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1.
Nitrogen forms of humic substances from a subalpine meadow soil,a lateritic red soil and a weathered cola and the effect of acid hydrolysis on N structures of soil humic substances were studied by using ^15N cross-polarization magic angle spinning nuclear magnetic resonance(CPMAS NMR) spectroscopy,Of the detectable ^15N-signal intensity in the spectra of soil humic substances 71%-79% may be attributed to amide groups ,10%-18% to aromatic/aliphatic amines and 6%-11% to indole-and pyrrole-like N.Whereas in the spectrum of the fulvic acid from weathered coal 46%,at least,of the total ^15N-signal intensity might be assigned to pyrrole-like N,14% to aromatic/aliphatic amines,and the reamining intensities could not be assigned with certainty,Data on nonhydrolyzable reside of protein-sugar mixture and a ^15N-labelled soil fulvic acid confirm the formation of nonhydrolyzable heterocyclic N during acid hydrolysis. 相似文献
2.
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
3.
^15N-labelled phenolic polymers were synthesized by reactions of p-benzoquinone and 1,4-diphenol with ^15N-labelled glycine and were studied by using ^15N CP-MAS NMR technique in combination with chemical approaches.Results showed that the proportion of polymer nitrogen as N-phenyl amino acid N was not as great as expected,only accounting for 5%-15%;and most of N in polymers occurred in the forms of amide,pyrrole-and indole-like nitrogen,aliphatic amines and isonitrile.It seems that great differences existed between synthetic humic acids and soil humic acids in the type and distribution of nitrogen forms. 相似文献
4.
In this paper,the nitrogen forms in newly-formed humic substances,including humic acid (HA),fulvic acid (FA) and humic acid in humin (HAI),were studied by using the ^15N CP-MAS NMR technique in combination with chemical approaches.Results show that the majority of nitrogen in HA,FA and HAI was in the amide form with some presented as aliphatic and/ or aromatic amines and some as pyrrole type nitrogen,although the contents of nonhydrolyzable nitrogen in them differed greatly from each other (15-55%). 相似文献
5.
Pot experiments were carried out to estimate N2 fixation by vetch,milk vetch,sickle alfalfa and broadbean in pure stand using a ^15N-labelled soil.Winter wheat was used as the non-fixing control.The 15N-labelled soil used was prepared by growing corn-wheat-corn successively on a nearly organic-matter-free Xiashu loess supplemented with adequate amounts of (15NH4)2SO4,P,K and micronutrients,then incorporating these 15N-labelled plant materials into the soil after each havest,and allowing the plant materials to be decomposed aerobically for 410d after incorporation of the plant material of the thire crop.The 15N enrichment of wheat plant-N varied slightly with organs,with a maximum difference of 9.8%,Based on 15N enrichment of soil N inferred from the mean value of the 15N enrichment in different organs of wheat 79%-91% of total N in the tops and 67%-74% of total N in the roots of legumes studied were derived from atmosphere .Estimate by isotope dilution method was in good agreement with that by the conventional difference method provided values obtained by the latter were corrected for seed N,and also with that from the measurement of N accumulated in the tops of the legumes. 相似文献
6.
Water-soluble,nondialyzable Maillard polymers were prepared by reacting D-xylose with ^15N-glycine (and /or glycine)at 6８℃ and pH 8.0 at equimolar concentrations of 1,0.5 and 0.1 mol L^-1,respectively, for 13 days and partitioned into acid-insoluble(MHA) and acid-soluble(MFA) fractions.The nitrogen froms in these polymers were studied by using the ^15N cross polartisation-magic angle spinning nuclear magnetic resonance(CPMAS NMR) technique in combination with chemical methods .The ^15N nuclear magnetic resonance(NMR) data showed that while the yield,especially the MHA /MFA ratio,varied considerably with the concentrations of the reactants,the nitrogen distribution patterns of these polymers were quite similar. From 65% to 70% of nitrogen in them was in the secondary amide and /or indole form with 24%-25% present as aliphatic and /or aromatic amines and 5% to 11% as pyrrole and /or pyrrole-like nitrogen,More than half (50%-77%) of the N in these polymers were nonhydrolyzable,The role of Maillard reacion in the formation of nonhydrolyzable nitrogen in soil organic matter is discussed. 相似文献
7.
Phenolic polymers synthesized by reactions by reactions of p-benzoquinone with 15N-labelled protein or (15NH4)2SO4 were studied by using 15N CP-MAS NMR technique in combination with chemical approaches.Results showed that more than 80% of nitrogen in quinone-protein polymers was in the form of amide with some present as aromatic and /or aliphatic amine and less than 10% of nitrogen occurred as heterocyclic N.The nitrogen distribution in the non-hydrolyzable residue of the quinone-protein polymers was basically similar to that of soil humic acid reported in literature with the exception that a higher proportion of N as heterocyclic N and aromatic amine and a lower proportion of N as amide and aliphatic amine were found in the former than in the latter,More than 70% of total nitrogen in quinone-(NH4)2OS4 polymer was acid resistant ,of which about 53% occurred as pyrrole,nitrile and imion type N.The possible roles of the reactions of phenols or quinones with proteins in the formation of humic acid.especially the non-hydrolyzable nitrogen in humicacid,are discussed. 相似文献
8.
N Transformation of Green Manure Incorporated Directly of Returned into Soil After Feeding Pig and Its Efficiency 总被引：1，自引：0，他引：1
15N－labelled green manure was used to feed pigs.Its nitrogen recovery by pig body,feces and uring was 23.5%,23.8%and 28.8% respectively,totalling 76.1%.Feces and green manure coordinated respectively with equal amount of CO(NH2)2-N as well as urine alone were applied as basic fertilizer in microplot experiments,The 15N recovery from feces and urine was equivalent to 2.51%and 4.82%by rice grain,and 0.98% and 1.94% by straw respectively,and soil residual ^15N from them took 13.3% and 4.90% of the ^15N in green manure,After feeding pigs with green manure and returning their feces and uringe into soil,the ^15N recovery by pig body and rice grain was 30.8%,and that by pig body,and rice plant as well as soil residual took 52.7% of the 15N in feed.^15N loss was 23.9% in pig feeding and 23.4% in rice planting.When green manure was incorporated directly into soil,its 15N recovery by grain was 26.65%,that by rice plant plus soil residual was 65.2%,and the loss was 34.8%. 相似文献
9.
Chemical characteristics of humic substances in soils with different mineralogical characteristics and under different utilization paterns in Zhangpu,Fujian Province,together with two pairs of cultivated soils in North China Plain were studied by chemical analysis,visible and IR spectroscopy and ^13C NMR spectrometry.For soils in Zhanpu the HA/FA ratio and both the aromaticity and the degree of humification of HA were higher in soils with montmorillonite as the predominant clay mineral than in those with kaolinite as the predominant clay mineral,provided these soils were under the same utilization pattern.While for each pair of soils with similar mineralogical characteristics the HA/FA ratio was higher and the C/H ratio and the contnet of carboxyl group of HA were lower in paddy soil than in upland soil.Among the upland soils(or paddy soils)studied the Ha/FA ratio of soil in Zhangpu with kaolinite as the predominant clay mineral was the lowest,and that of soil in Zhangpu with montmorillonite as the predominant clay mineral was the highest .the lowest.and that of soil in Zhangpu with montmorillonite as the predominant clay mineral was the highest It was concluded that the presence of montmorillonite favored the fromation and maturation of humic acid. 相似文献
10.
Two soils with relatively high(Soil 1)and low(Soil 2) ammonium fixation capacities were used in this study to examiune the effect of ammonium fixation on the determination of N mineralized from soil microbial biomass.Organism suspension was quantitatively introduced to Soil 1 at various rates.Both fumigation-incubation (FI) and fumigation-extraction (FE) methods were used to treat the soil.The amount of fixed NH4^ increased with increasing rate of organism-N addition.A close correlation was found between the amount of fixed ammonium and th rate of organism-m addition.The net increases of fixed NH4^ -N were equivalent to 38% and 12% of the added organism-N for FI and FE treatments,rspectively,in this specific soil.To provide isotopic evidence,^15N-labelled organism-N was added to Soils 1 and 2 at 121.4 mg N kg^-1.In FI treatment,22 and 3mg N kg^-1 of labelled N were found in the fraction of fixed NH4^ -N in Soile 1 and 2 respectively;while in FE treatment,9 mg N kg^-1 of labelled N was found in the fraction of fixed NH4^ -N in Soil 1 only.There was no labelled N in the fraction of fixed NH4^ -N in Soil 2.In all of the unfumigated (check) soils,there was little or no labelled N in the fixed fractions,probably because the organism-N added was easily mineralized and nitrified.A mean of 0.64 for KN value,the fraction of N mineralized in the killed microbial biomass,as obtained with inclusion of the net increase of fixed NH4^ -N,The corresponding value calculated with exclusion of the net increase of ficed NH4^ -N was 0.46 ,It was concluded that ammonium fixation was a problem in deterination of KN,particularly for soils with a high ammonium fixation capacity, Results also showed that microbial biomass N measurement by FFE method was less affected by ammonium process than that by FI method. 相似文献
11.
Variations in the amount and composition of immobilized nitrogen (N) in major soil organic matter fractions were investigated
in a 730-day soil incubation experiment using 15N-labeled urea and 15N nuclear magnetic resonance spectroscopy with the cross polarization/magic angle spinning (15N CPMAS NMR) method. After 730 days, 24.7% of the applied N was recovered from the soil as organic N. The urea-derived N recovered
from humic acids and humin decreased from 11.2 and 33.8% of the applied amount after 14 days to 1.6 and 20.4% after 730 days,
respectively. When these values were corrected for the microbial biomass (MB) N, they ranged from 9.0 to 1.2% and 28 to 18%,
respectively. The proportion of urea-derived N recovered from fulvic acids was low, ranging between 0.4 and 5.8% (with MB
N) or 5.6% (without MB N) of the applied amount, whereas that from water-soluble nonhumic substances (WS-NHS; NHS in the fulvic
acid fraction) remained high, 28–33% of the applied amount after correction for the contribution of MB N up to day 365, and
decreased to 0.9% thereafter. The 15N CPMAS NMR spectra of humic acids, fulvic acids, and humin showed the largest signal at −254 to −264 ppm, corresponding to
peptide/amide N. The proportions of heterocyclic, peptide/amide, guanidine/aniline, and free amino N in the urea-derived humic
acid N were 3–7, 83–90, 5–7, and 2–4%, respectively. More than 80% loss of the urea-derived humic acid N did not markedly
alter their composition. No time-dependent variations were also observed for the proportions of respective N functional groups
in humin N, which were 3–5, 71–78, 12–17, and 6–10% in the same order as above. These results suggest the greater importance
of physical stability than structural variation for the initial accumulation of organic N in soil. 相似文献
12.
Jeferson Dieckow João Mielniczuk Heike Knicker Cimélio Bayer Deborah P. Dick Ingrid Kögel-Knabner 《Biology and Fertility of Soils》2005,42(2):153-158
This study was conducted to investigate the influence of land-use systems (grassland and cropland) and of long-term no-till cropping systems [bare soil, oat/maize (O/M), pigeon pea+maize (P+M)] on the composition of organic N forms in a subtropical Acrisol. Soil samples collected from the 0- to 2.5-cm layer in the study area (Eldorado do Sul RS, Brazil) were submitted to acid hydrolysis and cross-polarization magic angle spinning (CPMAS) 15N and 13C nuclear magnetic resonance (NMR) spectroscopies. The legume-based cropping system P+M contained the highest contents of non-hydrolysable C and N, hydrolysable C and N, amino acid N and hydrolysed unknown N. The relative proportion of non-hydrolysable N was higher in bare soil (30.0%) and decreased incrementally in other treatments based on the total C and N contents. The amino acid N corresponded to an average of 37.2% of total N, and was not affected by land use and no-till cropping systems. The non-hydrolysable residue contained lower O-alkyl and higher aromatic C concentrations, as revealed by CPMAS 13C NMR spectroscopy, and higher C:N ratio than the bulk soil. No differences in the bulk soil organic matter composition could be detected among treatments, according to CPMAS 13C and 15N NMR spectra. In the non-hydrolysable fraction, grassland showed a lower concentration of aromatic and a higher concentration of alkyl C than other treatments. From CPMAS 15N NMR spectra, it could be concluded that amide N from peptide structures are the main organic N constituent. Amide structures are possibly protected through encapsulation into hydrophobic sites of organic matter and through organomineral interaction. 相似文献
13.
The aims of this study were to determine the degree of lignin degradation and to investigate changes in the chemical composition of the organic matter in the forest floor in an N fertilized Norway spruce forest soil. Needle litter and mor humus were collected from the field experiment at Skogaby in southern Sweden (56°33′N; 13°13′E). The spruce stand had been fertilized for 11 years with 100 kg N ha−1 yr−1 as (NH4)2SO4. The degree of lignin degradation was determined with alkaline CuO oxidation followed by HPLC analysis. The chemical composition of the organic matter was characterized by CPMAS 13C NMR. Tannin was specifically analyzed using dipolar dephasing CPMAS 13C NMR and the N distribution was studied by CPMAS 15N NMR.The C-to-N ratios in the fertilized Oi and Oe layers were significantly lower than in the unfertilized layers (24 compared to 34 and 23 compared to 27, respectively). Neither the sum of the CuO oxidation products (Vanillyls+Syringyls+Cinnamyls expressed as VSC) nor the acid-to-aldehyde ratio ((Ac/Al)V) showed any significant treatment effects. The content of aromatic C (including phenolic C) was significantly lower in the unfertilized than in the fertilized Oi layer (18 versus 21%). In the unfertilized soil, VSC was positively correlated (r=+0.63, p<0.05) with the C-to-N ratio, whereas the phenolic C content was negatively correlated (r=−0.61, p<0.05). The tannin index showed a tendency of increasing from Oi to Oe layers in both treatments. Most of the organic N was found as amide-N, whereas no heterocyclic N was detected. We have not been able to show any major C structural changes due to N fertilization. We suggest that the significantly higher content of aromatic and phenolic C in the fertilized Oi layer is due to an initial stimulation of the microbial community. 相似文献
14.
Summary Two soils from Pakistan (Hafizabad silt loam and Khurrarianwala silt loam) and one from Illinois, USA (Drummer silty clay loam) were incubated with 15N-labelled soybean tops for up to 20 weeks at 30°C. Mineralization of soybean 15N was slightly more rapid in the Pakistani soils, and after 20 weeks of incubation, 50%, 53%, and 56% of the applied 15N was accounted for as (NH4
++NO3
–)-N in Drummer, Hafizabad, and Khurrarianwala soils, respectively. Potentially mineralizable N (determined by anaerobic incubation) varied between 1.5% and 10% of the applied 15N in the three soils at different stages of incubation; somewhat higher percentages were mineralizable in the Pakistani soils than in the Drummer soil. From 3.7% to 9% of the applied 15N was accounted for in the microbial biomass. From 10% to 32% of the applied N was recovered in the humic acid and fulvic acid fractions of the organic matter by sequential extraction with Na4P2O7 and NaOH; from 12% to 49% was recovered in the humin fraction. Of the three soils, Drummer soil contained more 15N as humic and fulvic acids. In all cases, the 15N was approximately equally distributed between the humic and fulvic acid fractions. A significant percentage of the humin 15N (52%–78%, equivalent to 8%–34% of the applied 15N) occurred in non-hydrolyzable (6 N HCl) forms. Of the hydrolyzable 15N, 42%–51% was accounted for as amino acid-N followed in order by NH3 (17%–30%), hydrolyzable unknown forms (20%–22%), and amino sugars (6%–2%). The recovery of applied 15N for the different incubation stages was 87±22%. Recovery was lowest with the Khurrarianwala soil, presumably because of NH3 volatilization losses caused by the high pH of this soil. 相似文献
15.
The chemistry of soil organic nitrogen: a review 总被引：6，自引：0，他引：6
1. From the data presented herein it is possible to deduce the following distribution of total N in humic substances and soils: proteinaceous materials (proteins, peptides, and amino acids) – ca. 40%; amino sugars – 5–6%; heterocyclic N compounds (including purines and pyrimidines) – ca. 35%; NH3–19%; approximately 1/4 of the NH3 is fixed NH4 +. Thus, proteinaceous materials and heterocyclics appear to be major soil N components. 2. Natural 15N abundance levels in soils and humic materials are so low that direct analysis by 15N NMR is very difficult or impossible. To overcome this difficulty, the soil or humic material is incubated with 15N-enriched fertilizer. Even incubation in the laboratory for up to 630 days does not produce the same types of 15N compounds that are formed in soils and humic materials over hundreds or thousands of years. For example, very few 15N-labelled heterocyclics are detected by 15N NMR. Does this mean that heterocyclics are not present? Or are the heterocyclics that are present not labelled under these experimental conditions and therefore not detected by the 15N NMR spectrometer ? Another possibility is that a large number of N heterocyclics occur in soils, but each type occurs in very low concentrations. Until the sensitivity is improved, 15N NMR will not provide results that can be compared with data obtained from the same soil and humic material samples by chemical methods and mass spectroscopy. 3. What is most important with respect to agricultural is that all major N forms in soils are available to organisms and are sources of NH3 or NH4 + for plant roots and microbes. Naturally, some of the NH3 will enter the N cycle. 4. From chemical and pyrolysis-mass spectrometric analyses it appears that N heterocylics are significant components of the SOM, rather than degradation products of other molecules due to pyrolysis. The arguments in favor of N heterocyclics as genuine SOM components are the following: a) Some N-heterocyclics originate from biological precursors of SOM, such as proteinaceous materials, carbohydrates, chlorophyll, nucleic acids, and alkaloids, which enter the soil system as plant residues or remains of animals. b) In aquatic humic substances and dissolved organic matter (DOM) at considerably lower pyrolysis temperatures (200 to 300°C), free and substituted N-heterocyclics such as pyrroles, pyrrolidines, pyridines, pyranes, and pyrazoles, have been identified by analytical pyrolysis (Schulten et al 1997b). c) Their presence in humic substances and soils was also detected without pyrolysis by gel chromatography – GC/MS after reductive acetylation (Schnitzer and Spiteller 1986), by X-ray photoelectron spectroscopy (Patience et al. 1992), and also by spectroscopic, chromatographic, chemical, and isotopic methods (Ikan et al. 1992). 5. While we can see light at the end of the tunnel as far as soil-N is concerned, further research is needed to identify additional N-containing compounds such as N- heterocyclics, to determine whether these are present in the soil or humic materials in the form in which they were identified or whether they originate from more complex structures. If the latter is correct, then we need to isolate these complex N-molecules and attempt to identify them. 相似文献
16.
《Communications in Soil Science and Plant Analysis》2012,43(2):148-168
A glasshouse incubation experiment was conducted to study the carbon (C) and nitrogen (N) mineralization of municipal solid waste compost (MSWC) added at differential rates to a laterite soil where cassava has been continuously cultivated for the past 10 years. The rate of C mineralization from added substrates increased with increasing rates of addition of MSWC. Available N significantly increased with increase in the rate of application of MSWC. There was a decreasing trend in E465/E665 ratio of humic acid as we increased the rate of application of MSWC from 2.5 to 20 t ha?1. The Cross Polarization Magic Angle Spinning (CPMAS) 13C NMR spectral analysis revealed that there are differences in the rate of humification of added MSWC, and application of MSWC at 15 t ha?1 resulted in least humification with the greatest alkyl C, lowest aromatic C, and greater O-alkyl C content. The decomposition rate (R) was found to be greater for this treatment. The residual C in soil was found to increase over time coincident with greater rates of MSWC application, indicating increased C stabilization, which could improve soil quality. 相似文献
17.
不同碳源添加对钙质土高累积硝态氮向土壤有机氮库转化的研究 总被引：3，自引：0，他引：3
QIU Shao-Jun JU Xiao-Tang J. INGWERSEN GUO Zi-De C. F. STANGE R. BISHARAT T. STRECK P. CHRISTIE ZHANG Fu-Suo 《土壤圈》2013,23(2):205-212
Excessive amounts of nitrate have accumulated in many soils on the North China Plain due to the large amounts of chemical N fertilizers or manures used in combination with low carbon inputs. We investigated the potential of different carbon substrates added to transform soil nitrate into soil organic N (SON). A 56-d laboratory incubation experiment using the 15 N tracer (K15 NO3 ) technique was carried out to elucidate the proportion of SON derived from accumulated soil nitrate following amendment with glucose or maize straw at controlled soil temperature and moisture. The dynamics and isotopic abundance of mineral N (NO3 and NH+4 ) and SON and greenhouse gas (N2O and CO2 ) emissions during the incubation were investigated. Although carbon amendments markedly stimulated transformation of nitrate to newly formed SON, this was only a substitution effect of the newly formed SON with native SON because SON at the end of the incubation period was not significantly different (P > 0.05) from that in control soil without added C. At the end of the incubation period, amendment with glucose, a readily available C source, increased nitrate immobilization by 2.65 times and total N2O-N emission by 33.7 times, as compared with maize straw amendment. Moreover, the differences in SON and total N2O-N emission between the treatments with glucose and maize straw were significant (P < 0.05). However, the total N2O-N emission in the straw treatment was not significantly (P > 0.05) greater than that in the control. Straw amendment may be a potential option in agricultural practice for transformation of nitrate N to SON and minimization of N2O emitted as well as restriction of NO3-N leaching. 相似文献
18.
《Soil Science and Plant Nutrition》2013,59(5):535-544
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