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1.
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.  相似文献   

2.
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.  相似文献   

3.
To investigate the chemical heterogeneity of humic substances in relation to molecular size, fulvic and humic acids were extracted and purified from the surface horizon of a Humic Gleysol in northern Switzerland. A fractionation scheme using hollow‐fibre ultrafiltration cartridges was developed and used to obtain four size fractions of the humic acid with nominal molecular weight ranges > 300 kDa, 100–300 kDa, 30–100 kDa, and 10–30 kDa. The fulvic acid and all humic acid fractions were characterized by size exclusion chromatography, elemental analysis (C, H, N, S), as well as spectroscopic techniques including UV‐VIS, CP‐MAS 13C‐NMR, FT‐IR, and fluorescence spectroscopy. Clear chemical differences between the humic acid size fractions were observed. Smaller size fractions of the soil humic acid contained more chargeable functional groups and a larger percentage of aromatic carbon than the larger size fractions. Conversely, the percentage of aliphatic carbon increased with increasing apparent molecular weight. The chemical composition of the smallest humic acid fraction differed clearly from the fulvic acid fraction, despite similar apparent molecular size and carboxyl carbon content. Small humic acids contained much more aromatic carbon and less aliphatic carbon than the fulvic acid fraction. Apparently, humic size fractions differ in their chemical composition, which can have important implications for their environmental behaviour.  相似文献   

4.
Preparations of humic acids (HAs) were isolated from a gray forest soil by sequential alkaline extraction. From a sample of 500 g, HA preparations of 2.24, 0.23, and 0.20 g were obtained from the first, second, and third alkaline extracts, respectively. The structure of the preparations was determined by 13C NMR spectroscopy. At each next extraction step, the portion of aliphatic fragments in the HA preparations increased and the content of aromatic structures decreased. The conclusion was drawn that a single extraction is sufficient for obtaining a representative HA sample.  相似文献   

5.
Elemental composition and solution 13C NMR spectra for six humic acid fractions with different particle sizes (i.e. 3K, 10K, 30K, l00K, 300K, and 500K) which were prepared from a humic acid in an Umbric Andosol by successive gel permeation chromatography were determined. Elemental composition of the particle size fractions clearly differed from one another. Contents of nitrogen and hydrogen increased with the increase of the particle size. Small and middle particle size fractions (3K to l00K) showed low contents of hydrogen and nitrogen corresponding to those in typical Andosol humic acids, while the contents in the large fractions (300K and 500K) were distributed in the ranges of those in the other humic acids. As the particle size increased, the HIC ratio increased whereas the O/H decreased. In the HIC versus OIC diagram, the large particle size fractions (300K and 500K) were observed in the area around humic acids with a low humification degree. Variation of the chemical structural properties with particle size differences was assumed, based on the analysis of the HIC versus OIH and HIC versus OIC diagrams. The changes of the carbon species with particle size differences were examined based on the 13C NMR spectra. As the particle size increased, the aliphatic C content increased whereas the carboxylic and aromatic C content decreased and, therefore, the aromaticity decreased. In addition, a negative correlation (r= -0.977) was found to be significant at 0.1% level between the HIC ratios and aromaticity. The peak strength around 30 ppm assigned to chains of methylene group increased remarkably with the increase of the particle size. It was suggested that the changes of the content of the aliphatic carbon with the decrease of the particle size may depend on the changes of the aliphatic chain length. In conclusion, these findings suggest that the Andosol humic acid molecule may be composed of humic acid components with long chains of aliphatic groups for the larger particle size fractions, and of their homologous series through the reduction of the length of the aliphatic long chain for the smaller particle size fractions. These assumptions were compatible with those made in a series of studies previously reported.  相似文献   

6.
Spectroscopic techniques including X-ray photoelectron spectroscopy (XPS) can identify particular chemical groups of humic acids (HA) from “Terra Preta de Índios” (TPI) or Amazonian dark earth, the highly fertile anthropogenic soil found in the Amazonian region. The high fertility and resilience of these soils cannot be explained by their chemically inert pyrogenic C content alone, but the natural aging of this C generates reactive carboxyl functional groups attached directly to the recalcitrant polycondensed aromatic backbone. Through spectroscopic techniques used in this work, the HA fraction (the alkaline-soluble organic matter that precipitates at low pH) of the TPI soil was compared with humic and fulvic acids, obtained by oxidizing activated charcoal with sodium hypochlorite. The yields recovery of HA-like substances was 12 and 28 wt% by using 10 and 20 cmol L?1 of oxidizing agent, respectively. X-ray photoelectron spectroscopy, energy dispersive X-ray, and solid-state 13C nuclear magnetic resonance (13C NMR) spectroscopies were used to evaluate the elements and structures present in all samples. XPS C 1 s spectra of HA extracted from TPI soil and from prepared HA showed aromatic structures (C?=?C and π–π* shake-up satellite peak) bounded to carboxyl groups (COOH). The morphology and polycondensation level of aromatic C were evaluated by scanning electron microscopy (SEM). The similarities of the spectra indicated that the used method was efficient to obtain an organic amendment similar to TPI soil organic matter.  相似文献   

7.
腐植酸的组成结构及其对作物根系调控的研究进展   总被引:2,自引:0,他引:2  
[目的]综述腐植酸的结构及其对作物根系调控方面的研究进展,为腐植酸的进一步资源化利用提供理论依据.[主要进展]1)腐植酸结构复杂、功能多样,由C、H、O、N和S等元素构成.腐植酸是多价酚型芳香族化合物与氮化合物的缩聚物,其裂解产物主要有烷烃类、饱和醇类、非饱和线性醇类、吡啶类等,其形成机制主要基于氨基糖缩合理论、多酚理...  相似文献   

8.
中国黑土上腐殖酸和腐殖物质的提取及其描述   总被引:7,自引:0,他引:7  
Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC even after 23 successive HA extractions. In addition, the atomic C/H ratio decreased during the course of extraction while C/O increased; the E4/E6 ratio from the UV analysis decreased with further extraction while E~/E3 increased; the band assigned to aliphatic carbon (2 930 cm-1) in the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) spectra gradually increased with progressive extraction; the calculated ratio of the sum of aromatic carbon peak heights to that of aliphatic carbon peak heights from DRIFTS spectra declined with extractions; and nuclear magnetic resonance (NMR) data suggested that HA aliphatic carbons increased with extractions while aromatic carbons decreased. Thus, hydrophobicity and aliphaticity of HAs increased with extractions while polarity and aromaticity decreased. These data showed substantial chemical, structural, and molecular differences among the 23 HAs and two humin fractions. Therefore, these results may help explain why soil and sediment humin fractions have high sorption capacity for organic contaminants.  相似文献   

9.
Abstract

The choice of prospective type of farming requires knowledge about the specific relationships that exist between farm management practices and base environmental conditions. Nowadays the protection of soil organic carbon is one of the main tasks, because organic carbon in addition to soil fertility can act in elimination of soil contamination and carbon sequestration. Field experiments were focused on the effect of intensive farming without organic inputs versus grassland on organic carbon content. Organic carbon content (Cox) and humic substance fractions (C-humic acids and fulvic acid fractions), hot water extractable carbon and selected microbial characteristics in Eutric Cambisol were monitored during the period 1999–2010. A priming effect of soil cultivation was detected immediately after tillage. Arable soil with ‘intensive’ crop sequences (exclusively cash crops, cereals, oil plants) and with an optimal level of chemical inputs (mineral fertilizers, pesticides), but without organic farmyard manure had lower content of all carbon forms compared with grassland. 13C NMR spectroscopy and thermal analysis (TGA) were applied to characterize humic acid (HA) structure and stability. More carbon, less oxygen and more aromatic compounds were detected in grassland HA. Slight differences were found in HA thermo-oxidative stability and degradability, which was probably caused by changes in elemental composition and structure. Even the land use had no significant effect on basic microbiological characteristics (basal respiration, microbial biomass and qCO2); the physiology of the microbial community of grassland was altered by a higher ability to utilize L- and D-glutamic acid. The L/D ratio of glutamic acid mineralization indicated no occurrence of stress in soil for both types of farming. It has been demonstrated that although losses of carbon as a result of land-use conversions are generally more rapid, gains of carbon in grassland followed by changes in management practices can also occur.  相似文献   

10.
《Geoderma》2006,130(1-2):77-96
Base- and acid-hydrolysable fractions of humic acids (HAs) isolated from a forest soil, an agricultural soil and a lignite deposit were analysed, and comparisons were made between the base hydrolysable lipid (bound lipid), carbohydrate and amino acid signatures of the different humic acids.Bound lipids differ depending on the humic acid origin. Their composition were rather similar for the two soil humic acids, with three main lipid classes identified: (i) aliphatic components, (ii) aromatic components and (iii) sterols and triterpenols. The aliphatic subfraction was the most abundant and consisted predominantly of cutin- and suberin-derived moieties some of which could be clearly related to the vegetation. A minor bacterial input was indicated by the presence of short chain α- and β-hydroxyalkanoic acids. Aromatic subfraction contributed to a low amount to the total base hydrolysates and consisted mainly of lignin-derived methoxyphenols. Present in trace amounts, sterols and triterpenols are mainly of higher plant origin. The base hydrolysate from lignite humic acid markedly differs. Bound lipids released from lignite HA comprised almost exclusively aliphatic components, largely dominated by long chain alkanoic acids. Lignin-derived moieties, hardly detected, consisted solely of vanillic and 4-hydroxybenzoic acids indicating a much higher degree of lignin alteration in lignite humic acid. Sterols and triterpenols were absent.Although the composition of monosaccharides released upon acid hydrolysis was rather uniform irrespective of the humic acid origin, the distribution changed with the degree of humification of the HAs. Ratios of (Galactose+Mannose) to (Xylose+Arabinose) increased from soil to lignite humic acids. The high values of the ratios indicate that carbohydrates are primarily of microbial origin.In all humic acids neutral and acidic protein amino acids dominated. Non protein amino acids were only minor components consisting mainly of hydroxy proline and ornithine. The amino acid distributions of both soil HAs were similar. The amino acid distribution of lignite HA resembled that of soil HAs except for the following differences: (1) the absence of hydroxy proline and the greater abundance of ornithine suggesting a higher microbial contribution to the amino acids as the degree of humification increases, (2) the higher contribution of polar amino acids suggesting a preferential preservation of these amino acids possibly by interaction with the humic acid surface through hydrogen bonds.  相似文献   

11.
The structure of humic acids (HAs) in zonal soil types—soddy-podzolic soils (two samples), gray forest soil (one sample), and chernozems (two samples)—was quantitatively studied by 13C NMR spectros-copy. In the series considered, the content of unsubstituted carbon in the aromatic fragments of HAs increased, and the fraction of unsubstituted aliphatic structures decreased. HAs of soddy-podzolic soils were found to be enriched with carbohydrate fragments compared to HAs of chernozems and gray forest soil. The carbon skeleton of HAs from typical rich chernozem contained significantly more aliphatic and carbohydrate fragments compared to typical chernozem, which probably reflected the lower degree of HA transformation in rich chernozem.  相似文献   

12.
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.  相似文献   

13.
有机物料对白土土壤胡敏酸结构特征的影响   总被引:7,自引:0,他引:7  
【目的】研究有机物料施入对白土土壤的腐殖质含量组成和胡敏酸(HA)结构特征的影响,为明确不同腐殖质组分对土壤肥力的影响提供理论依据。【方法】供试土壤为江苏省溧阳市南渡镇"白土改良大田示范试验核心区"的南方中低产水稻土(白土)。试验设秸秆还田(ST)、施有机肥(OM)和对照(CK,不施有机物)3个处理,培肥3年。同时采集试验田周围相邻的江苏省耕地质量监测点(2007~2013年)的每年施化肥(LAF)和长期不施肥(NF)的两种处理土壤进行比对研究。分别测定土壤的基本理化性质及其腐殖质含量的组成,并提取土壤胡敏酸(HA)固体样品利用红外光谱和元素分析来进行结构表征。【结果】秸秆还田和施有机肥处理的有机碳、全氮含量明显高于对照;与对照相比,施有机物料土壤HA的E4/E6比值增加,且秸秆还田施有机肥对照。红外光谱显示,试验区域和耕地监测点的不同处理土壤HA均在1650 cm-1处(酰胺I带)和1550 cm-1处(1500~1580 cm-1酰胺II带伸缩振动)有特征吸收。施有机肥和秸秆还田处理土壤HA的2920/1720、2920/1650比值显著大于对照。在元素组成上,OM、ST处理的土壤腐殖质(HA)中C、H、N的含量比均高于CK,相对长期施化肥(LAF)和不施肥(NF)的土壤有明显提高,而氧元素的含量呈降低的趋势;OM和ST处理土壤HA的[H]/[C]和[O]/[C]原子数比均低于CK;与LAF和NF处理相比,试验区域各处理土壤腐殖质的[H]/[C]和[O]/[C]原子数比均有明显降低。【结论】有机物料施入土壤后可增加土壤有机碳含量,改善土壤理化性质,提高作物产量和品质,且施入土壤的有机物料可转化为新的腐殖质,降低土壤的腐殖化程度。土壤腐殖质(HA)的红外光谱分析说明,白土土壤HA具有明显的酰胺类化合物特征。有机物料施入后使得土壤脂族性增强,羧基量减少,芳香度降低;秸秆还田和施有机肥处理与对照相比,土壤HA的[H]/[C]和[O]/[C]比均有下降的趋势,且HA的氮素含量明显增加,这显示有机物料施入后白土土壤腐殖质发生"脱水"过程,同时也反映了白土土壤腐殖质形成的特征。  相似文献   

14.
Solid state13C nuclear magnetic resonance(NMR)spectroscopy is a common tool to study the structure of soil humic fractions;however,knowledge regarding carbon structural relationships in humic fractions is limited.In this study,mobile humic acid(MHA)and recalcitrant calcium humate(CaHA)fractions were extracted from eight soils collected from six US states and representing a variety of soils and ecoregions,characterized by this spectroscopic technique and analyzed for statistical significance at P≤0.05.We found that the abundances of COO and N–C=O functional groups in the MHA fractions were negatively correlated to soil sand content,but were positively correlated to silt,total N and soil organic carbon contents.In contrast,the abundances of the COO and N–C=O functional groups were only positively correlated to the content of clay in the CaHA fractions,indicating that the two humic fractions were associated with diferent soil components.The two13C NMR peaks representing alkyls and OCH3/NCH were negatively correlated to the peaks representing aromatics,aromatic C–O and N–C=O/COO.Comparison of the sets of data from13C NMR spectroscopy and ultrahigh resolution mass spectrometry revealed that the aromatic components identified by the two methods were highly consistent.The comparison further revealed that protein in MHA was associated with,or bound to,the nonpolar alkyl groups,but a component competitively against(or complementary to)aromatic groups in the MHA composition.These observations provided insight on the internal correlations of the functional groups of soil humic fractions.  相似文献   

15.
固态13C和15N核磁共振法研究15N标记土壤的腐殖质组分   总被引:1,自引:0,他引:1  
Five humic fractions were obtained from a uniformly ^15N-labelled soil by extraction with 0.1 mol L^-1 Na4P2O7,0.1mol L^-1 NaOH ,and HF/HCl-0.1 mol L^-1 NaOH,consecutively,and analyzed by ^13C and ^15N CPMAS NMR (cross polarization and magic angle spinning nuclear magnetic resonace).Compared with those of native soils humic fractions studied as a whole contained more alkyls ,methoxyls and O-alkyls,being 27%-36%,17%-21%and 36%-40%,respectively,but fewer aromatics and carboxyls(bein 14%-20% and 13%-90%,respectively),Among those humic fractions ,the humic acid(HA)and fulvic acid(FA) extracted by 0.1 mol L^-1 Na4P2O7 contained slightly more carboxyls than corresponding humic fractions extracted by 0.1 mol L^-1 NaOH ,and the HA extacted by 0.1 mol L^-1 NaOH after treatment with HF/HCl contained the least aromatics and carboxyls.The distribution of nitrogen functional groups of soil humic fractions studied was quite similar to each other and also quite similar to that of humic fraction from native soils.More than 75% of total N in each fraction was in amide from,with 9%-13% present as aromatic and /or aliphatic amines and the remainder as heerocyclic N.  相似文献   

16.
The humic acids (HAs) isolated by conventional procedure from rhizosphere (r) and bulk (c) soils were analyzed by means of chemical and physico-chemical techniques. Two different crops were selected, tomato (T) and artichoke (A), and each HA was fractionated by size-exclusion chromatography (SEC) into three fractions with increasing molecular size, respectively, Fraction I (FrI) < Fraction II (FrII) < Fraction III (FrIII). Elemental analysis data indicated greater N and S contents in the rhizosphere T-HAs, with respect to rhizosphere A-HA, which suggests the occurrence in the former ones of a large amount of organic nitrogen- and sulfur-containing compounds that are released by the rhizodeposition processes. Further, the three HA fractions from the bulk soils of the two series showed a gradual increase of C, H, and N contents, and a decrease of O and S contents and C/N and C/H ratios. These results suggested that the lowest molecular size fractions are richer in oxygenated functional groups, whereas the higher molecular size fractions are richer in N-containing groups and structural C- and H-containing units. The three HA fractions from the rhizosphere soils of the two series showed a gradual decrease in C content, and an increase of H, N, and O contents, which suggests the possible incorporation into soil HAs of a multitude of C-containing compounds of low molecular size released by plant roots. The FT-IR data, in general, suggested that the contents of carboxylic, phenolic and N-containing groups and polysaccharide-like components in HAs from rhizosphere soils are larger than those of HAs from the corresponding bulk soils. Further, the FrI fraction consisted mainly of simple structural units, likely quinonic and phenolic units with a prevalent aromatic character, whereas the FrII and, especially, FrIII fractions featured a mixed aliphatic/aromatic nature and a greater molecular complexity. The extent of these differences appeared to depend on the plant species and age, and is mainly due to the partial incorporation into rhizosphere HAs of typical root exudate components, such as amino acids, amides, aliphatic and aromatic acids of low molecular size, polysaccharides and sugars, fatty acids and sterols, and enzymes.  相似文献   

17.
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.  相似文献   

18.
A series of humic matter samples isolated from a soil sequence, different oxisols, size‐fractionated from a vermicompost humic acid and subjected to chemical modifications, were characterized by CPMAS 13C‐NMR spectroscopy. The relative signal areas in chemical shift regions of NMR spectra of the four sets of samples were analysed by principal component analysis (PCA). Hierarchical cluster analysis (HCA) was applied to build a classification model, which allowed the recognition of humic matter according to its origin. The relationship between carbon species and biological activity of humic acids, as promoters of lateral root emergence, was obtained by applying PLS multivariate analysis. This showed that lateral root emergence was mostly related to NMR parameters such as the hydrophobicity index (HB/HI) and the 40–110 and 160–200 ppm chemical shift regions (hydrophilic carbon HI), while the content of hydrophobic (HB) carbon in humic samples was negatively correlated with induction of lateral root hair. Our results represent a step further in the structure‐bioactivity relationship of natural humic substances and confirm their role as plant root growth promoters.  相似文献   

19.
Abstract

Although the application of manure to upland fields is believed to induce changes in the quality of humic substances in soil as well as the quantity, the direction and extent of these changes have not been elucidated. To understand temporal variations in humic acids, periodically collected soil samples from two fields, a Typic Hapludult (Togo) and a Pachic Melanudand (Kuriyagawa), with cattle manure and chemical fertilizer (CF) were examined. The content and degree of humification (darkening) of the humic acids were distinctly greater in Kuriyagawa than in Togo soil. Corresponding to the difference in the degree of humification, molecular size distribution, elemental composition, infrared (IR) spectra, and 13C cross polarization/magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectra of humic acids differed between the two soils. Manure application at 40 Mg ha?1 year?1 for 16 years (Togo) and at 80 or 160 Mg ha?1 year?1 for 19 years (Kuriyagawa) resulted in greater humic acid content compared with plots with CF only because of its increase in the manured plots and/or decrease in the CF plots. Manure application at an extremely high rate (160 Mg ha?1 year?1) resulted in higher H content and greater signal intensities of alkyl C, O-alkyl C and amide C=O in the 13C CPMAS NMR and/or IR spectra. Although humic acids with larger molecule sizes increased in all the manured plots, differences between the humic acids from the plots with and without manure applied at practical levels in the elemental and spectroscopic analyses were small or scarce. These results were considered to be because of the similarity between the indigenous soil humic acids and the manure-derived ones in Togo soil (a low degree of humification) and because of the abundance of highly-humified humic acids in Kuriyagawa soil.  相似文献   

20.
To assess the effect of continuous organic material (OM) application on soil humic acids, the amount and chemical characteristics of humic acids in various types of soils (n = 10) were compared between plots treated with farmyard manure (FYM) or rice straw compost (RSC) plus chemical fertilizer (CF) and plots treated with CF alone. The degree of humification (degree of darkening), molecular size distribution and 13C cross polarization/magic angle spinning nuclear magnetic resonance spectra of humic acids from CF‐treated soils showed wide variation among the soils. Humic acid content was generally larger in OM + CF soils than in corresponding CF soils, and the stable C isotopic ratio suggested partial replacement of indigenous humic acids with OM‐derived ones even where no apparent increase in humic acid content was observed. The rate of OM application and the indigenous humic acid content were related positively and negatively, respectively, to the apparent accumulation rate of humic acids among soils. The degree of humification of humic acids was generally smaller in OM + CF soils than in CF soils. Humic acids extracted from FYM and RSC exhibited chemical characteristics typical of humic acids having a smaller degree of humification, which suggested the contribution of OM‐derived humic acids to the differences between OM + CF and CF soil humic acids, such as larger average molecular sizes and smaller and larger proportions of aromatic C and O‐alkyl C, respectively, relative to total C in the OM + CF soil humic acids. Little change was observed in the chemical characteristics of humic acids when the degree of humification of indigenous humic acids was small. The effect of OM application on the chemical characteristics of humic acids was most conspicuous in soils containing humic acids having an intermediate degree of humification, possibly resulting from the combination of accelerated degradation of indigenous humic acids and the accumulation of OM‐derived humic acids.  相似文献   

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