黑土的酶活性

近年来,土壤的熟化实质问题引起了人们越来越大的注意.这主要是因为,揭示土壤的熟化实质,有助于定向地培肥土壤和有效地调控土壤肥力的演变进程.1978年,我们在先前工作的基础上,进一步对不同开垦年限、不同熟化度黑土的熟化实质问题进行了研究.本文着重讨论黑土的酶活性及其与土壤腐殖物质和其他肥力因素的相关性.     

Studies on the humus forms of forest soils

Samples described in the previous paper were analyzed for humus composition by the method of Kumada el al,, elementary composition of humic acids, nitrogen distribution among humic acid, fulvic acid, and humin, and organic matter composition by the modified Waksman method. The samples obtained by physical fractionation from each horizon of Higashiyama soil were as follows: f₁ and f₂ from the L layer, f₁, f₂ and f₃ from the F layer, f₁ f₂, sand, silt, and clay fractions from the H-A and A horizons.

With the progress of decomposition, the following tendencies were rather clearly observed.

The extraction ratio of soluble humus, amounts of humic acid and fulvic acid, and PQ, value tended to increase with some exceptions. The degree of humification of humic acid proceeded. Most humic acids belonged to the Rp type, but those of the clay fractions belonged to the B type.

As for the elementary composition of humic acid, transitional changes from the Lf₁ to the clay fraction of the A horizon were observed. But differences in elementary composition among humic acids were far less, compared with those among whole fractions.

Nitrogen contents in humic, fulvic, and humin fractions increased with the progress of decomposition and humiliation, and the largest relative increase was found in fulvic acid nitrogen.

According to the modified Waksman's method, the amounts of residues and protein increased, while the total amounts of each extract, except for the HCl extract, and the amounts of sugars and starch, phenolic substances, hemicelluloses and pectin, and cellulose decreased. Sugars and starch comprised only a small portion of the hot water extract, and polyphenols substances comparable to sugars and starch were also found in the extract. Hemicelluloses and pectin accounted for only about one-half of the HCl extract. Several characteristic differences in the elementary composition of extracts and residues were found.

Pheopigments existed in benzene-ethanol extracts and their amounts seemed to decrease from Lf₁ to Ff₂.     

A COMPARISON OF THE POLYCARBOXYLIC ACIDS EXTRACTED BY WATER FROM AN AGRICULTURAL TOP SOIL WITH THOSE EXTRACTED BY ALKALI

Humic and fulvic acids were isolated from an agricultural soil by conventional means. The same soil was extracted with water and the organic matter freed of inorganic and low molecular weight substances. The usual chemical differences between humic acid and fulvic acid were confirmed and the water extract was shown to resemble fulvic acid quite closely. Further fractionation of the fulvic acid and water extract showed that the elemental composition, carboxyl and acidic hydroxyl contents, molecular weights, and infrared spectra of the purified polycarboxylic acids were virtually identical. Both promoted the same growth response in cultured isolated tomato roots. It is suggested that the qualitative similarity of fulvic acid to the polycarboxylic acid extracted by water justifies the use of the more easily isolated fulvic acid in physiological experiments on the direct effects on plants of soil organic matter.     

川南坡地不同退耕模式对土壤腐殖质及团聚体碳和氮的影响

通过对川南坡地进行退耕试验,研究坡地退耕成慈竹林、杂交竹林、桤木+慈竹林和弃耕地对土壤腐殖质及团聚体碳和氮的影响。结果表明,坡地退耕5年后土壤腐殖质(胡敏酸、富里酸和胡敏素)、活性腐殖质(活性胡敏酸和活性富里酸)及团聚体碳和氮含量、胡敏酸与富里酸比值和胡敏酸E4/E6值,以及可浸提腐殖质(胡敏酸和富里酸)、活性腐殖质及>0.25mm各粒径团聚体碳和氮分配比例均增加,并呈现出慈竹林>杂交竹林>桤木+慈竹林>弃耕地>农耕地的变化规律。土壤团聚体有机碳(氮)含量及其分配比例随土壤团聚体粒径的增加呈现出"V"形变化,其最小值分别出现在2～1mm和0.5～0.25mm粒径。说明川南坡地退耕对增加土壤腐殖质及团聚体碳和氮含量、改善土壤肥力状况和促进土壤碳固定具有重要的作用和意义。     

Humus composition of soils under forest, coffee and arable cultivation in hilly areas of south Sumatra, Indonesia

To understand the effect of land use changes on the composition of humus in tropical soils, samples from land under primary forest, secondary forest, coffee plantation, and arable crops were investigated at three sites in south Sumatra, Indonesia. Total carbon and total nitrogen contents were 1.7 to 4.3 times and 1.1 to 2.8 times greater in the topsoil under primary forest than under the other types of land use. Following change from primary forest to other uses, the proportion of humic acids in the organic matter of the topsoils decreased while that of the fulvic acid fraction increased. Within the range of land uses, differences in the yields of humic acids and fulvic acid fractions were, respectively, larger and smaller than those in total carbon content. The humic acids were classified into the low and middle classes in the degree of humification. Absorption due to the green fraction of humic acids, Pg, was detected in the UV‐visible spectra of almost all the humic acids. No relation was observed between the degree of humification of humic acids or the strength of Pg absorption in their spectra and land use change. The fulvic acid fractions were fractionated on insoluble polyvinylpyrrolidone (PVP) into the adsorbed fractions consisting of humic substances and the non‐adsorbed fractions consisting of non‐humic substances. A positive correlation between the amount of the fulvic acid fraction and the percentage of the PVP‐adsorbed fraction within it indicated that the variation in the amount of the fulvic acid fraction was attributable to acid‐soluble humic substances. The ionization difference spectra of solutions between pH 12 and pH 7 suggested that the chemical structures of the PVP‐adsorbed fulvic acids have been altered by land use change.     

Fractionation of organo-mineral complexes by sedimentation and density techniques

Soil samples were fractionated by sedimentation in water and by flotation in heavy liquids to separate complexed and uncomplexed organic and inorganic components. Flocculation of clays in heavy organic liquids was delayed by addition of a surfactant. Heavy liquids and surfactants sorbed by soil components were removed by washing with acetone-water mixtures.In a sample of a red-brown earth, the organic carbon and nitrogen contents were highest in the finest separates. In samples of a ground-water rendzina and a chernozemic soil, the coarse clay and silt separates had the highest organic carbon and nitrogen contents. Organic matter was concentrated in low density fractions in all separates. Carbon/nitrogen ratios were lowest in the finer and heavier separates. Calcium, and to a lesser extent manganese, iron and phosphorus, were concentrated in low density fractions: thus these elements appear to be associated with organic matter and may be important in organo-mineral complex formation. Carbonates, titanium, iron, silicon and potassium were concentrated at the highest densities.Organic fractions < 2.06 g cm^?3 from sand size separates were insoluble in alkali and had wide carbon/nitrogen ratios characteristic of plant debris. The light fractions from fine silt and coarse clay separates were more soluble in alkali but showed high ratios of humic to fulvic materials and high absorption at 280 nm. Such materials were considered to be microbial cell debris and were associated with high contents of disordered aluminium and iron oxides and expanding lattice silicates in 1 to 5 μm aggregates.Heavier fractions, particularly of finer clay separates, contained more fulvic and humic materials of a more aliphatic nature than those in < 2.06 g cm^?3 fractions. It is suggested that physical sorption on clay surfaces may be more important in these fractions. Ellite and kaolinite were concentrated in medium density fractions, and contents of some iron oxides and titanium minerals were highest in fractions > 2.06 g cm^?3. Such minerals plus quartz and feldspars were associated with minor amounts of organic matter or possibly were not involved in organo-mineral associations.     

The Yields and Carbon and Nitrogen Balances in the Polyfactorial Field Experiments

The polyfactorial long-term field experiments have been founded in 1979 in several experimental stations located in different soil and climatic conditions, representing a climate and pedosequence of arable soils in the Czech Republic. Four of these experiments exist till the present time. Essentially, the same experimental design that includes different fertilisation with farmyard manure and/or with mineral fertilisers (N, P, K), liming and stand density, each in five levels with four replications, have been applied for all these experiments. Practically, the same eight year crop rotations were applied during the first and second rotations. A conventional tillage has been applied. Organic carbon and nitrogen contents in soil, dry matter of the main and second products, nitrogen uptake by the main and second products and carbon and nitrogen balances have been evaluated in six selected variants of organic and mineral fertilisation over the time period 1996 to 2000.     

Cadmium occurrence in soil organic matter and its availability to wheat seedlings

Experiments were performed concerning the influence of soil organic matter on Cd availability to wheat seedlings. Cadmium added to soil was bound by alkali soluble humic substances through linkages so strong that it was not removable by seedlings under toxic limit. Cadmium linked by organic matter was principally found in fulvic acids, and after polyamide chromatography of the latter, all fulvic Cd was completely recovered in first fraction which contained the major part of aminoacid compounds. These findings suggest that interactions between Cd and proteic substances, frequently reported in studies on animal tissues, are active in soil too.     

生物腐植酸对新疆甘草产地沙退化土壤修复效果评价——以土壤养分指标为例

应用生物腐植酸对新疆甘草产地沙退化土壤进行了改良,研究了施用生物腐植酸后第90~190天内土壤全氮和有机碳含量的动态变化,并对第190天时土壤其他各主要养分指标的变化进行了分析,最后通过主成分聚类分析法对第190天时生物腐植酸的修复效果进行了综合评价。结果表明:施用生物腐植酸可以在190d内显著提高土壤全氮和有机碳等主要养分含量,最佳施用量为450kg.hm-2,土壤全氮、有机碳、碱解氮、速效磷、速效钾、土壤可提取腐殖质碳、富里酸碳和胡敏酸碳含量分别比对照提高了21.6%、15.9%、36.6%、20.0%、13.9%、21.0%、17.4%和25.2%。主成分分析结果显示,按不同施用量生物腐植酸的修复效果进行排序,为450kg.hm-2750kg.hm-2600kg.hm-2300kg.hm-2150kg.hm-2CK。     

New methodology to assess the quantity and quality of humic substances in organic materials and commercial products for agriculture

Purpose

The traditional method to determine humic content (humic and fulvic acids) in commercial fertilizers, biostimulants, and organic materials is based on the oxidation of the organic carbon contained in the basic-soluble but acid-insoluble fraction (humic acids) and the basic-acid soluble fraction (fulvic acids) of their alkaline water extracts. This methodology, merely operational, makes it impossible to distinguish if the quantified carbon corresponds to substances with “humic” chemical nature or to non-humic organic matter but with similar solubility properties to those of humic matter. The aim of this work is to develop a new methodology that not only quantifies the humic content in commercial products (and raw materials) but also assesses the humic quality of the quantified organic matter.

Materials and methods

To this end, humic and fulvic (-like) fractions have been isolated/purified from several humic and non-humic materials and characterized by means of elemental analysis and UV-visible, fluorescence, and infrared spectroscopies, and these data have been used to perform a discriminant analysis (DA).

Results and discussion

The model obtained from the DA is able to discriminate humic and fulvic fractions from apparently humic or fulvic ones and provides discriminant classification functions that have proven to successfully predict the “humic quality” of the fractions isolated from commercial products, after their elemental and spectroscopic characterization.

Conclusions

Therefore, the combination of the fractionation, characterization, and evaluation by the DA is proposed as an effective methodology for quantifying and assessing the quality of the humic content claimed in the labels of commercial products.

     

长期施肥对小麦-玉米作物系统土壤腐殖质组分碳和氮的影响

通过对华北平原小麦–玉米轮作农田生态系统18年田间施肥试验,研究了长期不同施肥处理对耕层（0—20 cm）土壤腐殖质及活性腐殖质组分碳和氮的影响。试验设化肥NPK不同组合（NPK、NP、NK、PK）,全部施用有机肥（OM）,一半有机肥+化肥NPK（1/2OMN）及不施肥（CK）共7个处理。结果表明,各施肥处理均能在不同程度上增加土壤腐殖质（胡敏酸、富里酸和胡敏素）及活性腐殖质（活性胡敏酸和活性富里酸）组分碳和氮含量,提高可浸提腐殖质（胡敏酸和富里酸）及活性腐殖质组分碳和氮分配比例;但施肥对土壤活性腐殖质组分碳和氮含量的增加率均分别高于腐殖质组分碳和氮。各处理土壤腐殖质及活性腐殖质组分碳和氮含量均为OM处理最高,且有机肥与化肥NPK配施高于单施化肥各处理;而化肥处理中NPK均衡施用效果最好。说明施用有机肥、有机肥与化肥NPK配施及化肥NPK均衡施用是增加土壤腐殖质及活性腐殖质组分碳和氮的关键;活性腐殖质组分碳和氮较腐殖质组分碳和氮对施肥措施的响应更灵敏。     

The distribution of the stable carbon isotope (13C/12C) in fractions of soil organic matter

The carbon-isotopic composition of fulvic and humic acid from the A horizons of eight soil types, developed under a wide variety of climatological conditions, was measured. The fulvic acid is always enriched in ¹³C as compared with the humic acid from the same soil by a rather constant factor of 0.9?. The fulvic acids are isotopically closer to the plant source of the organic matter and thus represent an intermediate stage in the formation of humic substances. Depth sections of peat soil showed that carbon isotopes can be used to evaluate the dynamic nature of the fulvic-acid fraction. With depth, a transfer of carbon groups from polysaccharides to fulvic acid is seen. Based on isotopic evidence it is shown that in addition to formation of β-humus, part of the fulvic acid is condensed with depth to a stable humic fraction — humin.     

Dissolved organic matter in lysimetric water of mountain forest soils in the southern Sikhote Alin

The fractional composition of dissolved organic matter and the chemical nature of humic and fulvic acids were studied in lysimetric waters from forest soils of different altitudinal zones in the Sikhote Alin Range. The elemental composition, infrared absorption spectra, concentrations of acid functional groups, and pK spectra of humic and fulvic acids were determined. Fulvic acids predominated in the upper soil horizons, and fraction of nonspecific dissolved organic substances predominated in the lower mineral horizons. The portion of humic acids in the humus horizons markedly decreased from the low-mountain soils to the high-mountain soils; the nitrogen content of humic and fulvic acids decreased in the same direction. Three classes of carboxyl and phenolic groups were determined in pK-spectra of humic and fulvic acids. The soils of high-mountain zones had stronger acidic properties of humic and fulvic acids in comparison with the soils of low-mountain zones. The determined characteristics of the composition of dissolved organic matter and the trends of their changes contribute to our knowledge of pedogenetic processes in the altitudinal sequence of forest landscapes of the Sikhote Alin Range.     

沈阳市郊玉米连作土壤有机质组成及其对土壤结构的影响

通过对沈阳市郊玉米连作土壤的有机质、结构情况以及二者相互关系研究表明,土壤中有机质大致范围在16.31gkg-1～23.72gkg-1,腐殖质大致范围在15.17gkg-1～21.49gkg-1,非腐殖质大致范围在1.14gkg-1～2.59gkg-1;在腐殖质各组分中,胡敏素的含量最高,约占腐殖质总量的58.93%～66.34%,胡敏酸约占16.26%～22.87%,富里酸约占16.82%～18.20%,胡富比约在0.95～1.32之间;干筛处理后>0.25mm的土壤团聚体占到80%以上,其中以>2mm团聚体为主,湿筛处理后>0.25mm的土壤团聚体仅占20%左右,其中0.25～0.5mm团聚体为主,水稳性系数在17.33%～35.67%。对有机质及其各组分与土壤各级团聚体做的相关分析结果表明,有机质与0.25～5mm粒径组的团聚体呈显著相关,与>5mm团聚体不相关,且胡敏酸主要影响1～5mm大团聚体的形成。     

不同施肥措施对白土腐殖质组成的影响

以白土稻区4年大田定位试验为基础,设置2种翻耕深度(10 cm、20 cm,分别标记为T10、T20)和4种施肥措施(单施化肥、化肥+畜禽粪肥、化肥+秸秆还田、化肥+绿肥,分别标记为F、F+M、F+S、F+G),通过腐殖质组成修改法分别提取表层土壤水溶性物质、胡敏酸、富里酸和胡敏素,研究不同施肥措施对白土腐殖质各组分碳含量的影响。结果表明:单施化肥措施下,翻耕20 cm处理(T20+F)土壤总有机碳和腐殖质各组分碳含量均低于翻耕10 cm处理(T10+F),但差异未达显著水平。在翻耕20 cm的基础上增施有机肥能显著提高土壤总有机碳和腐殖质各组分碳含量,增施畜禽粪(T20+F+M)、秸秆还田(T20+F+S)和增施绿肥(T20+F+G)3处理的土壤总有机碳、胡敏酸、富里酸和水溶性物质碳含量较T20+F处理分别提高14.57%~30.64%、10.36%~30.57%、0.74%~12.31%和14.25%~26.80%。增施有机肥显著提高胡敏素碳含量,T20+F+M、T20+F+S和T20+F+G处理较T20+F处理提高18.87%~35.78%。4年不同翻耕与施肥措施对白土腐殖质性质未产生显著影响。增施有机肥能一定程度上提高土壤PQ值、胡富比、E4/E6值和色调系数。相关性分析表明,胡敏素、胡敏酸、富里酸碳含量与总有机碳含量间均存在显著或极显著正相关,与水溶性物质碳含量间无明显相关性。     

沈阳市郊日光温室土壤有机碳组成特征研究

对沈阳市郊东陵、于洪、苏家屯、新城子四区蔬菜栽培15年左右的日光温室土壤有机碳组成特征进行了研究,以相应温室外的露地栽培土壤为对照,结果表明:日光温室蔬菜栽培的有机肥用量远远高于温室外露地栽培。随着有机肥用量增加,温室土壤水溶性碳、腐殖酸碳的增加比例小于胡敏素碳的增加比例。各区温室土壤总有机碳、非腐殖质碳、腐殖质碳数量的平均值分别是温室外露地的1.76～3.06倍、3.41～5.23倍、1.57～2.99倍。温室土壤中非腐殖质所占比例较对照露地的大,其水浮物碳占总有机碳比例是对照露地的1.80～2.63倍,温室和露地土壤水溶性物质碳占总有机碳的百分比大多低于2%。温室土壤胡敏酸碳、富里酸碳、胡敏素碳数量均高于对照露地,但有1/3以上的温室土壤H/F低于对照露地土壤。由于不同农户的水、肥管理水平差异较大,不同温室土壤的总有机碳及各组分的碳变异性较大。     

Effect of cultivated plants on physico‐chemical characteristics of humic substances of soils amended by sewage sludge

Abstract

Humic substances were extracted from raw sewage sludge samples as well as an alluvial slightly alkaline soil [Typic Xerofluvent (So)], a clay loam soil [Calcixerollic Xerochrept (M)] and the corresponding field plots amended with different rates of sewage sludge and cultivated with corn and cotton respectively, in a two‐year field experiment. These substances have been characterized by chemical and spectroscopic methods. The chemical analyses showed that humic acids (HAs) and fulvic acids (FAs), were effected by the cultivated plant. Humic substances extracted from field plots with cotton showed higher carbon, but less nitrogen (N), total acidity and carboxylic groups content, as compared with those under corn. Generally HAs and FAs extracted from the fields plots amended with sewage sludge had higher N content, lower values of total acidity, carboxylic groups and carbon contents than those from the unamended soils. The FT‐IR spectra of humic (HAs) and fulvic (FAs) acids extracted from sewage sludge indicated the presence of high percentage of aliphatic carbon, polysaccharides and proteinaceous materials. The spectra of the humic matter in the field plots showed less aliphatic but increased amide stretch in comparison with the sludge. The absorption due to C=O in carboxylic groups of the FAs was not pronounced, though the presence of polysaccharides and protein decomposition products was clearly indicated.     

Bodenatmung,Stickstoffmineralisation und Humusabbau ostafrikanischer Böden nach Trocknung und Wiederbefeuchtung

Soil respiration, nitrogen mineralization and humus decomposition of East African soils after drying and remoistening Soil respiration and nitrogen mineralization of 51 East African cultivated, savanna and forest soils were compared after 3 and 21 weeks of air drying. The average soil respiration after 21 weeks of drying was 1.221 ± 0.106 times higher than that after 3 weeks of drying whereas the average nitrogen mineralization was not increased significantly (factor 1.132 ± 0.256). The increase in soil respiration was correlated positively with the water soluble organic matter. During air dryings of 3 days and moist incubations of 4 days at 30°C, which were repeated 20 times in 10 soils, 3–10% of the organic carbon and 8–19% of the organic nitrogen (low humus vertisol 69%) were mineralized. Changes in the amount and the extinction of humic and fulvic acids were considered to be indicative for an increased humification during the drying and remoistening of soils.     

Acid properties of fulvic and humic acids isolated from two acid forest soils under different vegetation cover and soil depth

We studied the acid‐base properties of 16 fulvic acids and 16 humic acids isolated from the surface (3–15 cm) and subsurface (> 45 cm) horizons of two types of acid forest soils, derived respectively from amphibolite and granite rocks, under five different types of vegetation. The observed differences between the contents of humic substances in the two types of soils were related to the degree of Al‐saturation of the soil organic matter, as indicated by the molar ratio between pyrophosphate extractable Al and C. Humic fractions were characterized in terms of elemental composition, and CPMAS ¹³C NMR spectrometry. The contents of carboxylic and phenolic groups were estimated by potentiometric titrations conducted in 0.1 m KNO₃ in a nitrogen atmosphere. The fulvic acids contained more carboxylic groups but less phenolic groups than the humic acids: the ratio of phenolic to carboxylic groups in the humic acids was 0.48 ± 0.10 and in the fulvic acids 0.23 ± 0.05. The mean values of the protonation constants of each of the humic substance fractions can be used as generic parameters for describing the proton binding properties. The fulvic acids isolated from the subsurface horizon of the soil contained between 2.6 and 23% more carboxylic groups, and the humic acids between 8 and 43% more carboxylic groups than those isolated from the surface horizon of the same soil.     

Carbon and nitrogen in operationally defined soil organic matter pools

Humic substances [humic acid (HA), fulvic acid (FA), and insoluble humin], particulate organic matter (POM), and glomalin comprise the majority (ca 75%) of operationally defined extractable soil organic matter (SOM). The purpose of this work was to compare amounts of carbon (C) and nitrogen (N) in HA, FA, POM, and glomalin pools in six undisturbed soils. POM, glomalin, HA, and FA in POM, and glomalin, HA, and FA in POM-free soil were extracted in the following sequence: (1) POM fraction separation from the soil, (2) glomalin extraction from the POM fraction and POM-free soil, and (3) co-extraction of HA and FA from the POM fraction and POM-free soil. Only trace amounts of HA and FA were present in the POM fraction, while POM-associated glomalin (POM-glomalin) and POM alone contributed 2 and 12%, respectively, of the total C in the soil. Mean combined weights for chemically extracted pools from POM and from POM-free soil were 9.92 g glomalin, 1.12 g HA, and 0.88 g FA kg⁻¹ soil. Total protein and C, N, and H concentrations showed that glomalin and HA were, for the most part, separate pools, although protein was detected in HA extracts. Even though percentage carbon was higher in HA than in glomalin, glomalin was a larger (almost nine times) operationally defined pool of soil organic C. Glomalin was also the largest pool of soil N of all the pools isolated, but all pools combined only contained 31% of the total N in the soil.