA1 improved the stability of urease in the solution, especially at the alkaline condition.     

Elementary composition of humic acids

The author made a study of the elementary composition of various humic acids; L and SrL humic acids used in the previous report¹⁾, and two lowmoor humic acids.     

Molecular parameters of humic acids

Several molecular parameters of humic acids isolated from the soils of the most important genetic types are discussed.The material obtained makes it possible to establish limiting values of the molecular weights of humic acids and indicate the tendencies in their changes.The selected parameters characterise the submolecular, molecular and supramolecular levels of the organisation of humic acids. It has been shown that the most important indices include the molecular-weight distribution, molecular weight and the molecular form of humic acids.     

Absorption spectra of humic acids

For the purpose of explaining the forming process of soil humic acids, the author determined the absorption spectra of various humic acids. From soils and peats which were pretreated with 5% HCl at 70°C for 30 minutes or from those which were not, humic acids were extracted by treating with 0.5% NaOH at boiling temperature for 30 minutes. In these humic acids, the one which is extracted after acid pretreatment is provisionally designated as SrL humic acid and the other as L humic acid. The supernatant alkaline solutions obtained by centrifuging the above mentioned extracts were acidified with hydrochloric acid, and precipitated humic acids were filtered and washed with water until Cl' free. Humic acids were dissolved in 0.1% NaOH and ultrafiltered using collodion membrane. The filtrates were acidified with hydrochloric acid and humic acids were collected by centrifuging, transferred on the filter paper, washed with dilute hydrochloric acid and water successively, then air-dried and pulverized.     

Optimal isotherm model and explanatory characteristics associated with metal ion adsorption on humic acids isolated from forest soils

Journal of Soils and Sediments - Understanding the mechanisms of interaction between humic acids (HAs) and metal ions in soil media is essential for integrated environmental and agricultural...     

Several properties of humic acids

In the preceding paper¹), it was shown that the elementary composition of soil humic acid changed regularly with the progress of humification. Afterwards, the author conducted several experiments on the base exchange capacity, the content of hydrolysable nitrogen, the resistance to oxidizing reagent, the electrolyte coagulation and X-ray analysis of various humic acids. These experimental resu1ts will be given in this report.     

Persulfate oxidation of humic acids extracted from three different soils

Three soil humic acids were degraded by a new mild chemical oxidation method using potassium persulfate at pH 2.0. The method degraded 30–40% of the starting material. The type and relative quantities of the products or fragments released as determined by GC/MS varied with the source of the polymers. Humic acid extracted from an Inceptisol yielded fatty, benzenecarboxylic and phenolic acids; humic acid from a Typic Chromoxerert produced largely dialkyl phthalates, and humic acid from an Humic Haplorthod gave only branched and straight-chain fatty acids. It is suggested that the method may be used to advantage as a first oxidant in a sequential degradation.