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.     

外源腐殖酸对三种土壤无机磷组分的影响

磷是植物生长所需的大量元素之一,然而磷肥的当季利用率一般只有10%~25%,75%~90%的磷肥以不同形态的磷酸盐积累在土壤中[1]。因此,磷在土壤中的存在形态,以及施肥对磷素形态的影响一直受到人们的广泛关注[2~5]。植物直接吸收利用的磷大部分为无机磷[6],已有研究表明,有机酸能明显提高土壤有效磷含量[7~10],而有效磷含量的增加与土壤中无机磷形态的变化密切相关。面对当前土壤中累积的大量磷元素,而植物可利用的磷却十分低的现象,如何激活并利用土壤中难溶态磷一直是土壤研究工作者高度关注的问题。腐殖酸类物质作为一种潜在的有机资源,越来越受到土壤学者的关注[11,12],特别是腐殖酸对磷肥增效作     

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.     

Hydrophobicity of electrophoretic fractions of different soil humic acids

Purpose

The fractionation of soil humic acids (HAs) according to their hydrophobicity is a common procedure in the study of this polydispersed complex natural mixture, so that reversed-phase high-performance liquid chromatography (RP-HPLC) is used resulting in humic components of differing hydrophobic/hydrophilic properties. However, a comparative study of the hydrophobicity of fractions isolated from different soil HAs have not been addressed so far.

Materials and methods

The RP-HPLC with online absorbance detection was used for analysis of International Humic Substances Society soil standard HAs, chernozem soil HAs, and their electrophoretic fractions A, B, and C?+?D, obtained by tandem size exclusion chromatography–polyacrylamide gel electrophoresis. The strong relationship between hydrophobicity, electrophoretic mobility (EM), molecular size (MS), specific absorbance at 280 nm and aromaticity of HAs fractions was found.

Results and discussion

Independently of soil HAs genesis fraction A with lowest EM and highest MS is essentially more hydrophobic (60–73 % of the fraction amount remained adsorbed on the RP column) than medium EM and MS fraction B (33–47 % of the fraction amount remained adsorbed on the RP column). The lowest hydrophobicity belongs to fraction C?+?D with highest EM and lowest MS.

Conclusions

The most hydrophilic aromatic fraction C?+?D seems to have been bound with other mostly aliphatic hydrophobic fractions A and B through non covalent (possibly hydrogen) bonds. These data could be relevant to better understanding the overall makeup of soil HAs and their structural organization.     

Interactions of humic substances with allophanic compounds

Abstract

Organic matter from two Chilean Andisols, Vilcun and Osorno soils, were extracted and fractionated into humic (HA) and fulvic acids (FA). Humic acid were chemically characterized and their molecular weight (MW) distribution was obtained by gel permeation chromatography. The HA from the Vilcun soil had a lower MW than the HA from the Osorno soil and consequently had a higher acidity. Humic acid were used to coat synthetic allophanic materials which carried ferrihydrite coatings. The isoelectric point (IEP) of the synthetic allophanic materials was reduced from 8.6 to near 3.0 and surface area was reduced from 450 m²/g to 120 m²/g depending on the HA level. The surface pKa values showed that the HA buffer capacity generally reduced the surface acidity of allophahic materials, but the HA from the Vilcun soil at a higher HA level which slightly increased the surface acidity due to an observed lower condensation degree. Phosphate (P) adsorption capacity was reduced to a greater degree in the HA from the Osomo soil model than in the HA Vilcun one, indicating a positive correlation with surface acidity. The differential isosteric heat of P adsorption (?H) showed similar energy sites at lower P adsorbed levels in the Osorno and Vilcun soil models, but that with over 40% surface coverage, the Vilcun soil model had higher energetic reaction than the Osorno one.     

Interactions of allophane with humic acid and cations

Allophanic soils are known to accumulate organic matter, but the underlying mechanism is not well understood. Here we have investigated the sorption of humic acid (HA) by an allophanic clay in the presence of varied concentrations of either CaCl₂ or NaCl as background electrolytes. Both the HA and the clay were separated from New Zealand soils. Much more HA was sorbed in CaCl₂ than in NaCl of the same ionic strength. Apparently Ca²⁺ ions were more effective than Na⁺ ions in screening the negative charge on HA. In CaCl₂ the HA molecule might also assume a more compact configuration than in NaCl. In the presence of CaCl₂ sorption increased, reached a maximum, and then declined as the concentration of HA in solution was increased. This behaviour was not observed in NaCl where sorption showed a gradual and steady increase with HA concentration. We propose that ligand exchange occurs between the surface hydroxyl groups of allophane and the carboxylate groups of HA. As a result, the allophane–HA complex acquires negative charges, requiring the co‐sorption of extraneous cations (Ca²⁺ or Na⁺) for charge balance. The Ca²⁺ co‐sorbed can attract more HA to the complex possibly by a cation‐bridging mechanism, giving rise to a maximum in sorption. The decline in sorption beyond the maximum may be ascribed to a decrease in the concentration of free Ca²⁺ ions through binding to HA molecules in solution. The increase in supernatant pH may be attributed to a ligand exchange reaction between the surface hydroxyls of allophane and the carboxylate groups of HA, and proton binding to the allophane–HA complex.     

几种胡敏酸还原容量的表征与比较

还原容量(RC)是衡量胡敏酸(HA)还原特性的重要指标。采用饱和H2振荡法和土壤溶液法对HA分别进行化学和微生物预处理,分别以硝酸铁(Fe(NO3)3)、柠檬酸铁(FeCit)作电子受体,测定了三种HA(上海巨枫SH,天津光复TJ,缙云山JY)的本底还原容量(NRC),化学还原容量(CRC),微生物还原容量(MRC)。对不同电子受体条件下、不同初始状态和不同种类的胡敏酸的RC进行比较。结果表明：三种HA中,以缙云山土壤提取的胡敏酸RC值最高,还原容量最大,分别为20.21?0.26mmolc mol-1C (NRC)、26.02?1.12mmolc mol-1C (CRC)和29.29?1.56mmolc mol-1C (MRC)。两种电子受体中,采用Fe(NO3)3得到的RC明显高于在FeCit条件下。另外,溶液态HA的RC明显高于固态。由此证明胡敏酸还原容量是一个相对量;其容量大小不仅和自身结构、性质有关,也受到HA初始形态和不同电子受体的影响。对比三个还原容量指标发现CRC和MRC显著大于NRC,而CRC和MRC之间无明确大小关系,因此用CRC来表征HA被微生物还原后的还原容量(MRC)还需作进一步验证。     

Interactions of ferricyanide with humic soils and charred straw

The iron‐cyanide complexes ferricyanide, [Fe^III(CN)₆]^3?, and ferrocyanide, [Fe^II(CN)₆]^4?, are anthropogenic contaminants in soil. We studied the interactions of ferricyanide with humic soils and charred straw (maize and rye, both charred at 300, 400 and 500°C) by batch experiments and Fourier transform infrared (FTIR) spectroscopy. All soil samples sorbed ferricyanide (up to 8.4 g kg^?1). Precipitation of a manganese ferrocyanide after reduction of ferricyanide in the moderately acidic to neutral soils was deduced from both FTIR spectroscopy (CN absorption bands at 2069–2065 cm^?1) and geochemical modelling. Ferricyanide was also adsorbed onto the charred straw. The amounts of iron‐cyanide complexes adsorbed increased with increasing charring temperature, with a maximum of 1.71 g kg^?1. An absorption band at 2083 cm^?1 indicated weakly adsorbed intermediates of the reduction of ferricyanide to ferrocyanide. This band disappeared in the samples charred at higher temperature, whereas a band at 2026 cm^?1 was present in all spectra and became intensified in the high‐temperature straw. We attribute this band to ferrocyanide forming inner‐sphere complexes, presumably with quinone species of the organic matter. The band at 2026 cm^?1 was also present in the spectra of the soils, indicating that soil organic matter also adsorbs ferrocyanide. However, in humic soils the main processes of ferricyanide interaction include reduction to ferrocyanide and precipitation as manganese ferrocyanide. Quantitatively, adsorption on highly aromatic substances plays only a less important role as compared with precipitation.     

On artificial humic acids

I. Absorption Spectra of Some Artificial Humic Acids

It is a well known fact that numerous dark brown or black and amorphous substances cap be produced from organic compounds by purely chemical processes. Some of them are called artificial humic acids, and have been used as a model of soil humic acids by many workers. But it is doubtful whether such artificial humic acids are considered to be a model of soil humic acids, even if there can be found any similarities in their properties. However it may be an useful method for the study of humus formation to compare artificial humic acids with soil humic acids, and to make efforts to find a good model or to prepare artificial humic acids comparable to soil humic acids under laboratory conditions. For this purpose, first of all, the author prepared artificial humic acids from glucose, hydroquinone and lignin, and their absorption spectra were determined.     

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.     

有机物料腐解过程胡敏酸的分级研究

采用培养试验,在研究玉米秸、绿豆秸、猪粪、羊粪4种有机物料腐解过程腐殖物质的组成(H/F比)、胡敏酸性质动态变化的基础上,利用酒精沉淀法对胡敏酸进行分级,研究了不同腐解期胡敏酸的级分组成变异。结果表明,有机物料腐解形成的胡敏酸以级分3、4、5所占比例较多,级分1、2相对较少。级分3在整个腐解过程明显增加;级分1、2前期有所波动,后期呈增加趋势,级分4、5以减小趋势为主。胡敏酸性质变化与其级分组成变化有密切关系。     

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.     

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.     

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.     

Comparison of carbon skeletal structures in black humic acids from different soil origins

Andosols are characterized by an abundance of black humic acids (HAs) belonging to Type A with a high content of aromatic carbon (C) in particular condensed aromatic C. Black HAs are also observed in other soils, such as Chernozems and the subsoil of paddy field, and extracted after washing with an acid or using chelating agent such as sodium pyrophosphate (Na₄P₂O₇). However, contribution of condensed aromatic structures to those soil HAs are unknown. To obtain the information about C skeletal structures of black HAs in soils other than Andosols, HAs were obtained from 2 Chinese Chernozem samples, 2 subsoil samples from Japanese paddy fields (Fulvisols), and a Rendzina-like soil (Cambisols) as well as an Andosol sample (reference) by successive extraction with 0.1 M NaOH (HAs₁) and 0.1 M Na₄P₂O₇ (HAs₂), and ¹³C nuclear magnetic resonance and X-ray diffraction 11-band profile analyses were applied. In the black HAs₂ from the non-Andosol samples, the proportion of C present as aromatic C, size of C layer planes, and relative C layer plane content ranged from 52 to 59%, 0.48 to 1.92 nm (mean size, 0.76–0.91 nm), and 58 to 100 AU (arbitrary unit) mg^?1, respectively, with a positive correlation between total C layer plane content and the degree of humification. Those ranges were similar to the distribution ranges of Andosols HAs₁ reported by our previous study.     

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.     

Depolymerization and degradation of humic acids with sodium perborate

Two humic acids of different origin (peat and soil) were degraded with a 5% sodium perborate solution (140°C). This degradation process consists mainly of a stoichiometric production of hydrogen peroxide while the perborate is reacting with carboxyl groups of the oxidized polymers. A single perborate treatment degraded more than 40% of the humic acids to soluble products, but a 5-step oxidation was necessary for total degradation, the sample being transformed into soluble oligomers with properties similar to those of fulvic acids. The oligomeric fractions with lowest molecular weights, including individual molecules (soluble in ethyl acetate), were purified by adsorption chromatography and studied by GC-MS after methylation. The higher molecular weight fractions of oligomers were recovered over polyvinylpyrrolidone, eluted by alkali, and purified by ion-exchange chromatography (47% peat HA; 25% soil HA).Degradation products included alkanes, fatty acids and dicarboxylic acids. Aromatic compounds (mainly phenolic, benzenecarboxylic and cinnamic acids), amounted to 24–50% of the total volatile degradation products. There were striking differences between peat and soil humic acids, the former yielding typical lignin degradation products. Independently checked, the perborate degradation products were not the same as those obtained by mild treatment with hydrogen peroxide under alkaline conditions.     

Quinoid groups in humic acids

Quinoid groups of humic acids from various sources (soil, peat, brown and oxidized coals) can undergo reversible redox transformations, this being a fundamental property of this class of natural compounds.Kinetic oxidation curves for reduced humic acids indicate the presence of various types of quinoid groups.The specificity of a previously suggested technique for determining quinones in humic acids has been corroborated. Exhaustive carbonyl reduction by sodium borohydride combined with reductometric methods for determining quinones in alkaline media make possible a better estimation of the ketone content in humic acids.When humic acids are reduced in an acid solution of tin chloride, rigorous conditions (4 h, 120°C, strong acid media) lead to an irreversible conversion of part of the quinone carbonyls and, as a result, the reaction proceeds nonstoichiometrically.     

Sephadex gel fractionation of humic acids

Using Sephadex G 50 gel filtration, three soil humic acids were separated into two to four fractions, which differed more or less in their spectrophotometric properties. The distribution of a humic acid fraction on an RF-Δlog K diagram was classified into two cases; in the first case, the RF increased and Δlog K decreased with the elution order, and in the second case, humic acid fractions distributed clockwise around the original humic acid.

A small amount of B type humic acid was separated by gel filtration from newly formed Rp type humic acid obtained from the mixtures of grass and soil materials incubated for four months under alternate field and air-dry conditions.