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1.
Soil organic matter (SOM) transformations caused by heating were analyzed using the stable carbon isotope (13)C as a tracer to follow C mineralization dynamics and C transfers between different organic compartments. A (13)C-labelled soil, obtained by incorporation of (13)C-enriched Lolium perenne phytomass into a pine forest soil, was heated for 10 min at 385 degrees C to reproduce conditions typical of a forest fire and changes in total C content, potential C mineralization activity and C distribution between the different soil organic fractions were determined. Changes caused by heating on the potential soil C mineralization, determined by laboratory aerobic incubation, reveal alterations to the SOM biodegradability; some stabilized SOM showed an increase in biodegradability, whereas less stabilized SOM became more resistant to microorganisms. Chemical fractionations of SOM allowed us to monitor changes in its composition. As a consequence of heating, the less polymerized humic fractions were the most strongly affected, with the total disappearance of fulvic acids. A significant increase in the quantity and degree of polymerization of the humic acids at the expense of other more (13)C-enriched substances was also found. Finally, a large decrease in humin was observed, its solubilizable part disappearing completely, probably as a consequence of the incorporation of the byproducts into the free organic matter fraction. 相似文献
2.
以自然土壤和过氧化氢分级土壤为实验模拟样品,测定了菲在这些样品上的吸附一解吸等温线,用线性和Freundlich模型拟合了这些等温线.^13C NMR谱表明,随着土壤有机质腐殖化程度的加深,有机质将含有较多的长链烷烃化合物,含氧、氮化合物有所减少,芳香环的数量变化不大.吸附实验结果表明,土壤有机质含量与菲的吸附容量存在一定的线性相关关系.有机质腐殖质化程度较深的样品比原土壤具有更大的吸附容量,其吸附等温线表现出更为明显的非线性,而且具有更明显的解吸滞后现象.说明土壤中一些结构紧密和含极性官能团较少的有机质是引起菲的非线性吸附过程和解吸滞后现象的主要原因。 相似文献
3.
Andosols are usually formed from volcanic substrates, with thick A horizons high in organic carbon mainly in the form of stabilized humic fractions. The peculiar properties of these soils are, to large extent, affected by poorly crystalline materials like allophanes, imogolite and other Fe and Al oxyhydroxides that induce intense organo-mineral interactions which are considered to play a relevant role in OM protection against biodegradation as regards other soils developed under similar climatic conditions. Little is known about the molecular composition of this stabilized OM in a soil scenario often considered as an efficient C-sink in terms of C sequestration processes. Whole soil samples in addition to isolated humic and fulvic acids from organic A horizons of three soils with andic properties and one non-andic soil (Sodic Cambisol) from the island of Tenerife (Canary Islands, Spain) were analysed by double shot pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) in order to get some insight on the molecular composition of different structural domains of progressive structural stability. Clear differences were found between soils, both in thermal desorption and pyrolysis behaviour of humic substances. In general the results suggest large yields of aliphatic (both alkyl and carbohydrate-derived pyrolysis compounds) pointing to high-performance processes of incorporation of aliphatic humic constituents in andosols probably favoured by interactions with amorphous minerals, whereas in non-andic soils the latter are comparatively less stabilized and are removed in early pyrolysis stages as if they occurred as loosely joined, thermoevaporation-released products. In fact, compared to Cambisol, humic and fulvic acids from andic soils led to comparatively richer pyrograms and compound assemblages. The lack of similar amounts of these loosely joined, mainly aliphatic structures after thermal desorption of the whole andic soils indicate an origin for humic substances based on rapid sequestration of C-forms of recent (litter or microbial) origin. 相似文献
4.
Andosols are usually formed from volcanic substrates, with thick A horizons high in organic carbon mainly in the form of stabilized humic fractions. The peculiar properties of these soils are, to large extent, affected by poorly crystalline materials like allophanes, imogolite and other Fe and Al oxyhydroxides that induce intense organo-mineral interactions which are considered to play a relevant role in OM protection against biodegradation as regards other soils developed under similar climatic conditions. Little is known about the molecular composition of this stabilized OM in a soil scenario often considered as an efficient C-sink in terms of C sequestration processes.Whole soil samples in addition to isolated humic and fulvic acids from organic A horizons of three soils with andic properties and one non-andic soil (Sodic Cambisol) from the island of Tenerife (Canary Islands, Spain) were analysed by double shot pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) in order to get some insight on the molecular composition of different structural domains of progressive structural stability.Clear differences were found between soils, both in thermal desorption and pyrolysis behaviour of humic substances. In general the results suggest large yields of aliphatic (both alkyl and carbohydrate-derived pyrolysis compounds) pointing to high-performance processes of incorporation of aliphatic humic constituents in andosols probably favoured by interactions with amorphous minerals, whereas in non-andic soils the latter are comparatively less stabilized and are removed in early pyrolysis stages as if they occurred as loosely joined, thermoevaporation-released products.In fact, compared to Cambisol, humic and fulvic acids from andic soils led to comparatively richer pyrograms and compound assemblages. The lack of similar amounts of these loosely joined, mainly aliphatic structures after thermal desorption of the whole andic soils indicate an origin for humic substances based on rapid sequestration of C-forms of recent (litter or microbial) origin. 相似文献
5.
Liquid state, high resolution 13C NMR spectroscopy and mass spectrometry were used to study the composition and structure of soil organic matter (SOM) using
soil extracts from two long-term experiments at the Rothamsted Experimental Station. Both one- and two-dimensional NMR techniques
were applied. 13C NMR sub-spectra of the CH
n
(n=0...3) groups, obtained by the Distortionless Enhancement by Polarisation Transfer (DEPT) technique, were used for the
elucidation of the qualitative and quantitative composition of humic and fulvic acids in the soils. The chemical structure
of SOM was further analysed at the molecular level through Fast Atom Bombardment Mass Spectrometry (FABMS) and Gas Chromatography-Mass
Spectrometry (GC/MS). Humic and fulvic extract results were not only compared to each other, but also to the solid state 13C NMR results for the complete soil sample. 相似文献
6.
The effect of a recent vegetation change (<100 years) from C(4) grassland to C(3) woodland in central Queensland, Australia, on soil organic matter (SOM) composition and SOM dynamics has been investigated using a novel coupled thermogravimetry-differential scanning calorimetry-quadrupole.mass spectrometry-isotope ratio mass spectrometry (TG-DSC-QMS-IRMS) system. TG-DSC-QMS-IRMS distinguishes the C isotope composition of discrete SOM pools, showing changes in labile, recalcitrant and refractory carbon in the bulk soil and particle size fractions which track the vegetation changes. Analysis of evolved gases (by QMS) from thermal decomposition, rather than observed weight loss, proved essential in determining the temperature at which SOM decomposes, because smectite and kaolinite clays contribute to observed weight losses. The delta(13)C analyses of the CO(2) evolved at different temperatures for bulk soil and particle size-separates showed that most of the labile SOM under the more recent woody vegetation was C(3)-derived carbon whereas the delta(13)C values in the recalcitrant SOM showed greater C(4) contributions. This indicated a shift from grass (C(4))- to tree (C(3))-derived carbon in the woodland, which was also supported by the two-phase (13)C enrichment with depth, i.e. C(3) vegetation dominated the top soil (0-10 cm), but the C(4) contribution increased with depth (more gradual). This is perturbed by the inclusion of charcoal from forest fires ((14)C age incursions) and by the deep incorporation of C(3) carbon due to root penetration. 相似文献
7.
The conversion of grassland into cultivated land is a common agricultural practice, generally leading to the decrease of the soil organic matter (SOM) content. In this study, we analysed quantitative changes in carbon content. Additionally qualitative changes occurring in the soil organic matter composition on a molecular basis were assessed using Curiepoint pyrolysis coupled to gas chromatography and mass spectrometry (pyrolysis GC/MS). The aim of the study was to follow the development of SOM in grassland soil, after conversion into arable soil.Soil was sampled before the conversion (0 month) as well as 3 months, and 1 year after the conversion. The samples were treated with 10% HF to remove mineral material before being subjected to analysis of the bulk chemical composition by pyrolysis GC/MS. The relative contributions of single molecules were obtained by the integration of the total ion chromatogram.Pyrolysis products derived from lignins, proteins and polysaccharides were identified in all samples. SOM under grassland, arable land and converted grassland released similar pyrolysis products. Three months after the conversion, lignin-derived pyrolysis products were found at lower concentrations in the converted grassland soil. Principal component analysis showed that arable land, grassland and the converted grassland could be distinguished using the score plot of the 2nd and 3rd principal components. The differences induced by grassland conversion are only transitory and 1 year after the conversion, SOM has a similar composition as SOM of the initial grassland soil. 相似文献
8.
The simultaneous analysis of evolved gases and the determination of stable isotope composition (delta13C) as part of a thermal analysis experiment have been used to (a) distinguish bulk chemical hosts for carbon (C) and nitrogen (N) within a soil and (b) track labelled C within a soil sequestration experiment. C3 and C4 dung was applied to a pasture soil, and soil samples taken for analysis. The results of thermogravimetry-differential scanning calorimetry-quadrupole mass spectrometry-isotope ratio mass spectrometry (TG-DSC-QMS-IRMS) show that the proportion of more refractory C (lignin-like) is greater for the dungs than for the soil organic matter (SOM), and that this increases with time within the soil. Analysis of evolved gases shows that nitrogen is associated with the decomposition of more refractory C, and is not so strongly associated with the labile C component. IRMS analysis distinguished C3 and C4 dung, and allowed the amount of C from these sources to be estimated for the soil samples. Most dung C enters the refractory SOM fraction. This paper demonstrates the potential of TG-DSC-QMS-IRMS in the investigation of SOM. 相似文献
9.
The severe heating of soil during wildfires and prescribed burns may result in adverse effects on soil fertility due to organic
matter loss. No rapid and reliable procedure exists to evaluate soil organic matter (SOM) losses due to heating. Enthalpy
of SOM combustion correlates with organic matter content. Quartz is a ubiquitous mineral in soils and has a remarkably constant
composition and reversible α–β phase transition at 575 °C. We suggest that SOM content in heated and unheated soils can be
compared using the ratio of SOM combustion enthalpy on heating to the β–α quartz transition enthalpy measured on cooling of
the same sample. This eliminates the need to dry and weigh the samples, making possible field applications of the proposed
method. The feasibility of using the (Δ H
comb SOM)/( ΔH
β–α Qz) ratio was established with experiments on soil samples heated in the laboratory and the method was then used for evaluation
of SOM loss on two pile burn sites at UC Berkeley’s Blodgett Forest Research Station in Georgetown, California. 相似文献
10.
The environmental concern on soil exploitation, linked to global warming by the Kyoto protocol, is responsible for increasing
interest in the understanding of the role of the composition and structure of the soil organic matter (SOM) on soil carbon,
C, dynamics. Thermal analysis and nuclear magnetic resonance (NMR) are applied to study the thermal properties, the structure
and composition of the SOM of six samples with different C contents in order to improve the interpretation of results given
by thermal analysis. Results showed that the direct integral of the combustion peaks obtained by DSC and the percentage of
SOM given by TG were both directly related to the quantity of total soil C. Thus, soils with higher C content showed higher
energy content too. The combustion temperatures of the curves given by DSC are those reported for labile OM. NMR results indicated
the presence of aliphatic C, carbohydrates, and a weak signal in the aromatic C band in all the samples that was not detected
in the DSC curves. Only two samples showed carboxyl/carbonyl C which was not detected by DSC also. 相似文献
11.
The heating effect on the soil organic matter (SOM) of a Mediterranean soil was studied in two fractions (macro- and microaggregates) and in two environments (soil under canopy of Quercus coccifera and bare soil between plants). Samples were heated under laboratory conditions at different temperatures (220, 380 and 500°C) to establish their effects on the SOM quality and quantity by comparison with unheated control samples (25°C). The SOM content in the soil under canopy was higher than in the bare one and in the microaggregate fractions than in the macroaggregate ones. Increasing temperatures caused, in general, the decrease of SOM content in both soils as well as in both aggregate classes. The quality of SOM was determined after extraction with 0.1 M NaOH and analysed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Obtained pyrolysates were characterized by the presence of polyphenols and other aromatic pyrolysis products (lipids, polysaccharides, proteins and lignin derivatives). Some of the products in these control samples, and furthermore the presence of black carbon (BC) markers (e.g. benzene, pyridine and toluene), confirmed the occurrence of past wildfires in the study zone. The composition of the SOM extracted from the soils heated at 220°C, was quite similar to that obtained from unheated soils. The products derived from polysaccharides and lignin, and some coming from polyphenols, were not detected in the pyrolysates of the soil heated at 380 and 500°C. 相似文献
12.
The molecular composition of soil organic matter (SOM) in three agricultural fields under different managements, was evaluated by off-line thermochemolysis followed by gas chromatography mass spectrometry analysis (THM-GC-MS). While this technique enabled the characterization of SOM components in coarse textured soil, its efficiency in heavy textured soils was seriously affected by the interference of clay minerals, which catalyzed the formation of secondary artifacts in pyrolysates. Soil demineralization with hydrofluoric acid (HF) solutions effectively improved the reliable characterization of organic compounds in clayey soils by thermochemolysis, while did not alter significantly the results of coarse textured soil. A wide range of lignin monomers and lipids molecules, of plant and microbial origin, were identified in the pyrograms of HF treated soils, thereby revealing interesting molecular differences between SOM management practices. Our results indicated that clay removal provided by HF pretreatment enhanced the capacity of thermochemolysis to be a valuable and accurate technique to study the SOM dynamics also in heavy-textured and OC-depleted cultivated soils. 相似文献
13.
Large old trees are the dominant primary producers of native pine forest, but their influence on spatial patterns of soil properties and potential feedback to tree regeneration in their neighbourhood is poorly understood. We measured stable isotopes of carbon (delta(13)C) and nitrogen (delta(15)N) in soil and litter taken from three zones of influence (inner, middle and outer zone) around the trunk of freestanding old Scots pine (Pinus sylvestris L.) trees, to determine the trees' influence on below-ground properties. We also measured delta(15)N and delta(13)C in wood cores extracted from the old trees and from regenerating trees growing within their three zones of influence. We found a significant and positive gradient in soil delta(15)N from the inner zone, nearest to the tree centre, to the outer zone beyond the tree crown. This was probably caused by the higher input of (15)N-depleted litter below the tree crown. In contrast, the soil delta(13)C did not change along the gradient of tree influence. Distance-related trends, although weak, were visible in the wood delta(15)N and delta(13)C of regenerating trees. Moreover, the wood delta(15)N of small trees showed a weak negative relationship with soil N content in the relevant zone of influence. Our results indicate that large old trees control below-ground conditions in their immediate surroundings, and that stable isotopes might act as markers for the spatial and temporal extent of these below-ground effects. 相似文献
14.
Our understanding of forest biosphere-atmosphere interactions is fundamental for predicting forest ecosystem responses to climatic changes. Currently, however, our knowledge is incomplete partly due to inability to separate the major components of soil CO(2) effluxes, viz. root respiration, microbial decomposition of soil organic matter and microbial decomposition of litter material. In this study we examined whether the delta(13)C characteristics of solid organic matter and respired CO(2) from different soil-C components and root respiration in a Danish beech forest were useful to provide information on the root respiration contribution to total CO(2) effluxes. The delta(13)C isotopic analyses of CO(2) were performed using a FinniganMAT Delta(PLUS) isotope-ratio mass spectrometer coupled in continuous flow mode to a trace gas preparation-concentration unit (PreCon). Gas samples in 2-mL crimp seal vials were analysed in a fully automatic mode with an experimental standard error +/-0.11 per thousand. We observed that the CO(2) derived from root-free mineral soil horizons (A, B(W)) was more enriched in (13)C (delta(13)C range -21.6 to -21.2 per thousand ) compared with CO(2) derived from root-free humus layers (delta(13)C range -23.6 to -23.4 per thousand ). The CO(2) evolved from root respiration in isolated young beech plants revealed a value intermediate between those for the soil humus and mineral horizons, delta(13)C(root) = -22.2 per thousand, but was associated with great variability (SE +/- 1.0 per thousand ) due to plant-specific differences. delta(13)C of CO(2) from in situ below-ground respiration averaged -22.8 per thousand, intermediate between the values for the humus layer and root respiration, but variability was great (SE +/- 0.4 per thousand ) due to pronounced spatial patterns. Overall, we were unable to statistically separate the CO(2) of root respiration vs. soil organic matter decomposition based solely on delta(13)C signatures, yet the trend in the data suggests that root respiration contributed approximately 43% to total respiration. The vertical gradient in delta(13)C, however, might be a useful tool in partitioning respiration in different soil layers. The experiment also showed an unexpected (13)C-enrichment of CO(2) (>3.5 per thousand ) compared with the total-C signatures in the individual soil-C components. This may suggest that analyses of bulk samples are not representative for the C-pools actively undergoing decomposition. 相似文献
15.
The composition of lipids and fatty acids from the above-ground part of Origanum tytthanthum Gontsch. (Lamiaceae) is studied. Lipids from the air-dried plant material are enriched in glycolipids, essential fatty acids, and biologically active lipophilic substances. The free fatty acids include 15-methylhexadecanoic acid (0.5 % by GLC).Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 100–102, March–April, 2000. 相似文献
16.
Multivalent cations are suggested to influence the supramolecular structure of soil organic matter (SOM) via inter- and intra-molecular interactions with SOM functional groups. In this study, we tested the combined effect of cations, temperature treatment, and isothermal aging on SOM matrix properties. Samples from a peat and a mineral soil were either enriched with Na, Ca, and Al or desalinated in batch experiments. After treatment at 25, 40, 60, and 105 °C and after different periods of aging at 19 °C and 31 % relative humidity, we investigated the physicochemical matrix stability and the thermal stability against combustion. We hypothesized that multivalent cations stabilize the SOM matrix, that these structures disrupt at elevated temperatures, and that aging leads to an increase in matrix stability. The results show that cation-specific effects on matrix rigidity started to evolve in the peat only after 8 weeks of aging and were significantly lower than the temperature effects. Temperature treatment above 40 °C caused a non (or not immediately) reversible loss of water molecule bridges (WaMB) and above 60 °C a partly reversible melting process probably of semi-crystalline poly(methylene). Thermal stability increased with increasing cation valence and degree of protonation and was much less affected by temperature. Generally, Na-treated and control samples revealed lower thermal stability and lower increase in matrix rigidity with aging than those treated with Ca, Al, and H. We conclude that drying at elevated temperatures (>40 °C) may irreversibly change SOM structure via disruption of labile cross-links and melting of semi-crystalline domains. 相似文献
17.
Physical protection is one of the most important ways for stabilization of organic carbon in soils, and in order to properly manage soils as a sink for carbon, it is necessary to know how much organic carbon a given soil could protect and to have information on the molecular composition of this protected organic matter in soil. To this end, we studied individual horizons taken from a soil profile under Quercus rotundifolia stands over calcareous parent material. Horizons were subjected to a sequential extraction using solutions of sodium polytungstate (NaPT) of increasing density (1.6, 1.8 and 2.0) to differentiate five fractions: a free light, extractable without sonication, three occluded (extractable by sonication) and a dense (retained in the dense residue, after sonication). The obtained fractions were analyzed by preparative thermochemolysis followed by gas chromatography–mass spectrometry (GC/MS) in order to get some insight on the molecular composition. The total ion chromatograms obtained for the pyrolysates of both of the densimetric fractions show various series of fatty acids (as their methyl esters), n-alkanols (as their methyl ethers), methylated α,ω-diacids, methylated ω-hydroxyacids, various lignous subunits and permethylated deoxy aldonic acids derived from carbohydrates. The comparison of the distributions of the thermochemolysis products shows that organic carbon in the dense fractions of the deepest horizons were more influenced by a microbial reworking than the others dense fractions from the upper horizons. It is also the case for the occluded fraction 1 of the H horizon even the vegetal part of the organic carbon in that occluded fraction appears to have a non-woody origin. On the other hand, the dense fraction of the H horizon is strongly marked by vegetal origin. 相似文献
18.
The composition and molecular residence time of soil organic matter (SOM) in four particle‐size fractions (POM >200 µm, POM 63–200 µm, silt and clay) were determined using Curie‐point pyrolysis/gas chromatography coupled on‐line to mass spectrometry. The fractions were isolated from soils, either continuously with a C 3 wheat (soil 13C value = ?26.4‰), or transferred to a C 4 maize (soil 13C value = ?20.2‰) cropping system 23 years ago. Pyrograms contained up to 45 different pyrolysis peaks; 37 (ca. 85%) were identifiable compounds. Lignins and carbohydrates dominated the POM fractions, proteins were abundant, but lignin was (nearly) absent in the silt and clay fractions. The mean turnover time (MRT) for the pyrolysis products in particulate organic matter (POM) was generally <15 years (fast C pool) and 20–300 years (medium or slow C pools) in silt and clay fractions. Methylcyclopentenone (carbohydrate) in the clay fraction and benzene (mixed source) in the silt fraction exhibited the longest MRTs, 297 and 159 years, respectively. Plant‐derived organic matter was not stored in soils, but was transformed to microbial remains, mainly in the form of carbohydrates and proteins and held in soil by organo‐mineral interactions. Selective preservation of plant‐derived OM (i.e. lignin) based on chemical recalcitrance was not observed in these arable soils. Association/presence of C with silt or clays in soils clearly increased MRT values, but in an as yet unresolved manner (i.e. ‘truly’ stabilized, or potentially still ‘labile’ but just not accessible C). Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
19.
Pyrrole and acetonitrile, major pyrolysis products of soil humic substances, vary characteristically in abundance with the degree of humification of the organic matter in the soil. Their origin, however, is uncertain because of the large amount of unidentifiable soil nitrogen. A quantitative relationship between amino acid composition and pyrrole and acetonitrile abundances has been established by Curie-point pyrolysis-gas chromatography of a group of test proteins, using polystyrene as an internal standard. The pyrolysis yields of these products from three humic acids extracted from the surface horizons of Scottish brown forest soils (Cambisols or Ochrepts) were entirely accounted for by the known hydrolysable amino acid content and composition, and the products were related to individual amino acids. The peptide amino acid was also found to be the overall source of the aromatic pyrolysis products toluene, phenol and p-cresol. 相似文献
20.
The main objective of this research was to investigate to what extent the potential C dynamics of soil organic matter (SOM) are related to the degree of 13C enrichment with increasing depth in soil profiles under permanent grassland. The evolution of the C content and the 13C natural abundance (delta13C value) of SOM were investigated in three soil profiles (0-40 cm depth) under permanent grassland of varying texture (a loamy sand, a loam and a clay loam soil). The delta13C value of the SOM showed a gradual increase with increasing depth and decreasing C content in the profiles, ranging from 1.9 per thousand (loamy sand soil), 2.9 per thousand (clay loam soil) and 4 per thousand (loam soil) in relation to the delta13C value of SOM at the surface. The relationship between the 13C enrichment and total organic C content at different depths in the profiles (down to 40 cm depth in the loam and clay loam soil, down to 25 cm depth in the loamy sand soil) could be well described by the Rayleigh equation. The enrichment factors epsilon, associated with the Rayleigh approximation of the data, ranged from -1.57 per thousand (clay loam soil) to -1.64 per thousand (loamy sand soil) and -1.91 per thousand (loam soil). The potential C dynamics in four depth intervals from the profiles (0-10, 10-20, 20-30 and 30-40 cm depth) were determined by means of an incubation experiment. The C decomposition rate constants from the four sampling depths in the profiles showed a significant, positive correlation (y = 0.21x + 0.018, R(2) = 0.66, p < 0.005) with the corresponding Deltadelta13C values (change of the delta13C value per depth increment). A better correlation was obtained when only the data from the upper 20 cm in the profiles (y = 0.21x + 0.019, R(2) = 0.78, p < 0.05) were considered. These results suggest that the Deltadelta13C values in the surface layers of profiles under permanent grassland may serve as an indicator of the potential degradability or the stability of the SOM (in terms of C decomposition rate constants). 相似文献
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