Behavior of phenolic substances in the decaying process of plants

The behavior of phenolic substances in the decaying process of rice straw, ladino clover, and fanen leaves of red oak under moist conditions, and also of rice straw under various conditions were compared in the laboratory. The amounts of phenolic substances, divided into either humic acid and fulvic acid fractions, or ether-extractable, butanol-extractable and organic solvent-unextractable fractions, and the amounts of individual phenolic acids were periodically determined during incubation for 150 days. The following results were obtained.

1) The amounts and behavior of phenolic substances in various fractions differed considerably among the plant materials. The total amount of phenolic substances was remarkably larger in red oak leaves than in the others during the whole period of incubation. The amounts of phenolics in the fulvic acid fraction changed to a larger extent than those in the humic acid fraction during the decaying process of plant materials. The changes in total amount of phenolics in decaying red oak leaves and ladino clover were mainly due to changes in the level of relatively hydrophilic phenolics in the fulvic acid fraction, but the changes in decaying rice straw were mainly due to changes in the level of relatively lipophilic phenolics.

2) Rice straw and ladino clover, especially the former, contained large amounts of p-coumaric and ferulic acids, but these decreased rapidly in the early stage of the decaying process. The amounts in red oak leaves were small, but did not decrease markedly during incubation.

3) The changes in amounts of phenolics in both humic acid and fulvic acid fractions in the decaying process of rice straw were largely influenced by temperature, moisture, and pH, but not to a large extent by C/N ratio and the presence of soil. At higher temperatures under moist conditions, phenolic substances disappeared rapidly. Also, acidification of the system inhibited the degradation process.     

Behavior of phenolic substances in the decaying process of plants

The changes in amount of ether-extractable phenolic substances, individual phenolic adds, organic matter content, and pH value in the decaying process of rice straw were compared at 10, 30, and 50°C under moist and flooded conditions for 70 days.

1) The changes in pH value with time varied markedly according to temperature and water conditions.

2) Phenolic substances in the ether-extractable fraction obtained from the acidified solution of alkaline methanol extract contained undetected phenolic compounds in amounts larger than the phenolic adds detected by gas chromatography. pH value during incubation was hardly attributable to these phenolic substances because of their small quantity.

3) The changes in amount of the ether-extractable phenolic substances with time was mainly due to phenolic compounds other than phenolic acids, and influenced largely by the temperature and water conditions. Their formation and degradation took place rapidly at high temperatures under flooded conditions.

4) From the plots of individual phenolic acids vs. time, it was tentatively concluded that phenolic acids contalned in non-decayed straw were rapidly degraded in the earlier stage, and some of them were newly produced from ether-unextractable precursors in the later stage. These reactions occurred rapidly at high temperatures, especially under flooded conditions.

5) The content of p-hydroxybenzolc acid increased simultaneously with a rapid decrease in p-coumaric acid during the incubation ot straw. The relationship between vanillic acid and ferulic acid was the same.     

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.     

Behavior of phenolic substances in the decaying process of plants: I. Identification and Quantitative Determination of Phenolic Acids in Rice Straw and Its Decayed Product by Gas Chromatography

Phenolic acids in rice straw and its decayed product were surveyed and quantitatively analyzed by gas chromatography.

1) Thirteen kinds of phenolic acids in rice straw and its decayed product were identified. Besides p-hydroxybenzoic, vanillic, P-coumaric, and ferulic acids which had been already reported, nine phenolic acids were newly identified; these were benzoic, salicylic, syringic, protocatechuic, β-resorcylic, caffeic, sinapic, gallic, and gentisic acids.

2) A gas chromatographic analysis was applied to the micro-determination of major phenolic acids in rice straw and . the decayed products. The methanolic alkaline extracts from them were washed with ether, acidified, transferred into ether, trimethylsilylated, and injected into a gas chromatograph equipped with a silicon SE-30 column. The recoveries of p-coumaric, p-hydroxybenzoic, vanillic, and syringic acids were more than 90%, and ferulic and syringic acids were recovered at about 70%.

3) The content of each of the above described major phenolic acids in rice straw ranged from 0.002 to 0.037% per dry weight. p-Coumaric acid was contained in the largest amount. Ferulic and vanillic acids followed. In the decayed straw, these contents decreased to 0.002–0.017%. The whole phenolic substances in ether-extracted fraction were present at 0.34%, and the amount decreased to one-third during the decaying process.     

作物秸秆碳在土壤中分解和转化规律的研究

采用14C标记秸秆,在大田和实验室的研究结果表明,秸秆的分解速率主要取决于C/N比。施入土壤后,土壤微生物迅速增加,尤其是细菌。秸秆降解首先形成非结构物质,其中大部分转化为富里酸,进而转化为胡敏酸。分解产物对土壤腐殖质的更新,从腐殖质表面官能团或分子断片开始,逐步进行。非结构物质可与腐殖酸的单个分子产生交联作用,在一定条件下,交联的复合分子可进入腐殖质分子核心的成分中。腐殖酸单个组分在土壤中的转化和重新分配,仅仅与腐殖质表面官能团的反交换过程密切相关。粘土矿物选择性吸附胡敏酸,而且优先吸附胡敏酸中低分子成分。     

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.     

秸秆还田配施腐熟剂对低产黄泥田的改良作用

【目的】低产黄泥田是一种发育程度低的水稻土,土壤贫瘠,作物产量低。本文研究探讨了小麦、 水稻、 油菜秸秆还田及配施秸秆腐熟剂后秸秆还田对低产黄泥田的土壤改良效果。【方法】在荆门市双季稻区设置了单施化肥(对照),化肥配施小麦、 水稻、 油菜秸秆,化肥配施小麦、 水稻、 油菜秸秆同时添加秸秆腐熟剂等七个处理的田间试验。取样分析了这些处理对双季稻产量、 土壤理化性质、 土壤团聚体组成、 土壤腐殖质组成及结合形态的影响。【结果】1)在早、 晚稻上秸秆还田配施秸秆腐熟剂增加了稻谷的产量,比单施化肥最多增产1423.2 kg/hm2,增幅为23.5%; 添加秸秆腐熟剂也能够增加稻谷的产量,比单独秸秆还田最多增产653.8 kg/hm2,增幅为9.6%。与对照比较,油菜秸秆+腐熟剂处理晚稻显著增产。2)土壤有机质、 全氮、 碱解氮、 有效磷、 速效钾含量、 阳离子交换量秸杆+腐熟剂处理高于对应的秸秆还田处理,而土壤容重则下降。3)与对照比较,秸秆处理5 mm土壤风干团聚体含量增加3.78%~8.62%,0.25 mm土壤风干团聚体含量也都增加,0.25 mm水稳定性团聚体含量下降。秸秆还田有利于＞0.25 mm水稳定性大团聚体总量的增加,减少了土壤团聚体破坏率。4)与对照比较,秸秆处理的土壤水溶性物质、 土壤胡敏酸、 富里酸、 可提取腐殖物质总量、 胡敏素含量增加。添加腐熟剂后,胡敏酸与富里酸比值低于相对应的秸秆还田处理; 土壤松结合态腐殖质、 稳结合态腐殖质、 紧结合态腐殖质含量及结合态腐殖质总含量都有所增加。结合态腐殖质中松结合态腐殖质含量最高,所有的处理都在60%以上。【结论】秸秆还田配施秸秆腐熟剂不仅能够增加早稻和晚稻的稻谷产量,还提高了土壤有机质、 全氮、 碱解氮、 有效磷、 速效钾含量及阳离子交换量,降低了土壤容重。秸秆还田主要提高了＞0.25 mm风干团聚体、 水稳性大团聚体含量,减少了土壤团聚体破坏率。秸秆还田处理显著提高了土壤松结合态腐殖质含量和结合态腐殖质总含量。秸秆还田配施秸秆腐熟剂可以提高作物产量、 提高土壤肥力、 改善土壤结构、 增加土壤腐殖质含量与活性,能够改良低产黄泥田。化肥+油菜秸秆+秸杆腐熟剂处理是一种良好的低产黄泥田改良措施。     

Susceptibility of humic acid towards sodium amalgam

Three humic acids (HA-I) of different degrees of humification were treated with HCl (1:1). The hydrolyzed humic acids (HA-II) were subsequently degraded with Na-amalgam. The reduction products were divided into the following fractions: humic acid residues (HA-III), fulvic acid (FA), and ether-extractable lubstances (Et),

The humic acids used in this study were extracted from the following three soils; Inogashira (Volcanic ash soil), Kuragari (Drown forest soil, B_D type), and Higashiyama (Brown forest soil, rB_B type).

The experimental results are summarized as follows:

1. The RF values of HA-II, in the case of Inogashira and Kuragari, were higher, and the △log K values were lower than those of HA-I. The carbon and oxygen contents of HA-II were higher while the hydrogen, and nitrogen contents were lower than those of HA-I.

2. The total amount of carbon in HA-III. FA and Et added up to about 90% of the carbon present in HA-II. The carbon of HA-III found in HA-III after reduction tended to increase in the order: Inogashira>Kuragari>Higashiyama. In FA and Et, the opposite trend was followed.

In the case of Inogashira about 60% of the carbon of HA-II was found in HA-III.

3. The dark coloration of humic acid largely disappeared during the reductive treatment. As for the amorphous carbon-like structure detected in Inogashira, it was not found in the HA-III after reduction.

Therefore, it was presumed that the structures destroyed or saturated during the reductive treatment were the ones responsible for the essential properties of humic acid.     

The chemistry of humic and fulvic acids extracted from argentine soils—II. Permanganate oxidation of methylated humic and fulvic acids

Five humic and three fulvic acids, extracted from Argentine soils, were methylated and oxidized with KMnO* solution. The oxidation products were extracted into ethyl acetate, remethylated, separated by preparative gas chromatography and identified by comparing their mass and micro-IR spectra with those of authentic specimens.The major oxidation products from the humic acids were benzenetetra, -penta-, and -tricarboxylic and hydroxybenepentacarboxylic acid. The major compounds isolated from the fulvic acid oxidation products were aside from benzenecarboxylic and phenolic acids, substantial amounts of ethyl-benzylsulfonate and N-methyl-benzylsulfonamide, one complex aromatic ester and two anhydrides. The origin of the S-containing compounds is uncertain; they could be impurities. Weight ratios of benzenecarboxylic to phenolic acids averaged 5·8 for humic acids but only 0·9 for fulvic acids, suggesting an enrichment in phenolic structures in the fulvic acids. Possible structural arrangements for humic and fulvic acids are discussed.     

Effects of rice‐straw and phosphorus application on production and emission of methane from tropical rice soil

Rice‐straw amendment increased methane production by 3‐fold over that of unamended control. Application of P as single superphosphate at 100 μg (g soil)^–1 inhibited methane (CH₄) production distinctly in flooded alluvial rice soil, in the absence more than in the presence of rice straw. CH₄ emission from rice plants (cv. IR72) from alluvial soil treated with single superphosphate as basal application, in the presence and absence of rice straw, and held under non‐flooded and flooded conditions showed distinct variations. CH₄ emission from non‐flooded soil amended with rice straw was high and almost similar to that of flooded soil without rice‐straw amendment. The cumulative CH₄ efflux was highest (1041 mg pot^–1) in rice‐straw‐amended flooded soil. Appreciable methanogenic reactions in rice‐straw‐amended soils were evident under both flooded and non‐flooded conditions. Rice‐straw application substantially altered the balance between total aerobic and anaerobic microorganisms even in non‐flooded soil. The mitigating effects of single‐superphosphate application or low‐moisture regime on CH₄ production and emission were almost nullified due to enhanced activities of methanogenic archaea in the presence of rice straw.     

Chemical studies on soil humic acids

Seventeen samples of soil humic acids, two fractions of soil fulvic acid sample, and several related compounds such as lignin, tannin, flavonoid and artificial humic substances were decomposed in conc. KOH solution at 180°C. Succinic acid, glutaric acid, phloroglucin, p-hydroxybenzoic acid, vanillic acid, protocatechuic acid, 3,4-dihydroxy-5-methoxybenzoic acid, and gallic acid were detected in the degradation products of humic acids. The amounts of these degradation products were discussed in relation to the degree of humification or the sources of the humic acid samples. Succinic acid also resulted from glucose, polymaleic acid, and the humic acid and humin prepared from glucose, but glutaric acid resulted only from glucose humic acid and glucose humin but not from glucose and polymaleic acid. Succinic acid and glutaric acid were supposed to result from the same structural portions in humic acids because of the very significant positive linear correlation between their amounts. p-Hydroxybenzoic, vanillic, protocatechuic, and 3,4-dihydroxy-S-methoxybenzoic acids were presumed to result mainly from lignin structure in humic acids. Soil humic acids yielded small amounts of gallic acid although the yields by hydrolysable tannins were in large amounts. The yields of above-mentioned degradation products from humic acids decreased with increasing degree of humification. Phloroglucin resulting from ftavonoids including condensed tannins were also found in the degradation products of humic substances. Its yield showed no linear correlation with RF value of humic acid, and is presumed to be rather related to the vegetation at the sites of soil sampling.     

The alkaline hydrolysis of humic substances

A humic and a fulvic acid were subjected to four successive hydrolyses with 2NNaOH solution at 170°C for 3 h. Following each hydrolysis, the degradation products were extracted into ethyl acetate, methylated, separated by chromatographic techniques and identified by mass spectrometry and micro-IR spectrophotometry.One g of humic acid yielded 113.5 mg of aliphatic compounds (mainly n-C₁₆ and n-C₁₅) fatty acids), 72.1 mg of phenolics (principally guaiacyl and syringyl derivative) 17.1 mg of benzenepolycarboxylic acid esters and 30.4 mg of N-containing compounds (mainly secondary aromatic amides). Repeated attacks by the alkali on 1.0 g of fulvic acid released 103.8 mg of aliphatics, 133.8 mg of phenolics, 27.0 mg of benzenecarboxylic but 181.8 mg of N-containing compounds. Most of the latter appeared to have been formed during the second, third and fourth hydrolysis which produced reactive compounds that could abstract N from diazomethane which was used as methylating reagent. While 25.0% of the initial humic acid resisted repeated attacks by the alkali, practically all of the fulvic acid was converted into ethyl acetate-soluble products. The alkali-resistant humic acid residue produced high yields of benzenepolycarboxylic acids on alkaline permanganate oxidation.Alkaline hydrolysis, which is known to cleave CO bonds, was found to be relatively specific, although not very efficient, for the degradation of structural phenolic humic and fulvic acid components and for the concomitant liberation of adsorbed aliphatics and N-containing compounds, but was relatively ineffective for degrading aromatic structures linked by CC bonds.     

Influence of natural and synthetic humic substances on the activity of urease

The activity of a purified urease, obtained from Bacillus pasteurii, was inhibited by humic and fulvic acids obtained from an agricultural soil. Enzyme kinetic studies showed that the humic substances affected the affinity of the enzyme for its substrate (K_m) and the maximum velocity of the reaction (V_max). The V_max was inhibited to the same extent by both humic (HA) and fulvic (FA) acids, the precise effect depending on the pH and concentration of humic substance. At pH 4.0, HA concentrations of 25 pg cm^?3 and 10 μg cm^?3 inhibited the V_max by 38.5% and 20% respectively. HA and FA had similar effects on the K_m but in this case the lowering of the affinity of the enzyme for its substrate was not concentration dependent in the range 0–25 μg cm^?3 of humic substance. Typically, the affinity was decreased from a K_M of 50 mM in the control to 67 mM in the presence of HA and FA. The effects were not due primarily to the ash or N contents of the humic substances because de-ashed humic acid and synthetic model humic (made from catechol, guaiacol, pyrogallol, resorcinol and protocatechuic acid) and fulvic acid (made from polymaleic acid), containing virtually no ash or N, were equally as effective. The effect was not related to the phenolic monomers which, before polymerization, had no effect on urease activity.     

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.     

Decomposition and distribution of residual activity of some 13C-microbial polysaccharides and cells,glucose, cellulose and wheat straw in soil

Studies were made to determine the rate of decomposition of some ¹⁴C-labeled microbial polysaccharides, microbial cells, glucose, cellulose and wheat straw in soil, the distribution of the residual ¹⁴C in various humic fractions and the influence of the microbial products on the decomposition of plant residues in soil. During 16 weeks from 32 to 86 per cent of the C of added bacterial polysaccharides had evolved as ¹⁴CO₂. Chromobacterium violaceum polysaccharide was most resistant and Leuconostoc dextranicus polysaccharide least resistant. In general the polysaccharides, microbial cells, and glucose exerted little effect on the decomposition of the plant products. Upon incubation the ¹⁴C-activity was quickly distributed in the humic. fulvic and extracted soil fractions. The pattern of distribution depended upon the amendment and the degree of decomposition. The distribution was most uniform in the highly decomposed amendments. After 16 weeks the bulk of the residual activity from Azotobacter indicus polysaccharide remained in the NaOH extracted soil. From C. violaceum polysaccharide both the extracted soil and the humic acid fraction contained high activity. About 50–80 per cent of the residual activity from the ¹⁴C-glucose, cellulose and wheat straw amended soils could be removed by hydrolysis with 6 n HCl. The greater part of this activity in the humic acid fraction was associated with the amino acids and that from the fulvic acids and residual soils after NaOH extraction with the carbohydrates. About 8 16 per cent of the activity of the humic acid fraction was present in substances (probably aromatic) extracted by ether after reductive or oxidative degradation.     

Effect of soil depth on acid properties of humic substances extracted from an ombrotrophic peat bog in northwest Spain

The most southerly ombrotrophic peat bogs in Europe are in Galicia (northwest Spain). The humic matter in them originates from chemical processes in anaerobic conditions. We studied the acid properties of fulvic acids and humic acids isolated from two peat horizons of an ombrotrophic peat bog by potentiometric titration. Solutions containing 25, 50 and 100 mg l⁻¹ of each humic substance were titrated at ionic strengths 0.005 m , 0.01 m and 0.1 m (with KNO₃ as the inert electrolyte). Charge curves were analysed with a Donnan model to determine the intrinsic proton binding parameters. The concentration of the humic substance affected the charge curves more significantly at pH exceeding 6, and tended to disappear at greater concentrations. The proton binding conditional constants decreased with increasing ionic strength, this effect being more significant in the carboxylic groups with less affinity for protons. The proton binding constant of the carboxyl groups in a fulvic acid was one order of magnitude less than the value for the corresponding humic acid, whereas for the phenolic groups the values for both fractions were similar. The total content of acid groups was approximately 2 mol kg⁻¹ greater in the fulvic fraction than in the humic fraction. Both humic fractions from the lower horizon contained more acid groups than those from the upper horizon, mainly because the content of carboxyl groups increases with soil depth. Therefore, the humic substances in the lower horizon of the peat will be more negatively charged, which will affect their solubility and the binding of metal ions.     

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.     

Comparisons of soil organic matter and its fractions by pyrolysis mass-spectrometry

Pyrolysis mass-spectra from a sample of the A₁-horizon of a soil from southern Spain showed predominant peaks related to furan derivatives similar to those observed from complex polysaccharides in which not only hexoses but also pentoses and deoxyhexoses were constituent units. Smaller peaks, typical for protein materials and phenolic units, were also observed. On the other hand, typical peaks for the methoxyphenols of lignins were very small and indicated only limited amounts of undecomposed lignin residues in this soil sample. Peaks related to benzene or toluene were also very small.Humic acid samples from this soil showed much more prominent signals related to protein materials, benzene and phenolic derivatives and weaker polysaccharide-related signals than did the entire sample. Typical lignin related peaks were small or insignificant. Spectra from the grey or brown humidic acid fractions were much like those of the parent humic acid. Brown humic acid, however, showed stronger signals for nitrogen and sulphur compounds, indicating a higher content of protein-like materials in this fraction. Preparations of humic acid hydrolyzed by 6 N HCl showed in their pyrolysis products a marked increase in phenols and methoxyphenols.In its pyrogram, humin resembled humic acid, but signals for complex polysaccharides were more evident. Lignin-like materials seem not to be higher in this fraction. Hymatomelanic acid showed prominent signals related to polysaccharides and lignin. Pyrograms from the soil polysaccharides showed the characteristic pattern of a complex polysaccharide with the presence of fragments from polymers of amino acids or amino sugars. Fulvic acid spectra showed obvious dissimilarities to those from humic acid in that signals for protein, as well as those related to phenols, were low. Depending upon the isolation method, the fulvic acid preparations showed differing signals related to polysaccharide or phenolic materials.     

Characters of humus formed under rice cultivation

To characterize the nature of humus in paddy soils, a comparison was made between the properties of humus in paddy soils and those in adjacent unflooded arable soils.

Rice cultivation generally brought about a considerable increase in organic matter and in the PQ-value, with the exception of Andosol-paddy soils in which organic matter tended to decrease somewhat and the PQ-value remained virtually unchanged. The humification degree of humic acid as judged from Δ log k and RF values was generally lowered by rice cultivation except in the case of Yellow soil-paddy soil in which humic acid was originally low in the degree of humification.

The accumulation of poorly humified humic acid may be a characteristic feature common to all paddy soils. These changes by rice cultivation are observed only in the upper part of the profiles, and seem to be associated with seasonally flooded conditions ot paddy soils. Iron oxides accumulated in subsurface soil have virtually no effect on the properties of humus.