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1.
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   

2.
Humus dynamics in four Austrian forest soils The humus of four Austrian forest soils was characterized by means of a chromatographic and a mass spectrometric (δ13C, δ15N) method. With this combination it was possible to explain changes in the humic acid systems within the profiles. The leaching of humic acids in a Spodo-Dystric Cambisol and therefore the beginning of podsolization could be deduced. In a Stagno-Dystric Gleysol processes of dehumification were determined. The value of non humic substances was enhanced within the profile of a Fluvi-Calcaric Fluvisol. The δ15N-values increased in the four profiles much more with depth than the δ13C-values. This indicated the rapid mineralization of organic nitrogen.  相似文献   

3.
To determine whether there is a relationship between the composition of soil organic matter and the activity of the soil microbial biomass, the composition of the organic matter in 12 typical arable soils in Northwest Germany was investigated by wet chemical analysis and CPMAS cross polarization magic angle spinning 13C-NMR spectroscopy. The data were correlated with the microbial biomass as estimated by substrate-induced respiration. A strong correlation between the microbial biomass and alkylic C compounds was observed (r=-0.960***). Recalcitrant substances were enriched in this fraction, which were classified as humic acids according to the wet chemical procedure. The microbial decomposition of these humic acids is probably retarded, due to their chemical structure and/or physical bonding, when the soil microbial biomass activity is limited.  相似文献   

4.
We have tested to see if the generic set of NICA‐Donnan model parameters, used to describe isolated humic substances, can also describe soil humic substances in situ. A potentiometric back‐titration technique was used to determine the variable surface charge of two organic peat soils at three different ionic strengths. The non‐ideal, competitive‐adsorption NICA‐Donnan model was used to simulate the surface charge, by assuming a bimodal distribution of H+ affinity on the soil solid phase. The model provided an excellent fit to the experimental data. The Donnan volume, VD, varied slightly with ionic strength, although the variation was less than for humic substances in solution. The values obtained for the parameters that define the affinity distributions, the intrinsic proton binding constant (log Kiint) and the heterogeneity of the site (mi), were similar to those observed for isolated soil humic acids. The abundance of carboxylic groups in the whole soil represented 30% of the typical value for isolated soil humic acids. The composition of the organic matter of the whole soils, obtained by 13C CPMAS NMR, was comparable to the characteristic composition of soil humic acids.  相似文献   

5.
Recent developments in the application of nuclear magnetic resonance (n.m.r.) spectroscopy to soil science are reviewed. Progress in 1H, 13C and CP-13C n.m.r. spectroscopy of humic substances is reported. Methods of determining the fraction of aromatic carbon in soil organic matter extracts are discussed, and methods by which structural group analysis can be carried out on in situ organic matter of whole soils are reviewed.  相似文献   

6.
We studied the acid‐base properties of 16 fulvic acids and 16 humic acids isolated from the surface (3–15 cm) and subsurface (> 45 cm) horizons of two types of acid forest soils, derived respectively from amphibolite and granite rocks, under five different types of vegetation. The observed differences between the contents of humic substances in the two types of soils were related to the degree of Al‐saturation of the soil organic matter, as indicated by the molar ratio between pyrophosphate extractable Al and C. Humic fractions were characterized in terms of elemental composition, and CPMAS 13C NMR spectrometry. The contents of carboxylic and phenolic groups were estimated by potentiometric titrations conducted in 0.1 m KNO3 in a nitrogen atmosphere. The fulvic acids contained more carboxylic groups but less phenolic groups than the humic acids: the ratio of phenolic to carboxylic groups in the humic acids was 0.48 ± 0.10 and in the fulvic acids 0.23 ± 0.05. The mean values of the protonation constants of each of the humic substance fractions can be used as generic parameters for describing the proton binding properties. The fulvic acids isolated from the subsurface horizon of the soil contained between 2.6 and 23% more carboxylic groups, and the humic acids between 8 and 43% more carboxylic groups than those isolated from the surface horizon of the same soil.  相似文献   

7.
The carbohydrates in soil organic matter seem to be derived from undecomposed or partially decomposed plant and microbial residues, In soil, these carbohydrates exist chiefly in such from as polysaccharide hemicellulose, and their polyuronide has been the chief object of investigation1)-3). In various soil, the polyuronide is found in a large quantity in fulvic fraction of soil organic matter and has been considered as important in connection with the physical structure of soil4),5). According to Lynch 5), the carbohydrate content of humic acid is markedly smaller than that of fulvic acid. His work also indicates that a' considerable change is noted in the content and composition of the carbohydrate in humic acid because of the addition of some organic substances to the soils, or of the cultivation of virgin soils. Further, some investigators7) believe that uronic acid is introduced into the aromatic structure of the humic acid by changing into pentose and furan. Accordingly, it seems that the role of carbohydrate in the formation of soil humic acid should not be overlooked.  相似文献   

8.
The binding of metal to humic substances is problematical. The approaches for studying metal binding to organic matter are briefly reviewed. Ion-selective electrodes (Cu2+ and Pb2+) were used to measure metal complexation by a whole peat and an extracted humic acid (HA) fraction. Scatchard plots and calculation of incremental formation constants were used to obtain values for the binding constants for the metals onto both peat and HA. Both the peat and the humic acid had a larger maximum binding capacity for Pb2+ than for Cu2+ (e.g. at pH = 5 HA gave 0·188 mmol Cu2+ g?1 and 0·564 mmol Pb2+ g?1: peat gave 0·111 mmol Cu2+ g?1 and 0·391 mmol Pb2+ g?1). Overall, the humic acid had a larger metal binding capacity, suggesting that extraction caused conformational or chemical changes. The binding constants (K1) for Cu2+ increased with increasing pH in both peat and humic acid, and were larger in the peat at any given pH (e.g. at pH = 5 HA gave log K1= 2·63, and peat gave log K1= 4·47 for Cu2+). The values for Pb2+ showed little change with pH or between peat and humic acid (e.g. at pH = 5 HA gave log K1= 3·03 and peat gave log K1= 3·00 for Pb2+). In the peat, Cu2+ may be more able to bind in a 2:1 stoichiometric arrangement, resulting in greater stability but smaller binding capacity, whereas Pb2+ binds predominantly in a 1:1 arrangement, with more metal being bound less strongly. Whole peat is considered to be more appropriate than an extracted humic acid fraction for the study of heavy metal binding in organic soils, as this is the material with which metals introduced into an organic soil would interact under natural conditions.  相似文献   

9.
Electron microprobe studies on soil samples with varying heavy metal contamination. 2. Contents of heavy metals and other elements in aggregations of humic substances, litter residues and charcoal particles EMA point analysis show that the organic matter constituents of heavy metal contaminated soils are highly enriched with heavy metals. The maximal trace element accumulation were for Cu up to 13,000 mg/kg, for Zn up to 48,000 mg/kg, for Cd up to 2,100 mg/kg and for Pb up to 193,000 mg/kg. The affinity for the accumulation of the different heavy metals in aggregations of humic substances can be described by the sequence Cu > Pb ? Cd > Zn ? Ni > Co. In very strongly acidified humic top soil horizons the Pb and Cd accumulation in the organic matter constituents is in competition with the accumulation in Fe and Mn oxides. The heavy metal contents (especially of Cu) of the organic matter are often correlated with the content of organically bound calcium. The EMA results also show that high heavy metal amounts occur in combination with Ca-accumulations in the epidermis and the outer bark parenchym of decayed roots. EMA point analysis of the interior of fungus sclerotias show that sclerotias can contain high amounts of heavy metals, in particular lead (up to 49,700 mg Pb/kg). From statistical results of EMA point analysis follows that lead and other heavy metals attached to humic substances are not only bound as metal organic complexes but also as organic metal phosphate complexes. Also charcoal particles of polluted soils contain high amounts of heay metals. The accumulation affinity is quite similar to that of humic substances.  相似文献   

10.
Abstract

Regeneration of a soil with a high degree of desertification was conducted by the addition of different doses of municipal solid waste organic matter (MSW). Five years after this treatment, humic substances were extracted from these soils and characterized by spectroscopy and isoelectric focusing. No significant differences between E4/E6 ratio and ?log K (Log A400 nm‐log A600 nm) were observed for humic substances extracted from treated and untreated soils. However, the isoelectric focusing (IEF) technique established differences between the humic substances from control and treated soils. The focusing pattern of the former showed a well defined band at pH 9.1 which nearly disappeared in the soils with high doses of MSW (1–2 %). However the organic matter which focused at pH 5.8 was present in all soils.  相似文献   

11.
The definition of humusforms from soils under cultivation. II. Quantity and quality of soil organic matter In the new edition of the German textbook “Practical Studies in Soil Science” the authors presented a proposal of mapping humusforms in arable soils in order to characterize soil and site ecology (Schlichting et al., 1995). This proposal was developed from the definitions “Ochric”, “Mollic” and “Umbric” of the Soil Taxonomy and the FAO classification. The characterization of humusforms in 45 arable surface soils was carried out according to this proposal while soil organic matter (SOM) composition was investigated by means of wet chemistry and CPMAS 13C-NMR spectroscopy. “Mollic” in contrast to “Umbric” humusforms could be characterized by a higher carbonyl/carboxyl carbon content probably deriving from proteins, polysaccharides and humic substances. In addition the mollic epipedon contains 10% more litter compounds, whereas in the umbric epipedon humic acids are of major importance. The humin fraction in the mollic epipedon is thought to be raised by the formation of Ca-humates. Our data suggest, that with regard to microbial decomposition a surplus of available organic matter is present in the mollic horizons. The ochric-like epipedon has a much lower humus content compared to “Mollic” and “Umbric” horizons and exhibits the highest amounts of soluble organic matter as well as aromatic and carboxylic C-compounds in the humic fraction. Our data suggest, that SOM quantity and quality of the mollic, umbric and ochric epipedons differ substantially. These findings suggest that the proposal of Schlichting et al. (1995), which was extended by Blume & Beyer (1996), should be regarded as a useful basis to discuss the development of humusforms in soils under cultivation and facilitate soil survey in order to improve site characterization.  相似文献   

12.
Decomposition of organic matter in inundated wetland soils requires a number of interdependent microbial processes that ultimately generate CO2 and CH4. Largely as the result of anaerobic decomposition, wetland soils store globally significant amounts of organic carbon and are currently net sources of CH4 to the atmosphere. Given the importance of wetlands in the global carbon cycle, it is important to understand controls on anaerobic decomposition in order to predict feedbacks between wetland soils and global climate change. One perplexing pattern observed in many wetland soils is the high proportion of CO2 resulting from anaerobic decomposition that cannot be explained by any measured pathway of microbial respiration. Recent studies have hypothesized that humic substances, and in particular solid-phase humic substances in wetland soils, can support anaerobic microbial respiration by acting as organic electron acceptors. Humic substances may thus account for much of the currently unexplained CO2 measured during decomposition in wetland soils. Here we demonstrate that humic acids extracted from a variety of wetland soils act as either electron donors or electron acceptors and alter the ratio of CO2:CH4 produced during anaerobic laboratory incubations. Our results suggest that soil-derived humic substances may play an important, and currently unexplored, role in anaerobic decomposition in wetland soils.  相似文献   

13.
Rock fragments in soil can contain significant amounts of organic carbon. We investigated the nature and dynamics of organic matter in rock fragments in the upper horizons of a forest soil derived from sandstone and compared them with the fine earth fraction (<2 mm). The organic C content and its distribution among humic, humin and non‐humic fractions, as well as the isotopic signatures (Δ14C and δ13C) of organic carbon and of CO2 produced during incubation of samples, all show that altered rock fragments contain a dynamic component of the carbon cycle. Rock fragments, especially the highly altered ones, contributed 4.5% to the total organic C content in the soil. The bulk organic matter in both fine earth and highly altered rock fragments in the A1 horizon contained significant amounts of recent C (bomb 14C), indicating that most of this C is cycled quickly in both fractions. In the A horizons, the mean residence times of humic substances from highly altered rock fragments were shorter than those of the humic substances isolated in the fine earth. Values of Δ14C of the CO2 produced during basal respiration confirmed the heterogeneity, complexity and dynamic nature of the organic matter of these rock fragments. The weak 14C signatures of humic substances from the slightly altered rock fragments confirmed the importance of weathering in establishing and improving the interactions between rock fragments and surrounding soil. The progressive enrichment in 13C from components with high‐14C (more recent) to low‐14C (older) indicated that biological activity occurred in both the fine and the coarse fractions. Hence the microflora utilizes energy sources contained in all the soil compartments, and rock fragments are chemically and biologically active in soil, where they form a continuum with the fine earth.  相似文献   

14.
The pH buffering and aluminium solubility characteristics of acid soil are important in determining the soil's response to changes in precipitation acidity. The chemistry of soil organic matter (humic substances) plays a key role in both processes, yet is complex and still poorly understood. Nevertheless, models of humic substance chemistry have been developed, one of which is WHAM–S, which contains a model (Model V) of proton and metal binding at discrete sites on humic substances and considers electrostatic effects on the binding strength. Here we have tested the ability of WHAM–S to model solution pH and Al using batch titration studies on organic and mineral soil horizons from forested sites in Norway, Germany and Spain, with ambient pH values from 3.73 to 5.73. We optimized the model predictions by adjusting the amounts of soil aluminium and humic substances within defined limits, taking the contents of copper chloride‐extractable Al and the base‐extractable organic matter as starting values. The model simulated both pH and dissolved Al well with optimized amounts of aluminium and humic substances within the defined limits (root mean squared error for pH from 0.01 to 0.22, for p[Al]aq (total dissolved Al) from 0.03 to 0.49, five data points). Control of dissolved Al by dissolved organic matter was important particularly at above‐ambient pH. In two mineral horizons we improved the fits by assuming that Al could precipitate as Al(OH)3. The optimized model also gave reasonable predictions of pH and dissolved Al in supernatants obtained by repeated leaching of the soil horizons. The results show that humic substances dominate the control of pH and dissolved Al in most of the horizons studied. Control by Al(OH)3 occurs but is the exception.  相似文献   

15.
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   

16.
ABSTRACT

Hot-water- and water-extractable organic matter were obtained from soil samples collected from a rice paddy 31 years after the start of a long-term rice experiment in Yamagata, Japan. Specifically, hot-water-extractable organic carbon and nitrogen (HWEOC and HWEON) were obtained by extraction at 80°C for 16 h, and water-extractable organic carbon and nitrogen (WEOC and WEON) were obtained by extraction at room temperature. The soil samples were collected from surface (0–15 cm) and subsurface (15–25 cm) layers of five plots that had been treated with inorganic fertilizers alone or with inorganic fertilizers plus organic matter, as follows: PK, NPK, NPK plus rice straw (RS), NPK plus rice straw compost (CM1), and NPK plus a high dose of rice straw compost (CM3). The soil/water ratio was 1:10 for both extraction temperatures. We found that the organic carbon and total nitrogen contents of the bulk soils were highly correlated with the extractable organic carbon and nitrogen contents regardless of extraction temperature, and the extractable organic carbon and nitrogen contents were higher in the plots that were treated with inorganic fertilizers plus organic matter than in the PK and NPK plots. The HWEOC and WEOC δ13C values ranged from ?28.2% to ?26.4% and were similar to the values for the applied rice straw and rice straw compost. There were no correlations between the HWEOC or WEOC δ13C values and the amounts of HWEOC or WEOC. The δ13C values of the bulk soils ranged from ?25.7% to ?23.2% and were lower for the RS and CM plots than for the PK and NPK plots. These results indicate that HWEOC and WEOC originated mainly from rice plants and the applied organic matter rather than from the indigenous soil organic matter. The significant positive correlations between the amounts of HWEOC and HWEON and the amount of available nitrogen (P < 0.001) imply that extractable organic matter can be used as an index for soil fertility in this long-term experiment. We concluded that the applied organic matter decomposed more rapidly than the indigenous soil organic matter and affected WEOC δ13C values and amounts.  相似文献   

17.
In highly weathered tropical conditions, soil organic matter is important for soil quality and productivity. We evaluated the effects of deforestation and subsequent arable cropping on the qualitative and quantitative transformation of the humic pool of the soil at three locations in Nigeria. Cultivation reduced the humic pool in the order: acetone‐soluble hydrophobic fraction (HE) > humic acid (HA) > humin (HU) > fulvic acid (FA), but not to the same degree at all three sites. The C and N contents, as well as the C/N ratios of humic extracts, were large and not substantially influenced by land use. The δ13C values of the humic extracts were invariably more negative in forested soils thereby showing a dilution of δ13C signature with cultivation from C3 to C4 plants. The δ13C values of apolar HE fractions were generally more negative, indicating a reduced sensitivity compared with other humic fractions to turnover of crop residues. The contents of hydrophobic constituents (alkyl and aromatic C), as revealed by cross‐polarization magic angle spinning (CPMAS) 13C‐NMR spectroscopy, in HA, FA and HU were generally < 50%, with the exception of larger hydrophobicity in HU in the forested soil at Nsukka and HA in that at Umudike. The HE fraction contained significantly more apolar constituents, and consequently had a larger intrinsic hydrophobicity than the other humic fractions. The larger reduction of apolar humic constituents than of the less hydrophobic humic fractions, when these soils were deforested for cultivation, indicates that at those sites the stability of accumulated organic matter is to be ascribed mainly to the selective preservation of hydrophobic compounds.  相似文献   

18.
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   

19.
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20.
X－ray photoelectron spectroscopy(XPS) was applied to examine the N structures of soil humic substances and some of their analogues.It was found that for soil humic substances XPS method gave similar results as those obtained by ^15N CPMAS NMR (cross-polarization magic-angle spinning nuclear magnetic resonance) method.70%-86% of total N in soil humic substances was in the form of amide,and 6%-13% was presented as ammes,with the remaining part as heterocyclic N.There was no difference in the distribution of the forms of N between the humic substances from soils formed over hundreds or thousands of years and the newly formed ones.For fulvic acid from weathered coal and benzoquinone-(NH4)2SO4 polymer the XPS results deviated significantly from the ^15N CPMAS NMR data.  相似文献   

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