Leaf litter decomposition in a chaparral ecosystem, Southern California

Decomposition losses from leaves of three evergreen chaparral species, scrub oak (Quercus dumosa), ceanothus (Ceanothus crassifolius), and manzanita (Arctostaphylos glauca), were quantified over a 2-y field exposure using litterbags. Changes in ash-free dry mass, C, and N were monitored at 2- to 6-month intervals at four replicate sites composed of patches of these three chaparral species. Three proximate C fractions were extracted from fresh and decomposing litter samples: polar and non-polar extractives (EXT), acid-solubles (ACID), and acid-insolubles (KLIG). The chemical structure of fresh and decomposed litter was additionally characterized using high-resolution solid-state ¹³C NMR spectroscopy, while morphological properties were examined by scanning electron microscopy (SEM). After 2 y, the litters had lost between 20.7%±1.2 (Ceanothus) and 35.2%±6.8 (Quercus) of their original ash-free dry mass. The manzanita decomposed at a significantly faster rate than the other two litter types during the first few months of field exposure. Yet, after 2 y, mass loss was greater for the oak. Differences in decomposition rates could not be accounted for based on a single litter quality index. Fresh manzanita exhibited a significantly higher N content, which could explain its initially faster decay rate. Fresh oak litter, on the other hand, had a relatively high ACID and O-alkyl C (O-ALK) content, which may have been responsible for its decay pattern. Fresh ceanothus contained a relatively low KLIG content, yet it decomposed more slowly than the two other species. The solid-state ¹³C NMR spectra of the ceanothus litter had two peaks characteristic of proanthocyanidins, which likely contributed to the recalcitrance of this litter type. SEM revealed that ceanothus leaf surfaces were left nearly unchanged after field exposure. In comparison, the oak and manzanita leaf surfaces were pitted and covered by microbial growth to the point of being unrecognizable. Taken together, our results indicate that a combination of biological, physical and chemical factors need to be examined to clarify the different decomposition rates and patterns of these three chaparral species.     

Impact of long-term N fertilization on the structural composition of spruce litter and mor humus

The aims of this study were to determine the degree of lignin degradation and to investigate changes in the chemical composition of the organic matter in the forest floor in an N fertilized Norway spruce forest soil. Needle litter and mor humus were collected from the field experiment at Skogaby in southern Sweden (56°33′N; 13°13′E). The spruce stand had been fertilized for 11 years with 100 kg N ha⁻¹ yr⁻¹ as (NH₄)₂SO₄. The degree of lignin degradation was determined with alkaline CuO oxidation followed by HPLC analysis. The chemical composition of the organic matter was characterized by CPMAS ¹³C NMR. Tannin was specifically analyzed using dipolar dephasing CPMAS ¹³C NMR and the N distribution was studied by CPMAS ¹⁵N NMR.The C-to-N ratios in the fertilized Oi and Oe layers were significantly lower than in the unfertilized layers (24 compared to 34 and 23 compared to 27, respectively). Neither the sum of the CuO oxidation products (Vanillyls+Syringyls+Cinnamyls expressed as VSC) nor the acid-to-aldehyde ratio ((Ac/Al)_V) showed any significant treatment effects. The content of aromatic C (including phenolic C) was significantly lower in the unfertilized than in the fertilized Oi layer (18 versus 21%). In the unfertilized soil, VSC was positively correlated (r=+0.63, p<0.05) with the C-to-N ratio, whereas the phenolic C content was negatively correlated (r=−0.61, p<0.05). The tannin index showed a tendency of increasing from Oi to Oe layers in both treatments. Most of the organic N was found as amide-N, whereas no heterocyclic N was detected. We have not been able to show any major C structural changes due to N fertilization. We suggest that the significantly higher content of aromatic and phenolic C in the fertilized Oi layer is due to an initial stimulation of the microbial community.     

基于低场核磁和差示量热扫描的面条面团水分状态研究

为了解低水分面条面团中水分的存在状态,明确真空度及和面时间对水分状态的影响,该研究以3个小麦品种（济麦20、宁春4号、济麦22）磨制的面粉为材料,采用真空和面制作低水分面条面团（含水率35%）,采用低场核磁共振技术（LF-NMR,low-field nuclear magnetic resonance）和差示量热扫描（DSC,differential scanning calorimetry）2种技术,测定不同真空度（0、0.06、0.09 MPa）和搅拌时间（4、8、12 min）下面团中水分的形态和分布,并进一步分析2种技术测定水分形态结果的相关性。结果表明,在低水分面条面团中,水分主要以弱结合水形态存在。不同品种的小麦粉面团的水分形态及分布存在差异,强筋小麦粉（济麦20）制作面团的水分自由度较低。真空和面（0.06 MPa）可以促进水分与面筋蛋白的相互作用,降低面团中水分子流动性,促进水分结构化;而非真空或过高真空度均会导致面团中水分自由度增加。济麦20、济麦22小麦粉和面时间为8 min时,面团水分流动性较低;而宁春4号小麦粉面团在4 min时,水分自由度较低;继续搅拌,深层结合水减少、弱结合水增多。LF-NMR和DSC测得面团水分状态的结果具有一致性。LF-NMR测得的弱结合水峰面积百分比与DSC测得的可冻结水百分比具有相同的变化趋势（r=0.695）,且深层结合水峰面积百分比与非冻结水百分比具有相同的变化趋势（r=0.564）。研究结果为认识制面过程中水分的作用,优化和面工艺和调整产品特性提供参考。     

Near‐infrared spectroscopy can predict the composition of organic matter in soil and litter

The usefulness and limitations of near‐infrared reflectance spectroscopy (NIRS) for the assessment of several soil characteristics are still not sufficiently explored. The objective of this study was to evaluate the ability of visible and near‐infrared reflectance (VIS‐NIR) spectroscopy to predict the composition of organic matter in soils and litter. Reflectance spectra of the VIS‐NIR region (400–2500 nm) were recorded for 56 soil and litter samples from agricultural and forest sites. Spectra were used to predict general and biological characteristics of the samples as well as the C composition which was measured by ¹³C‐CPMAS‐NMR spectroscopy. A modified partial least‐square method and cross‐validation were used to develop equations for the different constituents over the whole spectrum (1st to 3rd derivation). Near‐infrared spectroscopy predicted well the C : N ratios, the percentages of O‐alkyl C and alkyl C, the ratio of alkyl C to O‐alkyl C, and the sum of phenolic oxidation products: the ratios of standard deviation of the laboratory results to standard error of cross‐validation (RSC) were greater than 2, the regression coefficients (a) of a linear regression (measured against predicted values) ranged from 0.9 to 1.1, and the correlation coefficients (r) were greater than 0.9. Satisfactorily (0.8 ≤ a ≤ 1.2, r ≥ 0.8, and 1.4 ≤ RSC ≤ 2.0) assessed were the contents of C, N, and production of DOC, the percentages of carbonyl C and aromatic C and the ratio of alkyl C to aromatic C. However, the N‐mineralization rate and the microbial biomass were predicted unsatisfactorily (RSC < 1.4). The good and satisfactory predictions reported above indicate a marked usefulness of NIRS in the assessment of biological and chemical characteristics of soils and litter.     

Kinetic Parameters of Gross N Mineralization of Peat Soils as Related to the Composition of Soil Organic Matter

Peat land has been considered as an alternative type of land for agricultural development especially in the tropics. In the present study, the N-supplying capacity, one of the most important soil properties in terms of crop production, of peat soils was examined. Ten peat soil samples were collected from Indonesia, Malaysia, and Japan. Gross N mineralization in the soil samples was estimated using a zero-order model, and kinetic parameters of mineralization were determined using a simple type model. Soil organic matter composition was investigated using ¹³C CPMAS NMR. Mineralization potential ( N ₀), apparent activation energy ( E _a), and mineralization rate constant ( k ) ranged between 571–2,445 mg kg⁻¹, 281–8,181 J mol⁻¹, and 0.009–0.020 d⁻¹, respectively. Although none of the parameters showed a significant correlation with the soil C/N ratio, a negative correlation was observed between the k value and the ratio of the proportion of alkyl C in total C to that of O -alkyl C estimated by ¹³C CPMAS NMR. The latter suggested that the k values were higher in the peat soils relatively rich in readily decomposable organic matter including carbohydrates.     

Can P NMR spectroscopy be used to indicate the origins of soil organic phosphates?

The relationship between organic P status of 4 soils, 20 microorganisms isolated from these soils (2 bacteria and 3 fungi for each soil) and 13 dominant plant species of typical natural ecosystems of these soils was evaluated. The soils used were represented by two pairs with different ratios of monoester and diester P, and of DNA and other diester P. A Dystric Podzoluvisol and an alpine Umbric Leptosol were characterized by a relatively high proportion of diester P including much DNA P, while a Calcic Chernozem and subalpine Umbric Leptosol had lower proportion of diesters containing relatively less DNA P. The proportions of P compounds in bacteria and plants were very similar on average, based on the monoester to diester P ratio and on the proportions of different diesters in alkaline extract, whereas fungi contained considerably higher proportions of monoesters and polyphosphates, and a higher proportion of phospholipids in the diester fraction. The results showed that the P_org composition of NaOH extracts from different soils was more similar to the composition of extracts from different groups of microorganisms. There was no clear correspondence between soil and microbial diester P proportion and composition. A high proportion of polyphosphate P including pyrophosphate P in soil extracts indicates a significant contribution of fungal P compounds in the soil while the monoester to diester P ratio, and DNA to non-DNA P ratio should be used with caution to interpret the origins of soil P_org. The relative contributions of microorganisms and plants to monoester and diester P in soils is only partially understood.     

Relationship between molecular characteristics of soil humic fractions and glycolytic pathway and krebs cycle in maize seedlings

A humic acid (HA) isolated from a volcanic soil was separated in three fractions of decreasing molecular size (I, II and III) by preparative high performance size exclusion chromatography (HPSEC). The molecular content of the bulk soil HA and its size fractions was characterized by pyrolysis-GC-MS (thermochemolysis with tetramethylammonium hydroxide) and NMR spectroscopy. All soil humic materials were used to evaluate their effects on the enzymatic activities involved in glycolytic and respiratory processes of Zea mays (L.) seedlings. The elementary analyses and NMR spectra of the humic fractions indicated that the content of polar carbons (mainly carbohydrates) increased with decreasing molecular size of separated fractions. The products evolved by on-line thermochemolysis showed that the smallest size fraction (Fraction III) with the least rigid molecular conformation among the humic samples had the lowest content of lignin moieties and the largest amount of other non-lignin aromatic compounds. The bulk HA and the three humic fractions affected the enzyme activities related to glycolysis and tricarboxylic acid cycle (TCA) in different ways depending on molecular size, molecular characteristics and concentrations. The overall effectiveness of the four fractions in promoting the metabolic pathways was in the order: III>HA>II>I. The largest effect of Fraction III, either alone or incorporated into the bulk HA, was attributed to a flexible conformational structure that promoted a more efficient diffusion of bioactive humic components to maize cells. A better knowledge of the relationship between molecular structure of soil humic matter and plant activity may be of practical interest in increasing carbon fixation in plants and redirect atmospheric CO₂ into bio-fuel resources.     

磺酸基官能化介孔材料MSU的合成及其酸性研究

为解决涉及一些较大分子的反应之固体酸催化问题,以价格便宜的硅酸钠为主要原料合成了磺酸基官能化介孔材料MSU,并采用固体核磁共振(SSNMR)等技术研究了所合成材料(MSU-SO3H)的结构和酸性.结果表明,合成的磺酸基官能化的MSU具有规整的介孔结构,其总体酸性略弱于微孔分子筛HZSM-5.     

Carbon and nitrogen degradation on molecular scale of grass-derived pyrogenic organic material during 28 months of incubation in soil

The present study focuses on the microbial recalcitrance of pyrogenic organic material (PyOM) on a molecular scale. We performed microcosm incubation experiments using ¹³C- and ¹⁵N-enriched grass-derived PyOM mixed with a sub soil material taken from a Haplic Cambisol. Solid-state ¹³C and ¹⁵N NMR studies were conducted to elucidate the humification processes at different stages of PyOM degradation. The chemical structure of the remaining PyOM after incubation was clearly different from the initial pyrogenic material. The proportion of O-containing functional groups was increased, whereas that of aryl C and of N-containing heterocyclic structures had decreased, probably due to mineralisation and conversion to other C and N groups. After 20 months of incubation the aryl C loss reached up to 40% of the initial amount and up to 29% of the remaining PyOM C was assigned to carboxyl/carbonyl C and O-aryl C. These reactions alter the chemical and physical properties of the char residue and make it more available for further microbial attack but also for adsorption processes. Our study presents direct evidence for the degradation of N-heterocyclic domains in charred plant remains adding new aspects to the understanding of the N cycling in fire-affected ecosystems.     

土壤腐殖质氮结构的X-光电能谱研究

X－ray photoelectron spectroscopy(XPS) was applied to examine the N structures of soil humic substances and some of their analogues.It was found that for soil humic substances XPS method gave similar results as those obtained by ^15N CPMAS NMR (cross-polarization magic-angle spinning nuclear magnetic resonance) method.70%-86% of total N in soil humic substances was in the form of amide,and 6%-13% was presented as ammes,with the remaining part as heterocyclic N.There was no difference in the distribution of the forms of N between the humic substances from soils formed over hundreds or thousands of years and the newly formed ones.For fulvic acid from weathered coal and benzoquinone-(NH4)2SO4 polymer the XPS results deviated significantly from the ^15N CPMAS NMR data.