土壤有机质对菲的吸附-解吸平衡的影响

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。     

Application of DSC–TG and NMR to study the soil organic matter

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.     

Impact of landuse change on the molecular composition of soil organic matter

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.     

Influence of recent vegetation on labile and recalcitrant carbon soil pools in central Queensland, Australia: evidence from thermal analysis-quadrupole mass spectrometry-isotope ratio mass spectrometry

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.     

Chemical structure of soil organic matter

Journal of Thermal Analysis and Calorimetry - Selective preservation belongs among the important stabilization mechanisms of soil organic matter (SOM). Conceptually, it is based on non-covalent...     

Use of 13C to monitor soil organic matter transformations caused by a simulated forest fire

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.     

Application of simultaneous thermal analysis mass spectrometry and stable carbon isotope analysis in a carbon sequestration study

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.     

Application of pyrolysis-gas chromatography/mass spectrometry to study changes in the organic matter of macro- and microaggregates of a Mediterranean soil upon heating

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.     

Characterization of soil organic matter fractions from grassland and cultivated soils via C content and delta13C signature

Variations in (13)C natural abundance and distribution of total C among five size and density fractions of soil organic matter, water soluble organic C (WSOC) and microbial biomass C (MBC) were investigated in the upper layer (0-20 cm) of a continuous grassland soil (CG, C(3) vegetation), a C(3)-humus soil converted to continuous maize cultivation (CM, C(4) vegetation) and a C(3)-humus soil converted to a rotation of maize cultivation and grassland (R). The amounts of WSOC and MBC were both significantly larger in the CG than in the CM and the R. In the three soils, WSOC was depleted while MBC was enriched in (13)C as compared with whole soil C. The relative contributions to the total C content of C stored in the macro-organic matter and in the size fraction 50-150 microm decreased with decreasing total C contents in the order CG > R > CM, while the relative contribution of C associated with the clay- and silt-sized fraction <50 microm increased. This reflects a greater stability and physical protection against microbial degradation associated with soil disruption (tillage) of the clay- and silt-associated organic C, in relation to the organic C in larger size fractions. The size and density fractions from the CG soil showed significant differences in (13)C enrichment, indicating different degrees of microbial degradation and stability of soil organic C associated with physically different soil organic matter (SOM) fractions. Delta(13)C analysis of the size and density fractions from CM and R soils reflected a decreasing turnover rate of soil organic C with increasing density among the macro-organic matter fractions and with decreasing particle size.     

Effects of soil pH and organic matter on distribution of thorium fractions in soil contaminated by rare-earth industries

The labilities of thorium fractions including mobility and bioavailability vary significantly with soil properties. The effects of soil pH and soil organic matter on the distribution and transfer of thorium fractions defined by a sequential extraction procedure were investigated. Decrease of soil pH could enhance the phytoavailability and the potential availability of thorium in soil. Increase of organic matter reduced the phytoavailability of thorium, but enhanced the potential availability of it. The reasons why soil pH and soil organic matter affect thorium fractions were discussed, and the behavior of the effects of soil properties on thorium fractions was elucidated. Fourier-transform infrared (FTIR) spectra were employed to reveal the positive relationship between the amounts adsorbed in humic material and/or amorphous oxides and the content of soil organic matter.     

Application of scanning calorimetry to estimate soil organic matter loss after fires

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 (ΔH _{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.     

Kerogen as a geochemical marker of the thermal history of rocks

The study presents examples of the application of oxyreactive thermal analysis to the geological prospecting of bitumen deposits. Thermal analysis performed under properly chosen analytical conditions allows determination of characteristic features of organic matter and, at the same time, estimation of the thermal history of rocks. Thermal oxyreactivity curves document whether rocks were heated before or not. The results of the oxyreactive thermal analysis correlate well with the results of routine chemical analyses of organic matter (e.g. the composition of kerogen and bituminous fraction, Rock-Eval analysis and others). Our study clearly demonstrates that the composition of organic matter in facially, lithostratigraphically, and biogenetically identical rocks depends on their thermal history.     

Influence of heteroatom pre-selection on the molecular formula assignment of soil organic matter components determined by ultrahigh resolution mass spectrometry

Soil organic matter (SOM) is involved in many important ecosystem processes. Ultrahigh resolution mass spectrometry has become a powerful technique in the chemical characterization of SOM, allowing assignment of elemental formulae for thousands of peaks resolved in a typical mass spectrum. We investigated how the addition of N, S, and P heteroatoms in the formula calculation stage of the mass spectra processing workflow affected the formula assignments of mass spectra peaks. Dissolved organic matter extracted from plant biomass and soil as well as the soil humic acid fraction was studied. We show that the addition of S and P into the molecular formula calculation increased peak assignments on average by 17.3 % and 10.7 %, respectively, over the assignments based on the CHON elements frequently reported by SOM researchers using ultrahigh resolution mass spectrometry. The organic matter chemical characteristics as represented by van Krevelen diagrams were appreciably affected by differences in the heteroatom pre-selection for the three organic matter samples investigated, especially so for the wheat-derived dissolved organic matter. These results show that inclusion of both S and P heteroatoms into the formula calculation step, which is not routinely done, is important to obtain a more chemically complete interpretation of the ultrahigh resolution mass spectra of SOM.     

Effect of multivalent cations,temperature, and aging on SOM thermal properties

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.     

Quantification methods of Black Carbon: comparison of Rock-Eval analysis with traditional methods

Black Carbon (BC) quantification methods are reviewed, including new Rock-Eval 6 data on BC reference materials. BC has been reported to have major impacts on climate, human health and environmental quality. Especially for risk assessment of persistent organic pollutants (POPs) it is important to account for risk reduction caused by BC, as suggested for POP safety assessment in the framework of the new European Community Regulation on Registration, Evaluation, Authorization and Restriction of Chemicals (REACH). Four major classes of BC quantification methods are reviewed including application to BC reference materials. Methods include chemical oxidation, thermal oxidation, molecular marker, optical methods and Rock-Eval analyses. Residual carbon from Rock-Eval 6 analysis correlated well with BC data from 'gentle' methods like optical and molecular marker methods, which capture a major part of the BC continuum including labile fractions (e.g. char). In contrast, the temperature at which 50% of the organic matter was oxidized (T(50%)) in an oxidation-only Rock-Eval analysis, correlated well with data from chemothermal oxidation (CTO), which captures only refractory BC fractions (e.g. soot). Rock-Eval analysis can further be used for BC characterization through deconvolution of the dominant peaks of the thermogram and appears to be a powerful tool in BC analysis.     

Temperature-dependent shift from labile to recalcitrant carbon sources of arctic heterotrophs

Soils of high latitudes store approximately one-third of the global soil carbon pool. Decomposition of soil organic matter (SOM) is expected to increase in response to global warming, which is most pronounced in northern latitudes. It is, however, unclear if microorganisms are able to utilize more stable, recalcitrant C pools, when labile soil carbon pools will be depleted due to increasing temperatures. Here we report on an incubation experiment with intact soil cores of a frost-boil tundra ecosystem at three different temperatures (2 degrees C, 12 degrees C and 24 degrees C). In order to assess which fractions of the SOM are available for decomposition at various temperatures, we analyzed the isotopic signature of respired CO2 and of different SOM fractions. The delta13C values of CO2 respired were negatively correlated with temperature, indicating the utilization of SOM fractions that were depleted in 13C at higher temperatures. Chemical fractionation of SOM showed that the water-soluble fraction (presumably the most easily available substrates for microbial respiration) was most enriched in 13C, while the acid-insoluble pool (recalcitrant substrates) was most depleted in 13C. Our results therefore suggest that, at higher temperatures, recalcitrant compounds are preferentially respired by arctic microbes. When the isotopic signatures of respired CO2 of soils which had been incubated at 24 degrees C were measured at 12 degrees C, the delta13C values shifted to values found in soils incubated at 12 degrees C, indicating the reversible use of more easily available substrates. Analysis of phospholipid fatty acid profiles showed significant differences in microbial community structure at various incubation temperatures indicating that microorganisms with preference for more recalcitrant compounds establish as temperatures increase. In summary our results demonstrate that a large portion of tundra SOM is potentially mineralizable.     

Interrelations between soil respiration and its thermal stability

Biological transformation of organic matter in soil is a crucial factor affecting the global carbon cycle. In order to understand these complex processes, soils must be investigated by a combination of various methods. This study compares the dynamics of biological mineralization of soil organic matter (SOM) determined via CO₂ evolution during an 80-day laboratory incubation with their thermo-oxidative stability determined by thermogravimetry (TG). Thirty-three soil samples, originating from a wide range of geological and vegetation conditions from various German national parks were studied. The results showed a correlation between the amount and rate of respired CO₂ and thermal mass losses of air-dried, conditioned soils occurring around 100?°C with linear coefficients of determination up to R ²?=?0.85. Further, correlation of soil respiration with thermal mass losses around 260?°C confirmed previous observations. The comparison of TG profiles from incubated and non-incubated soils underlined the importance of thermal mass losses in these two temperature intervals. Incubated soils had reduced thermal mass losses above 240?°C and conversely an increased mass loss at 100?C120?°C. Furthermore, the accurate determination of soil properties by TG such as soil organic carbon content was confirmed, and it was shown that it can be applied to a wider range of carbon contents as was previously thought. It was concluded that results of thermal analysis could be a helpful starting point for estimation of soil respiration and for development of methods revealing processes in soils.     

Molecular turnover time of soil organic matter in particle‐size fractions of an arable soil

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 C₃ wheat (soil ¹³C value = ?26.4‰), or transferred to a C₄ 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.     

Molecular evaluation of soil organic matter characteristics in three agricultural soils by improved off-line thermochemolysis: The effect of hydrofluoric acid demineralisation treatment

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.     

Thermal stability of soil organic matter was affected by 23-yr maize and soybean continuous cultivation in northeast of China

Long-term continuous cropping affects the biochemical quality of soil organic matter (SOM), but whether the effects are relevant with their thermal stability is less clear. In northeast China, long-term continuous cropping occurred frequently owing to higher yield and economic interest requirement. To verify the thermal stability properties of SOM affected by the long-term continuous cropping, the study focused on 23-yr continuous cultivated maize and soybean plots, where the effect of cropping is likely to be detected. Bulk soils sampled in 1991 and 2014 were studied by thermogravimetry and differential scanning calorimetry (DSC). The results showed typical bimodal peaks in DSC curve in bulk Mollisols. A labile fraction peak was observed at 354–366 °C low-temperature zone and recalcitrant fraction one at high temperature of 430–438 °C. Energy density (J mg^?1 OM) was greater in soybean plots compared to maize plots; in contrast, long-term continuous maize cultivation also increased energy density, in reverse in soybean plots after 23-yr cultivation. The DSC-T₅₀, temperature at which half of energy release occurred, typically showed larger responses to long-term cultivation than crop species. Results obtained support the hypothesis of a potential link between long-term continuous cropping and the thermal stability of SOM, and a correlation with crop species.