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1.
A series of humic and fulvic acids isolated from different sources, size‐fractions separated from a humic acid, and three soils of different origin were subjected to CPMAS 13C‐NMR spectroscopy to obtain the distribution of their carbon contents. The relative areas of chemical shift regions in NMR spectra were used to apply a principal component analysis (PCA) to the three sets of samples. The multivariate analysis was successful in efficiently differentiating samples on the basis of the quality of their organic carbon content. The PC biplots based on two principal components distinguished objectively among samples as accurately as it was possible to do by subjective qualitative evaluation of the original spectra. In the case of the soils, a discriminant analysis (DA) was applied to build a classification model that allowed the validation of the three soils according to their origin. Percentage of validation in the classification model is expected to increase when a large number of NMR spectra are accumulated and/or the concentration of organic carbon in samples is enhanced. The multivariate analyses described are likely to become a useful tool to increase the importance of CPMAS 13C‐NMR spectra in the appraisal of natural organic matter variations in heterogeneous natural systems.  相似文献   

2.
Soil organic matter (SOM) is an important factor influencing aggregate stability. Interactions between SOM and soil structure are widely studied, although the subtle relationship between SOM content, pore size distribution and aggregate stability is not fully known. Here we investigate such a relationship by means of a long‐term experiment established in 1962 in northeastern Italy, which considers different fertilizer practices (organic, mineral and mixed) applied to a continuous maize crop rotation. We measured wet stability of 1–2 mm aggregates subjected to different pretreatments. Both soil physical properties (such as pore size distribution and hydrophobicity) and chemical properties (soil organic and humic carbon content) affecting aggregate stability were considered. The chemical structure of humic substances was characterized by thermal and spectroscopic analyses (TG‐DTA, DRIFT and 1H HR MAS NMR). The Pore‐Cor network model was then applied to evaluate the contribution of hydrophobicity and porosity to aggregate wetting. Our study suggests that SOM and its humic fraction can affect aggregate wetting and consequently slaking by modifying the pore size distribution with a shift from micropores (5–30 µm) and mesopores (30–75 µm) to ultramicropores (0.1–5 µm); hydrophobicity was also increased as a result of different humic composition. Spectroscopic analysis showed that hydrophobic compounds were mostly associated with complex humic molecules. Models of fast wetting dynamics, however, suggest that the contribution that hydrophobicity makes to aggregate stability, especially to soils with large carbon inputs, may not be the most significant factor.  相似文献   

3.
The conformational structure of dissolved humic substances is an important property that controls the reactivity of humus in the soil solution. High performance size-exclusion chromatography was used here to study the changes in molecular size of different humic substances brought about by addition of mineral (HCl) and monocarboxylic (formic, acetic, propionic, and butyric) acids. The CPMAS-NMR spectra showed that humic substances had varying chemical composition and that the ratio of hydrophilic to hydrophobic carbon (HI/HB) was greater for a humic acid from soil than for ones from oxidized coal and lignite. All humic substances showed a decrease in UV absorbance of chromatographic peaks when treated with either HCl or monocarboxylic acids. This was due to the hypochromic effect by which the absorptivity of associated molecules is decreased when they are separated. We attributed the molecular separation upon acid treatment to the formation of intermolecular hydrogen bonding that alters the original conformation stabilized mainly by weaker hydrophobic interactions. Addition of organic acids not only further decreased peak absorbances of humic acids but also caused their shift to larger elution volumes, indicating a larger conformational disruption than with HCl. The extent of the molecular size changes showed a relation to the number of carbons of monocarboxylic acids and to the HI/HB ratios of humic materials. The larger the carbon content of organic acids and the smaller the HI/HB ratio of humic materials, the larger was the decrease of the average molecular size of humic acids. These results suggest that dissolved humic substances associate predominantly by hydrophobic forces and that the apolar components of humic substances largely control their aggregation and reactivity in the environment.  相似文献   

4.
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   

5.
Mapping the chemical structures and organization of humic substances is vital for a fundamental understanding of their roles and interactions in the soil. One‐dimensional nuclear magnetic resonance (NMR) techniques have advanced our awareness of the composition of humic materials, but modern developments in two‐dimensional NMR are soon likely to make obsolete reliance on one‐dimensional spectra alone. The advantages of using heteronuclear two‐dimensional NMR spectroscopy are illustrated in this paper in studies of the structural units in a fulvic acid fraction isolated from the Bh horizon of a Podzol. The structures identified from the NMR (at 500 MHz) experiments can be summarized as: mono‐ and dicarboxylic acids (in about equal amounts), with an average chain length of about 10 carbon atoms (these are easily the major components); smaller amounts (about 10–20% of the acids) of esters and alcohols or ethers; some carbohydrate and amino acid residues (evidence from chemical shift data would suggest that these were likely to be in the form of chains); and very small amounts of 1,2‐, 1,4‐, and 1,3,4‐substituted benzenes and of cinnamic acids. The results suggest that applications of heteronuclear and multidimensional NMR spectroscopy will allow considerable progress to be made in understanding the nature of the structural units and their connectivities in humic molecules provided that the heterogeneity of the humic mixtures can first be decreased significantly.  相似文献   

6.
The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by 13C‐dilution analysis and CPMAS‐13C‐NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year‐long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ13C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS‐13C‐NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic‐rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of 13C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.  相似文献   

7.
Humus properties of 42 soil samples or humic extracts of Ap horizons of Cambisols and Luvisols, from different field plots, kept for a long time under continuous management conditions, have been studied by quantitative CPMAS 13C NMR-spectroscopy. The shift range of the spectra were divided into 8 regions, with carbon absorptions from 0–45 (aliphatics), 45–60 (OCH3), 60–80 (CO? CN), 80–110 (anomeric carbons), 110–140 (aryl—C), 140–160 (O-aryl-C) and 160–210 (COOH? C?O) ppm, respectively. Although soil samples and humic extracts were obtained from plots from different locations and sometimes widely differing organic carbon contents, variances in the relative absorptions of the selected ranges were rather small. Several absorptions were significantly correlated among each other or with soil carbon and microbial biomass contents. These correlations were discussed with the applied management and with other results about humus formation and properties. CPMAS 13C NMR-spectroscopy allows a reliable and comprehensive characterization of soil organic matter from soils without previous fractionation.  相似文献   

8.
In the present paper new findings in soil organic matter (SOM) research were reviewed with regard to non-aromatic species in order to make evident the recent conception about the chemical nature of humic matter structure. The main purpose of this paper was to unravel the manifold information of SOM investigations in order to characterize the classical humic matter fractions (fulvic acids, humic acids, humins) and bulk soil samples. Such common state-of-the-art information is missing in current SOM literature. In addition we focus on improvements in SOM research due to the application of the new instrumental methods such as NMR and pyrolysis-MS and its problems of analysis.  相似文献   

9.
The fate of organic matter during composting is poorly understood. Therefore, we analysed composts of sewage sludges and green wastes (44 samples representative of 11 stages of biodegradation) by conventional chemical methods: pH, humic (HA) and fulvic acid (FA) content, C, N and organic matter (OM) content, and by 13C CPMAS NMR to assess the decomposition process of the organic matter. Chemical changes clearly occurred in two phases: first, decomposition of OM during the first 2 months was characterized by decreased C/N ratios, OM content and increased pH; and second, a humification process with increased HA/FA ratios. NMR spectrum changes confirmed this pattern, with an increase in aromaticity and a decrease in alkyl C. A decrease of syringyl to guaiacyl ratio (S/G), a sign of lignin transformation, also indicated humification during composting. NMR spectroscopic properties of composts were also studied by means of principal components analysis (PCA) and revealed changes according to the degree of compost maturation. The factorial map presents a chronological distribution of composts on the two first principal components. The influences of eight chemical factors on the PCA ordination of composts as monitored by their evolution by NMR were also studied by multivariate analyses. PCA clearly indicated two phases: the rapid decomposition of organic matter followed by the formation of humic‐like substances. The first phase, that is ‘new’ composts, was strongly correlated with OM contents, pH and C/N ratios whereas the second phase, corresponding to ‘old’ compost, was correlated with pH, HA content and HA/FA ratio. These results confirm that knowledge of the formation of humic substances is indispensable to suitable monitoring of the composting process.  相似文献   

10.
The partitioning of chemical elements between the solid and solution phases in soil is fundamental in understanding processes such as leaching and bioavailability. Here I present a model in which the partitioning of Cd, Al and carbon in both mineral and organic soils can be simulated in the pH range 2–8. A two‐phase additivity approach simulates ion adsorption by the soils using a hydrous ferric oxide and humic type surface. A model for the partitioning of soil humic matter has also been developed in which the NICA–Donnan model calculates humic surface charge. Other key processes represented include mineral solubilization and solution speciation. Methods for deriving model input parameters either from analytical data or by parameter optimization were used. Acid ammonium‐oxalate‐extractable Fe was used to estimate the amount of hydrous ferric oxide, and reactive humic substances were estimated by a scaled down version of the International Humic Substances Society method for the extraction of humic and fulvic acid. For initial calculation the 0.1 m HCl‐extractable Al was used to estimate reactive Al. Optimization of reactive Al improved the fit of both the total dissolved Al data and the adsorbed Cd. The model for the solid–solution partitioning of humic substances could simulate reasonably well the release of carbon in the pH range 4–8 for both the organic and mineral soils.  相似文献   

11.
The objective of this study was to investigate differences in organic matter fractions, such as dissolved organic carbon and humic substances, in soils under different land uses. Soil samples were collected from the upper layer of arable lands and grasslands. Humic substances (HS) were chemically fractionated into fulvic acids (FA), humic acids (HA) and humins (HUM), and based on the separated fractions, the humification index (HI) and the degree of HS transformation (DT) were calculated. Dissolved organic carbon (DOC) was determined by cold (CWE) and hot water (HWE) extractions. Regardless of land use, the results indicated significant differences in soil organic carbon (SOC) and HS composition, with HA and HUM as the dominant fractions. Total SOC was higher in grassland (median = 17.51 g kg?1) than arable soils (median = 9.98 g kg?1); the HI and DT indices did not differ significantly between land uses (HI = 0.3–10.3 and DT = 0.2–6.2 for grasslands, p > 0.05; HI = 0.3–3.9 and DT = 0.2–20.1 for arable lands, p > 0.05). This indicates the relatively high stability of organic carbon and efficient humification processes in both land uses. Additionally, in arable soils lower CWE‐C (0.75 g kg?1) and higher HWE‐C (2.59 g kg?1) than in grasslands (CWE‐C = 1.13 g kg?1, HWE‐C = 1.60 g kg?1) can be related to farming practice and application of soil amendments. The results showed that both labile and humified organic matter are better protected in grassland soils and are consequently less vulnerable to mineralization.  相似文献   

12.
Abstract

Determinations were made of total soil organic matter (SOM), stable and labile organic fractions, biomass carbon (C), and chemical composition of several humus‐soil‐fractions in Chilean volcanic soils, Andosols and Ultisols. Their physico‐chemical properties and humification degree at different stages in edaphic evolution were also assessed. In addition, organic matter models were obtained by chemical and biological syntheses and the structures and properties of natural and synthetic humic materials were compared with SOM. Results indicate that Andosols have higher SOM levels than Ultisols, but the fraction distribution in the latter suggests a shift of the more stable fractions to the more labile ones. Moreover, contents of humines, and humic and fulvic acids suggest that Chilean volcanic soil SOM is highly humified. On the other hand, among the SOM labile fractions, carbohydrate and biomass are about 15% of the SOM which are one of the most important fractions in soil fertility.  相似文献   

13.
珠江三角洲地区土壤与表层沉积物有机质的性质结构研究   总被引：11，自引：1，他引：11  
通过分析海洋、河流、池塘和稻田四种热带 /亚热带土壤与表层沉积物及用化学方法分离的有机质 ,证明了土壤与沉积物有机质是高度不均匀的 ,除了包括腐殖酸和演化程度较深的干酪根外 ,强调了演化程度更深的碳黑的存在 ,并对不同有机质的来源、性质和结构进行了表征。腐殖酸和干酪根来源于生物体的演化 ,在结构上后者比前者致密 ;碳黑来源于化石燃料和生物体的不完全燃烧 ,具有更致密的结构 ,对有机质的非均质性影响很大。因此可认为 ,系统地研究土壤与表层沉积物有机质的非均质性及组分特征对了解地球表层的生物地球化学过程和疏水性毒害有机污染物在环境中的迁移具有重要的意义。  相似文献   

14.
Recent intensification of cropping and the attendant longer submergence of the soil for lowland rice in tropical Asia appear to have altered the nature of the soil organic matter, and perhaps also nutrient cycling. To identify the dominant forms of organic nitrogen in the soils we extracted the labile mobile humic acid (MHA) and the more recalcitrant calcium humate (CaHA) fractions from soils under several long‐term field experiments in the Philippines and analysed them by 15N‐nuclear magnetic resonance spectroscopy. Amide N dominated the spectra of all humic acid (HA) samples (60–80% of total peak area). Its proportion of total spectral area increased with increasing intensity of cropping and length of time during which the soil was flooded and was greater in the MHA fraction than in the CaHA fraction. Simultaneously the spectral proportion of free amino N and other chemical shift regions decreased slightly with increasing length of submergence. Heterocyclic N was detected at modest proportions (7–22%) and was more prevalent in more humified samples, especially in the CaHA of aerated soils. Correlations of spectral proportions of heterocyclic N with other properties of the HA, reported elsewhere, were highly significant. Correlations were positive with visible light absorption (r= 0.86) and concentration of free radicals (r= 0.85), both of which are indices of humification, and negative with concentration of H (r= ?0.86), a negative index of humification. Correlations of spectral proportions of amide N with these properties were also highly significant but in each case of opposite sign to that of heterocyclic N. Proportions of heterocyclic N declined with increasing duration of submergence. The results suggest that (i) 15N‐NMR can reproducibly measure some portion of heterocyclic N, (ii) formation of heterocyclic N is associated solely with gradual humification occurring over many years, and (iii) the abundant phenols in the submerged rice soils did not promote formation of heterocyclic N, and hence some other process is responsible for a substantial decrease in the availability of native N associated with intensive rice cropping.  相似文献   

15.
Spin counting on solid‐state 13C cross‐polarization (CP) nuclear magnetic resonance (NMR) spectra of two humic fractions isolated from tropical lowland soils showed that only 32–81% of potential 13C NMR signal was detected. The observability of 13C NMR signal (Cobs) was higher in the mobile humic acid (MHA) than in the calcium humate (CaHA) fraction, and increased with increasing intensity of irrigated rice cropping. NMR observability appeared to be related to the nature of the organic carbon, with phenol‐ and methoxyl‐rich samples having the higher values of Cobs. The Bloch decay (BD) technique provided more quantitatively reliable 13C NMR spectra, as evidenced by values of Cobs in the range 91–100% for seven of the eight humic fractions studied. The BD spectra contained considerably more aryl and carbonyl signal, and less O–alkyl and alkyl signal, with the greatest differences between CP and BD spectra observed for the samples with low Cobs(CP). The causes of low CP observability were investigated using the spectral editing technique RESTORE ( RE storation of S pectra via T CH and T O ne R ho (T1ρH) E diting). Rapid T1ρH relaxation was found to be primarily responsible for the under‐representation of carbonyl carbon, whereas inefficient cross‐polarization was primarily responsible for the under‐representation of aryl carbon in CP spectra. Proton NMR relaxation rates T1H and T1ρH were found to correlate with other NMR properties and also with cropping management. Non‐uniform rates of T1H relaxation in two of the CaHA fractions enabled the generation of proton spin relaxation editing subspectra.  相似文献   

16.
The influence of soil constituents including sand, silt, clay, organic substances, aluminium and iron on crust development and seedling emergence was investigated in a selection of 30 soils. After treatment with simulated rain, soil crust strength as measured by penetration resistance to an upward-moving probe tended to decrease with increasing total organic carbon content, but the relationship was not a simple one. Consideration of other factors showed that in some soils (soils of 1.5–2% total organic carbon), alkali-exractable carbon and clay contents had the greatest influence on penetration resistance values whereas in other soils (2.4–3% total organic carbon), coarse sand, fine sand, EDTA-extractable aluminium and humic acid carbon were highly correlated with penetration resistance. In a group of soils with around 4% total organic carbon, oxalate-extractable aluminium appeared to exert a dominant influence. There was a good correlation between humic acid carbon and penetration resistance after rain treatment in soils containing less than 40% sand. A similar relationship was also noted with EDTA-extractable iron.Combination of all factors in a multiple regression analysis accounted for a considerable proportion of the variation in penetration resistance of soils with and without simulated rain application and in seedling emergence of barley. Organic carbon, and the humic acid fraction in particular, were most important in determining crust strength for all soils as a group.A significant correlation between plastic limit moisture and the logarithm of penetration resistance is explained partially, at least, by the relationships that exist between organic carbon alone, clay alone and a combination of both, with variation in moisture.  相似文献   

17.
Humus properties in various Ap horizons from field plots, that have been cultivated in long-term experiments under different management conditions, were investigated by pyrolysis-field ionization mass spectrometry (Py-FIMS) and 13C-NMR spectroscopy. The results of Py-FIMS were evaluated by correlation and principal component analysis from reproducible data sets of bulk soil samples and extracted humic substances, and allowed a distinct discrimination on the basis of humus quality and composition. The chemical subunits suitable for discrimination are the major plant constituents carbohydrates, lignin, and proteinaceous materials as well as their humification products. The contribution of these compound classes to soil organic matter decreased with the intensity of management. CPMAS and solution 13C NMR spectra of soils and humic substances demonstrated that with more intense management, both the intensities of the phenolic region (140–160 ppm) and the aromatic region (110–140 ppm) decreased. The combination of both independent methods MS and NMR, together with microbiological and biochemical data, yields the general result that intensive soil management leads to a less active humus.  相似文献   

18.
Seeking to quantify the amount of refractory organic matter (ROM), which includes black carbon‐like material (BC), in marine sediments, we have applied a two‐step procedure that consists of a chemical oxidation with sodium chlorite of the demineralized sediments followed by integration of the aromatic C region in the remaining residues by solid‐state 13C nuclear magnetic resonance (NMR) spectroscopy. The efficacy for lignin removal was tested by analytical pyrolysis in the presence of tetramethyl ammonium hydroxide (TMAH). Riverine, estuarine and offshore marine sediment samples were collected from the southwest Atlantic coast of Spain, a site of geological and environmental interest. Measured contents of BC‐like material ranged between 3.0 and 45.7% of the total organic carbon. Greater relative BC contents were found in riverine sediments close to urban areas, which show an elevated input of anthropogenic organic material. The contents of BC‐like material in offshore marine sediments (5.5–6.1%) were similar to those previously reported for these kinds of samples. However, NMR and pyrolysis‐GC/MS of the isolated ROM reveals that abundant refractory aliphatic organic material remains in most of the marine samples after chlorite oxidation. We suggest that this pool of aliphatic carbon may play an important role as a stable carbon pool within the global C cycle.  相似文献   

19.
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.  相似文献   

20.
Abstract

In a previous communication in this journal, a fractionation scheme of soil organic matter (SOM) was presented (1). The goal of this paper is to discuss the reproducibility and verification of this procedure with an expanded data set of 150 samples. Litter compound analysis (LCA) is appropriate to detect small differences in the decomposition degree at a quantitative level which are not detectable with SOM morphology. In contrast, humic compound analysis (HCA) is not appropriate to characterize SOM with regard to quantitative data, because the detected carbon (C) (C recovery rate <800 mg/g TOC) reflects only parts of the total SOM. In addition selected, SOM fractions are determined with both extraction procedures. When counting C as polysaccharides in the LCA and as fulvic acid in the HCA, this gives recovery rates of much more than 100% (>1,200 mg/g TOC). These errors induce both an under‐ or an over‐estimation of C within the combination of the litter and humic compound analyses (LCA+HCA) and the conversion to 100% should not be used. Because of the method problems and limited chemical information provided with HCA, we propose using LCA and additional analytical instuments (e.g. NMR, pyrolysis) to further characterize structures in the non‐litter substances of the SOM pool.  相似文献   

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