固态13C和15N核磁共振法研究15N标记土壤的腐殖质组分

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.     

内蒙古草原碳、氮储量:气候与土壤质地的关系

Understanding the spatial variability of soil carbon(C) storage and its relationship with climate and soil texture is critical for developing regional C models and for predicting the potential impact of climate change on soil C storage. On the basis of soil data from a transect across the Inner Mongolian grasslands, we determined the quantitative relationships of C and nitrogen(N) in bulk soil and particle-size fractions(sand, silt, and clay) with climate and soil texture to evaluate the major factors controlling soil C and N storage and to predict the effect of climate changes on soil C and N storage. The contents of C and N in the bulk soil and the different fractions in the 0–20 and 20–40 cm soil layers were positively correlated with the mean annual precipitation(MAP) and negatively correlated with the mean annual temperature(MAT). The responses of C storage in the soil and particle-size fractions to MAP and MAT were more sensitive in the 0–20 cm than in the 20–40 cm soil layer. Although MAP and MAT were both important factors influencing soil C storage, the models that include only MAP could well explain the variation in soil C storage in the Inner Mongolian grasslands. Because of the high correlation between MAP and MAT in the region, the models including MAT did not significantly enhance the model precision. Moreover, the contribution of the fine fraction(silt and clay) to the variation in soil C storage was rather small because of the very low fine fraction content in the Inner Mongolian grasslands.     

日本常规耕作和有机耕作(翻耕与免耕)农田的动物区系(螨和线蚓)比较

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.     

森林生态系统中土壤有机质组分的固态13C核磁共振波谱表征

Forest management practices such as prescribed burning and thinning in forest ecosystems may alter the properties of soil organic matter (SOM).In this study,surface soils from field plots in the Bankhead National Forest,Alabama,USA,were used to investigate possible SOM transformations induced by thinning and burning.Elemental analysis and solid-state 13C cross polarization magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectroscopy were used to characterize SOM fractions in whole soils,humic substances,and density fractions.Our data revealed that the changes in SOM fractions due to the repeated burning carried out in the forest ecosystem studied were involved mainly with alkyl C,O-alkyl C,and carbohydrate functional groups,implying that most prominent reactions that occurred involved dehydrogenation,de-oxygenation,and decarboxylation.In addition,burning and thinning might have also affected the distribution and composition of free and occluded particulate SOM fractions.The limited structural changes in SOM fractions suggested that low-intensity prescribed fire in the forest ecosystem studied will not create major structural changes in SOM fractions.     

Chemical and spectroscopic characteristics of humic acid from a clay loam soil in Ontario after 52 years of consistent fertilization and crop rotation

Long-term fertilization and crop rotation can influence both organic C sequestration as well as the C composition of soils and the more resistant organic C compounds contained in humic acid(HA). This study examined the effects of fertilization and cropping type(monoculture corn(MC) and Kentucky bluegrass sod(KBS) and corn-oat-alfalfa-alfalfa rotation(RC)) on the HA composition of soil from a 52-year field study in southern Ontario, Canada. Humic acid samples were extracted from soil, and elemental analysis, infrared spectroscopy, solid state 13C nuclear magnetic resonance spectra, and electron paramagnetic resonance methods were used to determine the influence of the cropping type on the characteristics of HA. Both fertilization and cropping type affected the chemical characteristics of HA. Fertilization led to a 5.9% increase in C, a 7.6% decrease in O, and lower O/C and(N + O)/C ratios in HA as compared to the corresponding non-fertilized treatments. Rotation resulted in a lower proportion of C(48.1%) and a greater(N + O)/C ratio(0.7) relative to monoculture cropping. Infrared spectroscopy analysis showed that HA contained more C-O groups in fertilized soil than in non-fertilized soil under MC and KBS. Fertilization increased the O-alkyl-C, phenolic-C, and free radical contents of HA relative to non-fertilization treatments. Rotation decreased the aliphatic and carboxyl groups and increased the O-alkyl, carbohydrate, aryl, and phenolic groups and free radicals, relative to MC and KBS. Both long-term crop rotation and fertilization dramatically modified the soil HA composition. Significant relationships were observed between the molecular composition of HA and soil organic C. Hence, humic acid characterization could be used as an indicator of the long-term sustainability of crop management practices.     

利用方式和土壤肥力对土壤团聚体和养分的影响

The size distribution of water-stable aggregates and the variability of organic C, N and P contents over aggregate size fractions were studied for orchard, upland, paddy, and grassland soils with high, medium, and low fertility levels. The results showed that > 5 mm aggregates in the cultivated upland and paddy soils were 44.0% and 32.0%, respectively, less than those in the un-tilled orchard soil. Organic C and soil N in different size aggregate fractions in orchard soil with high fertility were significantly higher than those of other land uses. However, the contents of soil P in different size aggregates were significantly greater in the paddy soil as compared to the other land uses. Soil organic C, N and P contents were higher in larger aggregates than those in smaller ones. The amount of water-stable aggregates was positively correlated to their contribution to soil organic C, N and P. For orchard and grassland soils, the > 5 mm aggregates made the greatest contribution to soil nutrients, while for upland soil, the 0.25-0.053 mm aggregates contributed the most to soil nutrients. Therefore, the land use with minimum disturbance was beneficial for the formation of a better soil structure. The dominant soil aggregates in different land use types determined the distribution of soil nutrients. Utilization efficiency of soil P could be improved by converting other land uses to the paddy soil.     

造林恢复植被后土壤的化学计量学特征对其碳组分的影响

Afforestation is recognized as an important driving force for soil organic C(SOC) dynamics and soil element cycling.To evaluate the relationships between soil C:N:P stoichiometry and SOC fractions,soil C:N:P stoichiometry distributions at 0–200 cm soil depths were analyzed and the contents of SOC fractions were evaluated in 9 typical land-use systems on the Loess Plateau of China.The contents of light fraction organic C,particulate organic C(53,53–2 000,and2 000 μm),labile organic C,microbial biomass C,and dissolved organic C decreased with increasing soil depth and were higher in afforested soil than in slope cropland soil.Compared with the slope cropland,different vegetation types influenced soil C:N,C:P,and N:P ratios,especially when C:P and N:P ratios were significantly higher(P0.05).Moreover,SOC fractions at the 0–10 and 10–40 cm depths were particularly affected by soil C:P ratio,whereas those at the 40–100 and 100–200 cm soil depths were significantly affected(P0.05) by soil N:P ratio.These results indicate that changes in SOC fractions are largely driven by soil C:P and N:P ratios at different soil depths after afforestation.     

不同土地利用方式下上壤微生物群落水平生理图谱(CLP)与土壤碳、氮有效性之间的相互关系（英文）

The goal of this work was to assess soil microbial respiration,determined by the assay of community-level physiological profiling in an oxygen-sensitive microplate(O2-CLPP),in response to endogenous C and several individual C substrates in the soils with different organic C contents(as a function of soil type and management practice).We also used the O2-CLPP to determine the respiratory response of these soils to endogenous C and amended C substrates with N addition.A respiratory quotient(RQ) was calculated based on the ratio of the response to endogenous soil C vs.each C-only substrate,and was related to total organic carbon(TOC).For assessing N availability for microbial activity,the effect of N supplementation on soil respiration,expressed as N_(ratio),was calculated based on the response of several substrates to N addition relative to the response without N.Soils clustered in 4 groups after a principal component analysis(PCA),based on TOC and their respiratory responses to substrates and endogenous C.These groups reflected differences among soils in their geographic origin,land use and C content.Calculated RQ values were significantly lower in natural forest soils than in managed soils for most C-only substrates.TOC was negatively correlated with RQ(r = —0.65),indicating that the soils with higher organic matter content increased respiratory efficiency.The N addition in the assay in the absence of C amendment(i.e.,only endogenous soil C present) had no effect on microbial respiration in any soil,indicating that these soils were not intrinsically N-limited,but substrate-dependent variation in N_(ratio) within soil groups was observed.     

由木糖和15N标记的甘氨酸形成的美拉德氏聚合物的氮素形态

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.     

中国黑土上腐殖酸和腐殖物质的提取及其描述

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.     

Analysis of phosphorus in two humic acid fractions of intensively cropped lowland rice soils by 31P‐NMR

The organic forms of phosphorus in the soil appear to be changing as rice growing intensifies and the soil is flooded for longer in tropical Asia. To examine these changes, we extracted the labile mobile humic acid (MHA) and more recalcitrant calcium humate (CaHA) fractions from soils supporting long‐term field trials in the Philippines and analysed them by solution ³¹P‐nuclear magnetic resonance (NMR) spectroscopy. Diester P and sugar‐diester P accumulated moderately with increasing intensity of irrigated rice cropping, reaching a combined 42% of all MHA‐P for a triple‐cropped irrigated field compared with 28% for fully aerated fields growing dryland crops. The mono‐ to diester P ratio decreased by 43% for the MHA and CaHA from the aerated fields to the triple‐cropped field. Smaller effects on forms of P were noted for the rates and type of N, P and K fertilizer and site effects. The effects of treatment and site were more noticeable in the MHA than in the CaHA. The proportions in the NMR spectra were tightly correlated with visible light absorption, concentrations of organic free radicals and H, and ¹⁵N‐NMR spectral proportions, which indicate the degree of humification. The MHA and CaHA accounted for only 0.6–8.3% and 0.9–5.7%, respectively, of total P; most of the P is inorganic.     

Labile soil organic matter as a potential nitrogen source in golf greens

The loss of fertilizer N from golf greens can be high depending upon management (irrigation schedule, N source, rate and timing of fertilizer application) as well as soil conditions. Although soil organic matter (SOM) is acknowledged as a major source of N and other nutrients, its potential as an N source seems to be neglected in the management of golf greens. The susceptibility of SOM to degradation is one indication of how active a role SOM plays as a nutrient source. An extraction method developed by Olk et al. [Geoderma 65 (1995) 195] distinguishes humic acid fractions by their binding to dominant stabilizing soil cations and separates them into calcium-bound (CaHA) and non calcium-bound or mobile (MHA) fractions. Mobile humic acid is a relatively young, N-rich HA fraction that does not appear to form stable complexes with Ca. The MHA could therefore play a greater role in nutrient availability than CaHA. We determined C and N distributions within SOM extracted from these two HA fractions in 11 golf greens ranging in age from 4 to 28 yr. Because SOM in golf greens is recently formed, and MHA is an N-rich fraction representing an early stage of SOM evolution, we hypothesized that the MHA fraction would account for a larger proportion of soil organic N than CaHA. The amounts of both HA-C and HA-N increased significantly with green age. MHA accounted for a larger proportion (20-27%) of total soil C than CaHA-C (8-14%). MHA was also enriched in N compared to CaHA with consistently smaller C-to-N ratios. Thus, the greater abundance of MHA and its higher N concentration accounted for a larger proportion of soil organic N (24-45%). The equivalence of MHA-N ranged between 250 kg N ha⁻¹ for a 4 yr-old green and 775 kg N ha⁻¹ for a 21 yr-old green. Thus, soils of established greens contain significant quantities of labile SOM rich in N that could through mineralization supply part of the fertilizer N requirement of turf grass. A greater understanding of the dynamics of this resource is needed if we are to manage golf greens for optimal use without negative consequences to the environment.     

Changes in chemical properties of organic matter with intensified rice cropping in tropical lowland soil

Rice systems in Asia have intensified rapidly in the past 30 years, and significant areas of irrigated lowland rice are now supporting two or three rice crops per year. Our objective was to compare the chemical composition of soil organic matter (SOM) from four fields with different histories of rice cropping intensity and soil submergence: (i) a single-crop rainfed, dryland rice system without soil submergence, (ii) an irrigated rice and soybean rotation, and irrigated (iii) double- or (iv) triple-crop rice systems in which soil remains submerged during much of the year. In all four soils, extracted mobile humic acid (MHA) and calcium humate (CaHA) fractions were of modern age by ¹⁴C-dating, and represented about 20% of total N and organic C. The MHA was enriched in N and hydrolysable amino acids (AA) compared with CaHA in all soils. With increased frequency of irrigated rice cropping, however, there was a large increase in phenolic content of SOM. We speculate that slower lignin decomposition caused by deficiency of O₂ in submerged soil leads to incorporation of phenolic moieties into young SOM fractions. The increased phenolic character of these fractions may influence N cycling and the N supplying capacity of lowland soils supporting two or three annual crops of irrigated rice.     

Accumulation of heterocyclic nitrogen in humified organic matter: a 15N‐NMR study of lowland rice soils

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.     

Quantitative solid-state 13C NMR spectroscopy of organic matter fractions in lowland rice soils

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 (C_obs) 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 C_obs. The Bloch decay (BD) technique provided more quantitatively reliable ¹³C NMR spectra, as evidenced by values of C_obs 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 C_obs(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 (T_1ρH) E diting). Rapid T_1ρH 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 T_1H and T_1ρH were found to correlate with other NMR properties and also with cropping management. Non‐uniform rates of T_1H relaxation in two of the CaHA fractions enabled the generation of proton spin relaxation editing subspectra.     

Conserved chemical properties of young humic acid fractions in tropical lowland soil under intensive irrigated rice cropping

Increasing cropping intensity (i.e. number of crops per year) of irrigated rice seems to cause an accumulation of phenolic compounds in the soil organic matter (SOM). We have studied the chemical nature of SOM in a broad range of soil types at different sites with long-term double- and triple-crop irrigated rice trials. Accumulation of phenols, as measured by ¹³C nuclear magnetic resonance spectroscopy, was found in both the mobile humic acid (MHA) and calcium humate (CaHA) fractions at all sites, regardless of soil type, hydrology during the fallow, and with and without inorganic fertilizer or green manures. Although phenols accumulated consistently in MHA and CaHA, the C, N and hydrolysable amino acid concentrations, degree of humification and amounts of MHA and CaHA were significantly altered by crop management, and they varied from site to site. Our results are consistent with the hypothesis that the accumulation of phenols is a characteristic of the anaerobic, or nearly anaerobic, soil conditions that exist at the initial stages of SOM formation in submerged irrigated rice soils. By contrast, other SOM properties are additionally influenced by soil conditions that govern the degradation and turnover of existing SOM. The chemical properties of MHA and CaHA indicated that they are labile, and the quantities of these HA fractions were more sensitive to recent management than were total soil C or N.     

13C NMR characterization of humic acids from soils of a development sequence

Humic acids were isolated from nine topsoils in New Zealand tussock grasslands. Cross-polarization ¹³C NMR spectra of solid samples were used to estimate fractions of carbon contained in different types of chemical functional groups. The degree of oxygen substitution of aromatic rings showed a strong negative correlation with soil development. Aromaticities greater than 0.25 were found in humic acids from only the two least-developed soils.     

The significance of solid‐state 13C NMR spectroscopy of whole soil in the characterization of humic matter

Abstract

Differences in characteristics of humic matter were investigated by solid‐state CP/MAS ¹³C NMR spectroscopy of whole (nontreated) materials and their extracted humic fractions. Samples used in the analysis were lignite, a commercial humate AG, and the Bh horizons of a Mascotte and a Lawnwood soil. Humic fractions were extracted by the 0.1 M NaOH or Na₄P₂O₇ (pH 9.8) method. The humic (HA) and fulvic acid (FA) obtained were weighed and analysed for total acidity, carboxyl and phenolic‐OH group contents. Whole lignite, humate AG and soil samples, and the HA and FA fractions were analyzed by solid state CP MAS ¹³C NMR and infrared spectroscopy. Carbon, H, and N contents were determined by chemical analysis. NMR spectra of the combined HA+FA extracts resembled the spectra of the whole materials. No additional signals were detected, indicating that alien compounds were not produced during the extraction. The best spectra were obtained with HA samples produced by the NaOH method. These spectra closely resembled those of the untreated materials. Spectral and chemical differences noticed between the HA (or FA) fractions were attributed more to differences in origin than to the extraction procedure. Aliphatic, aromatic and carboxyl groups were the major components of HA from lignite and humate AG. In contrast, HA from the two Haplaquods were characterized by four major components: the aliphatic, polysaccharide, aromatic, and carboxyl groups. Regardless of origin, all the HA fractions contained similar functional groups, as indicated by their close similarities in infrared spectra.     

Chemical heterogeneity of humic substances: characterization of size fractions obtained by hollow-fibre ultrafiltration

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.     

In-source pyrolysis-field ionization mass spectrometry and Curie-point pyrolysis-gas chromatography/mass spectrometry of amino acids in humic substances and soils

With the aid of in-source pyrolysis-field ionization mass spectrometry (Py-FIMS) and Curie-point pyrolysis-gas chromatography/mass spectrometry (cPy-GC/MS) in the conventional electron impact mode, characteristic signals of 23 amino acid standards were described. Thermal and mass spectrometric fragmentation pathways of these amino acids differed with each method and complemented each other. Pyrolysis products assigned by Py-FIMS extended the range of signals for N-containing compounds in humic substances and soil organic matter and gave marker signals for free amino acids and their subunits in proteinaceous materials. These characteristic signals were correlated with the amino acid content in N-rich humic fractions consisting of seven fulvic acids and eight humic acids. The selected marker signals reflected 25–84% of the variances of the molar distribution of acidic, neutral, neutral aromatic, and basic amino acids in the humic fractions. In addition, a well described agricultural soil (0.08% amino acid N) was spiked with a standard amino acid mixture (0.08 mg amino acid N 100 mg^-1 dry soil) and produced enhancements of the relative abundances of the corresponding amino acid signals. Moreover, for 27 samples of whole agricultural soils of widely different origins, soil types, and vegetations, 15 selected amino acid indicators were correlated significantly with -amino N (r=0.76^***) and total N (r=0.65^***).