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.     

Post-harvest residue management effects on recalcitrant carbon pools and plant biomarkers within the soil heavy fraction in Pinus radiata plantations

Forest soils contain about 30% of terrestrial carbon (C) and so knowledge of the influence of forest management on stability of soil C pools is important for understanding the global C cycle. Here we present the changes of soil C pools in the 0-5 cm layer in two second-rotation Pinus radiata (D.Don) plantations which were subjected to three contrasting harvest residue management treatments in New Zealand. These treatments included whole-tree harvest plus forest floor removal (defined as forest floor removal hereafter), whole-tree, and stem-only harvest. Soil samples were collected 5, 10 and 15 years after tree planting at Kinleith Forest (on sandy loam soils) and 4, 12 and 20 years after tree planting at Woodhill Forest (on sandy soils). These soils were then physically divided into light (labile) and heavy (stable) pools based on density fractionation (1.70 g cm⁻³). At Woodhill, soil C mass in the heavy fraction was significantly greater in the whole-tree and stem-only harvest plots than the forest floor removal plots in all sampling years. At Kinleith, the soil C mass in the heavy fraction was also greater in the stem-only harvest plots than the forest floor removal plots at year 15. The larger stable soil C pools with increased residue return was supported by analyses of the chemical composition and plant biomarkers in the soil organic matter (SOM) heavy fractions using NMR and GC/MS. At Woodhill, alkyl C, cutin-, suberin- and lignin-derived C contents in the SOM heavy fraction were significantly greater in the whole-tree and stem-only harvest plots than in the forest floor removal plots in all sampling years. At Kinleith, alkyl C (year 15), cutin-derived C (year 5 and 15) and lignin-derived C (Year 5 and 10) contents in the SOM heavy fraction were significantly greater in stem-only harvest plots than in plots where the forest floor was removed. The analyses of plant C biomarkers and soil δ¹³C in the light and heavy fractions of SOM indicate that the increased stable soil C in the heavy fraction with increased residue return might be derived from a greater input of recalcitrant C in the residue substrate.     

Assessing management impacts on soil organic matter quality in subtropical Australian forests using physical and chemical fractionation as well as C NMR spectroscopy

Successful soil organic matter (SOM) quality assessment is needed to improve our ability to manage forest soils sustainably. Our objective was to use a multivariate data set to determine whether the land use conversion from native forest (NF) to hoop pine plantation and the following rotation and site preparation practices had altered SOM quality at three adjacent sites of NF, first (1R) and second rotation (2R, including tree planting row (2R-T) and windrow of harvest residues (2R-W)) of hoop pine plantations in southeast Queensland, Australia. Cross-polarization magic angle spinning ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy and sequential hot water and acid hydrolysis were conducted on SOM fractions separated by wet-sieving and density fractionation procedures to characterize SOM quantitative and qualitative relevant parameters, including carbon (C) functional groups, C and nitrogen (N) contents, C/N ratios, and C and N recalcitrant indices. Analysis of variance (ANOVA) and principal component analysis (PCA) of these multivariate parameters together indicated a complicated interaction between physical protection and biochemical recalcitrance, making the land use and management induced changes of SOM quality more complex. Knowledge of PCA based on the refined set of 41 SOM quantitative and qualitative parameters identified that principal component 1 (PC1), which explained 55.7% of the total variance, was most responsible for the management induced changes in soil processes. This was reflected by the dynamics of SOM regarding the aspects of total stock, soil basal and substrate induced respirations, gross and net N mineralization and nitrification, and microbial biomass, microbial diversity of C utilization patterns. Further, the macroaggregates (F_{250-2000 μm}) and the C/N ratio of acid extracts of SOM physical fractions, which represented the most informative and unique variables loading on PC1, might be the most promising physical and chemical measures for SOM quality assessment of land use and management impacts in subtropical Australian forests.     

Soil organic matter in urban soils: Estimation of elemental carbon by thermal oxidation and characterization of organic matter by solid-state C nuclear magnetic resonance (NMR) spectroscopy

To reduce soil destruction by urban sprawl, land use planning has to promote the use of soils within cities. As soil functions are now protected by law in Germany, urban soil quality has to be evaluated before soil management. We studied contributions from elemental carbon (EC) and soil organic matter (SOM) quality in topsoil horizons at seven sites in Stuttgart, Germany, differing in impurities by technogenic substrates. The most disturbed site was found at a disused railway area while high-density areas, public parks and garden areas showed varying degrees of disturbance by anthropogenic activities. For most soils, compounds derived from plant litter dominated organic matter (OM) quality characterized by nuclear magnetic resonance (NMR) spectroscopy. Although high contents of EC (up to 70% of soil organic carbon) were indicated by thermal oxidation, this was not confirmed by aromatic C intensities in NMR spectra. Only for the highly aromatic railway soil were results for elemental carbon by thermal oxidation and NMR similar. As other technogenic substrates beside EC like plastics may also contribute in the long-term to OM in urban soils, new analytical techniques are therefore required. This knowledge will promote the evaluation of urban soil properties and their sustainable use.     

Decomposition and substrate quality of leaf litters and fine roots from three exotic plantations and a native forest in the southwestern highlands of Ethiopia

Substrate quality and decomposition (measured as CO₂ release in laboratory microcosms) of fresh leaf litter and fine roots of Cupressus lusitanica, Pinus patula, Eucalyptus grandis and native forest trees were studied. Changes in litter chemistry in each forest stand were analysed by comparing fresh leaf litter (collected from trees) and decomposed litter from the forest floor. Elemental concentrations, proximate fractions including monomeric sugars, and cross polarisation magic-angle spinning (CPMAS) ¹³C NMR spectra were analysed in leaf litters, decomposed litter and fine roots. Leaf litters and fine roots varied in their initial substrate chemistry with Ca concentration in leaf litters being higher than that in fine roots. In each stand, fine roots had a higher acid unhydrolysable residue (AUR) (except for the Pinus stand), higher holocellulose concentration and lower concentration of water-soluble extractives (WSE) and dichloromethane extractives (NPE) than fresh leaf litter. Likewise, ¹³C NMR spectra of fine roots showed lower alkyl and carboxyl C, and higher phenolic (except P. patula), aromatic and O-alkyl C proportions than leaf litters. Compared with fresh leaf litter, decomposed litter had lower concentrations of potassium, holocellulose, WSE, NPE, arabinose and galactose, similar or higher concentrations of Mg, Ca, S and P, and higher concentrations of N and AUR. CPMAS ¹³C NMR spectra of decomposed litter showed a higher relative increase in signal intensity due to methoxyl C, aromatic C, phenolic C and carboxylic C compared with alkyl C. In a microcosm decomposition study, the proportion of initial C remaining in leaf litter and fine roots significantly fitted an exponential regression model. The decomposition constants (k) ranged between 0.0013 and 0.0030 d⁻¹ for leaf litters and 0.0010-0.0017 d⁻¹ for fine roots. In leaf litters there was a positive correlation between the k value and the initial Ca concentration, and in fine roots there was an analogous positive correlation with initial WSE. Leaf litters decomposed in the order Cupressus>native forest>Eucalyptus∼Pinus, and fine roots in the order Pinus>native forest>Cupressus∼Eucalyptus. In each stand the fine root decomposition was significantly lower than the leaf litter decomposition, except for the P. patula stand where the order was reversed.     

Immobilization of avian excreta-derived nutrients and reduced lignin decomposition in needle and twig litter in a temperate coniferous forest

The possible effects of excreta of the Great Cormorant Phalacrocorax carbo on decomposition processes and dynamics of nutrients (N, P, Ca, K, Mg) and organic chemical components (lignin, total carbohydrates) were investigated in a temperate evergreen coniferous forest near Lake Biwa in central Japan. Two-year decomposition processes of needles and twigs of Chamaecyparis obtusa were examined at two sites, control site never colonized by the cormorants (site C) and colonizing site (site 2). Mass loss was faster in needles than in twigs. Mass loss of these litter types was faster at site C than at site 2, which was ascribed to the decreased mass loss rate of acid-insoluble ‘lignin’ at site 2. Net immobilization of N, P, and Ca occurred in needles and twigs at site 2; whereas at site C, mass of these elements decreased without immobilization during decomposition. Duration of immobilization phase of these nutrients at site 2 was estimated to be 1.6 to 2.5 years in needles and 19.6 to 23.5 years in twigs. Immobilization potential (maximum amount of exogenous nutrient immobilized per gram initial material) was similar between needles and twigs for N and Ca but was about 10 times higher in twigs than in needles for P. δ¹³C in needles was relatively constant during the first year and then increased during the second year, whereas δ¹³C in twigs was variable during decomposition. Acid-insoluble fraction was depleted in ¹³C compared to whole needles (1.6-2.1‰) and twigs (2.0-2.5‰). δ¹⁵N of needles and twigs and their acid-insoluble fractions approached to δ¹⁵N of excreta during decomposition at site 2. This result demonstrated the immobilization of excreta-derived N into litter due to the formation of acid-insoluble lignin-like substances complexed with excreta-derived N. No immobilization occurred in K and Mg and their mass decreased during decomposition at both sites. Based on these results of nutrient immobilization during decomposition and on the data of litter fall and excreta amount at site 2, we tentatively calculated stand-level immobilization potential of litter fall and its contribution to total amount of N and P deposited as excreta. Thus, the potential maximum amount immobilized into litter fall (needles and twigs) was estimated to account for 5-7% of total excreta-derived N and P.     

l3C NMR spectra and elemental composition of fractions with different particle sizes from an andosol humic acid

Elemental composition and solution 13C NMR spectra for six humic acid fractions with different particle sizes (i.e. 3K, 10K, 30K, l00K, 300K, and 500K) which were prepared from a humic acid in an Umbric Andosol by successive gel permeation chromatography were determined. Elemental composition of the particle size fractions clearly differed from one another. Contents of nitrogen and hydrogen increased with the increase of the particle size. Small and middle particle size fractions (3K to l00K) showed low contents of hydrogen and nitrogen corresponding to those in typical Andosol humic acids, while the contents in the large fractions (300K and 500K) were distributed in the ranges of those in the other humic acids. As the particle size increased, the HIC ratio increased whereas the O/H decreased. In the HIC versus OIC diagram, the large particle size fractions (300K and 500K) were observed in the area around humic acids with a low humification degree. Variation of the chemical structural properties with particle size differences was assumed, based on the analysis of the HIC versus OIH and HIC versus OIC diagrams. The changes of the carbon species with particle size differences were examined based on the ¹³C NMR spectra. As the particle size increased, the aliphatic C content increased whereas the carboxylic and aromatic C content decreased and, therefore, the aromaticity decreased. In addition, a negative correlation (r= -0.977) was found to be significant at 0.1% level between the HIC ratios and aromaticity. The peak strength around 30 ppm assigned to chains of methylene group increased remarkably with the increase of the particle size. It was suggested that the changes of the content of the aliphatic carbon with the decrease of the particle size may depend on the changes of the aliphatic chain length. In conclusion, these findings suggest that the Andosol humic acid molecule may be composed of humic acid components with long chains of aliphatic groups for the larger particle size fractions, and of their homologous series through the reduction of the length of the aliphatic long chain for the smaller particle size fractions. These assumptions were compatible with those made in a series of studies previously reported.     

Seasonal dynamics of leaf- and root-derived C in arctic tundra mesocosms

We investigated contributions of leaf litter, root litter and root-derived organic material to tundra soil carbon (C) storage and transformations. ¹⁴C-labeled materials were incubated for 32 weeks in moist tussock tundra soil cores under controlled climate conditions in growth chambers, which simulated arctic fall, winter, spring and summer temperatures and photoperiods. In addition, we tested whether the presence of living plants altered litter and soil organic matter (SOM) decomposition by planting shoots of the sedge Eriophorum vaginatum in half of the cores. Our results suggest that root litter accounted for the greatest C input and storage in these tundra soils, while leaf litter was rapidly decomposed and much of the C lost to respiration. We observed transformations of ¹⁴C between fractions even when total C appeared unchanged, allowing us to elucidate sources and sinks of C used by soil microorganisms. Initial sources of C included both water soluble (WS) and acid-soluble (AS) fractions, primarily comprised of carbohydrates and cellulose, respectively. The acid-insoluble (AIS) fraction appeared to be a sink for C when conditions were favorable for plant growth. However, decreases in ¹⁴C activity from the AIS fraction between the fall and spring harvests in all treatments indicated that microorganisms consumed recalcitrant C compounds when soil temperatures were below 0 °C. In planted leaf litter cores and in both planted and unplanted SOM cores, the greatest amounts of ¹⁴C at the end of the experiment were found in the AIS fraction, suggesting a high rate of humification or accumulation of decay-resistant plant tissues. In unplanted leaf litter cores and planted and unplanted root litter cores most of the ¹⁴C remaining at the end of the experiment was in the AS fraction suggesting less extensive humification of leaf and root detritus. Overall, the presence of living plants stimulated decomposition of leaf litter by creating favorable conditions for microbial activity at the soil surface. In contrast, plants appeared to inhibit decomposition of root litter and SOM, perhaps because of microbial preferences for newer, more labile inputs from live roots.     

Modeling aerobic decomposition of rice straw during the off-rice season in an Andisol paddy soil in a cold temperate region of Japan: Effects of soil temperature and moisture

Submerged rice paddies are a major source of methane (CH₄) which is the second most important greenhouse gas after carbon dioxide (CO₂). Accelerating rice straw decomposition during the off-rice season could help to reduce CH₄ emission from rice paddies during the single rice-growth season in cold temperate regions. For understanding how both temperature and moisture can affect the rate of rice straw decomposition during the off-rice season in the cold temperate region of Tohoku district, Japan, a modeling incubation experiment was carried out in the laboratory. Bulk soil and soil mixed with 2% of δ¹³C-labeled rice straw with a full factorial combination of four temperature levels (?5 to 5, 5, 15, 25°C) and two moisture levels (60% and 100% WFPS) were incubated for 24 weeks. The daily change from ?5 to 5°C was used to model the freezing–thawing cycles occurring during the winter season. The rates of rice straw decomposition were calculated by (i) CO₂ production; (ii) change in the soil organic carbon (SOC) content; and (iii) change in the δ¹³C value of SOC. The results indicated that both temperature and moisture affected the rate of rice straw decomposition during the 24-week aerobic incubation period. Rates of rice straw decomposition increased not only with high temperature, but also with high moisture conditions. The rates of rice straw decomposition were more accurately calculated by CO₂ production compared to those calculated by the change in the SOC content, or in its δ¹³C value. Under high moisture at 100% WFPS condition, the rates of rice straw decomposition were 14.0, 22.2, 33.5 and 46.2% at ?5 to 5, 5, 15 and 25°C temperature treatments, respectively. While under low moisture at 60% WFPS condition, these rates were 12.7, 18.3, 31.2 and 38.4%, respectively. The Q₁₀ of rice straw decomposition was higher between ?5 to 5 and 5°C than that between 5 and 15°C and that between 15 and 25°C. Daily freezing–thawing cycles (from ?5 to 5°C) did not stimulate rice straw decomposition compared with low temperature at 5°C. This study implies that to reduce CH₄ emission from rice paddies during the single rice-growth season in the cold temperate regions, enhancing rice straw decomposition during the high temperature period is very important.