Studies on the properties of organic matter in buried humic horizon derived from volcanic ash

Abstract

Humic acids were extracted from the surface horizon Yu 1 and buried humic horizons (Yu 2, 800-864 AD; Yu 4, ca. 4,000 years B.P.; Yu 6, 7,000 years B.P.; Yu 7, ca. 10,000 years B.P.). The humic acids were filtered with ultramembranes with 20, 10, 5, 1 or 0.1 × 10' M.W. in this order and separated into five fractions; (>20), (20-10), (10-5), (5-1) and (1-0.1) × 10⁴ M.W. fractions. The elementary composition, functional groups, optical properties, and hydrolyzable total- and sugar-carbon contents of each humic acid fraction were determined, and the changes in properties of the humic acid with age after burial were discussed.

In horizons Yu 1 to Yu 6, the patterns of M.W. distribution of the >20 × 10⁴ to (1- 0.1) × 10⁴ fractions were rather similar. In contrast, Yu 7 was characterized by the predominance of (1-0.1) x 10' M.W. fraction and the presence of a small amount of <0.1 × 10⁴ M.W. fraction.

The chemical properties of humic acid (HA) fractions of each humic horizon and their changes with age after burial were as folIows:

1) Elementary composition of HA fractions of each humic horizon was rather similar to each other. The C% and C/N ratio increased, and the H%, N% and H/C ratio decreased in all HA fractions with age.

2) Total acidity and carboxyl contents of HA fractions of Yu 1 were higher in the lower M.W. fractions. These values increased with age up to Yu 4 or Yu 6 horizons, then decreased in the Yu 6 or Yu 7 horizon. The contents of carbonyl groups in all the HA fractions which were very low in Yu 1, showed a wide range of variations in Yu 2, intermediate values from Yu 4 to Yu 6 horizons then decreased in the HA fractions of Yu 7, except for the (>20) fraction.

3) The degree of humification of the HA fractions of Yu 1 judging from the RF and \sDlogK values, tended to be higher in higher M.W. fractions, and increased in all the HA fractions with age after burial.

4) Hydrolyzable total- and sugar-carbon contents were high in the HA fractions of Yu 1 and decreased with age.

5) Changes of elementary composition, degree of humification and hydrolyzable total- and sugar-carbon contents were conspicuous from the Yu 1 to Yu 2 horizons, and less significant afterwards.

6) The 0%, C/O ratio and phenolic OH content did not show any consistent change with age after burial.     

Amorphous clay materials of towada ando soils

Towada Ando soils consisted of five soils—Towada-a (1,000 years old), Towada-b (2,000 years old), Chuseri (4,000 years old), Nanbu (8,600 years old), and Ninokura soils (10,000 years Amorphous clay materials of these soils taken at different localities were studied by the combined use of selective dissolution and differential infrared spectroscopy, X-ray analysis, electron microscopy, etc.

The main clay minerals of Towada-a soils, present-day soils, were montmorillonite-vermic-ulite chloritic intergrades and opaline silica, or these minerals and allophane in the humus horizons, and allophane in the non-humus ones. Towada-b soils overlain by the Towada-a soils showed the clay mineralogical constituents similar to those of Towada-a soils. However, allophane was one of the main clay minerals in all the humus horizons as well as non-humus ones. The main clay minerals of Chuseri soils were allophane and layer silicates consisting chiefly of chloritic intergrades and chlorite in the humus horizons, and allophane in the non-humus ones. Opaline silica was present in minor amounts in the humus horizons of Chuseri soils, but nearly absent in Nanbu and Ninokura soils.

There were remarkable differences in the clay mineralogical composition of Nanbu and Ninokura soils with differences of their environmental conditions. Allophane and imogolite Were dominant in the clay fractions of both humus and non-humus horizons of very shallowly buried Nanbu soil which was subjected to the strong leaching process. Allophane was the main clay mineral of deeply buried Nanbu and Ninokura soils which showed the absence of notable accumulation of bases and silica. On the contrary, halloysite with a small amount of siliceous amorphous material appeared in very deeply buried Nanbu and Ninokura soils where bases and silica were distinctly accumulated. The amounts of halloysite in the clay fractions were larger in the humus horizons than non-humus ones, and in Ninokura soil than Nanbu soil.

Soil age, soil organic matter, and depositional overburden of tephras were observed to be conspicuous among various factors relating to the weathering of amorphous clay materials in Towada Ando soils.     

Studies on the properties of organic matter in buried humic horizon derived from volcanic ash

To investigate the relationship between age and the sugar composition in hydrolysates of the surface horizon and buried humic horizons with age up to 28,000 years B.P., the neutral sugars and amino sugars in soil hydrolysates were determined.

The ratios of total sugar carbon content to total carbon content of soil ranged from 2.68 to 4.13 percent. These values showed no distinct relationship with age.

Rhamnose, fucose, arabinose, xylose, mannose, galactose, glucose, g1ucosamine and galactosamine were present in the hydrolysates of all soil samples.

The polysaccharides of soil samples which have been buried for shorter periods were dominated by glucose, while those of soil samples buried for longer periods were dominated by mannose.

The proportion of hexoses showed a tendency to increase with age, while that of pentoses showed a tendency to decrease with age.     

Postpyrogenic Polycyclic Soils in the Forests of Yakutia and Transbaikal region

Periodical forest fires are typical natural events under the environmental and climatic conditions of central and southern Yakutia and Transbaikal region of Russia. Strong surface fires activate exogenous geomorphological processes. As a result, soils with polycyclic profiles are developed in the trans-accumulative landscape positions. These soils are specified by the presence of two–three buried humus horizons with abundant charcoal under the modern humus horizon. This indicates that these soils have been subjected to two–three cycles of zonal pedogenesis during their development. The buried pyrogenic humus horizons accumulate are enriched in humus; nitrogen; total and oxalate-extractable iron; exchangeable bases (Са⁺² and Mg⁺²); and the fractions of coarse silt, physical clay (<0.01 mm), and clay (<0.001 mm) particles in comparison with the neighboring mineral horizons of the soil profile. The humus of buried pyrogenic horizons is characterized by the increased content of humic acids, particularly, those bound with mobile sesquioxides (HA-1) and calcium (HA-2) and by certain changes in the type of humus.     

Characterization of Al/Fe—humus complexes in dystrandepts through comparison with synthetic forms

The Al/Fe—humus complexes in A₁ horizons of Dystrandepts from several parts of Japan were compared with synthetic complexes prepared from hydroxy ions and from two kinds of humic substances and at several pH values. Samples represented 26 A₁ horizons of soils differing in age, including some that had been buried. The comparisons were based chiefly on extractions of the synthetic complexes and the soil samples with solutions of sodium hydroxide-tetraborate and sodium pyrophosphate.The Al—humus complexes in the Dystrandept samples appeared to be similar to those of synthetic complexes prepared at pH 4–5. Those have OH/Al molar ratios of 0.7–2.5 1. Distribution of the data for the soil samples suggested further that the proportions of polymeric hydroxy Al ions increased as soils became older and also if they were buried. The Fe—humus complexes in the soil samples seemed to be like the synthetic complexes prepared with Fe and humus at pH 4–5 for the most part.     

Soil organic matter,C and N accumulation during natural succession and reclamation in an opencast sand quarry (southern Poland)

Abstract

The work presents study results on the formation of humus horizons, the accumulation of organic carbon and nitrogen as well as humus composition in successional and reclaimed soils in a sand mine cast in southern Poland. Research plots were designed in chronosequence: 5, 17, 20 and 25 years. Increased thickness of humus horizon and accumulation of organic carbon was reported both in successional soils and in reclaimed soils. However, in corresponding age groups of reclaimed soils these characteristics were two times as high as in successional soils. The estimated accumulation rate of organic carbon (C_org) was three times higher and total nitrogen (N_t) five times higher in reclaimed soils than in successional soils. In both types of soils there was an increase in the amount of carbon trapped with humic and fulvic acid (C_Ha + C_Fa) and structure of humic acids. Studies indicated that reclamation treatment significantly accelerated soil-formation in opencast sand mine.     

The distribution of PG (green fraction of P type humic acid) and the degree of humification of PB (brown fraction of P type humic acid) in soils of central Japan

Abstract

Pg contents of soils chosen from the major soil groups occurring in the mountain area of Central Japan were measured by the method presented by the author in a previous paper. The Pg contents of the soils ranged from 0 to 0.58 per cent of the dry soils. In podzolic soils, Pg contents were high in A horizons and gradually decreased with depth and in some cases of brown forest soils, Pg contents were highest in B horizons. The percentage of Pg in humic acid ranged from 0 to 8.6 per cent, and the highest value was observed in the C horizon of Dando Bo soil, Pg contents were high in humid and acidic soils containing much humic acid. Humidity, soil pH and humus content may affect the Pg accumulation by controlling the activity of Pg-producing fungi. ? log K values of Pb were calculated to estimate the degree of humification of P type humic acids and indicated that Pb's were relatively immature.     

Studies on the humus forms of forest soils

The results of humus composition analysis of each fraction separated physically from each horizon of the five forest soils used in the last paper (3) were presented.

Regular changes in humus composition were observed with the gradation of horizons and With the decrease in particle size. Most of the humic acids from plant residual fractions belonged to the Rp type; hurnic acids from the L layers showed a tannin-like character which disappeared with the progress of decomposition, and humic acids from the smaller particle fractions of the layers contained a Pg fraction.

As for humic acids from the A horizon, they all belonged to the P or B type and contained a Pg fraction. In addition, it was concluded that the humification process in the mineral layer Was clearly different from that in the organic layer.     

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.     

红松人工林腐殖质组成及其结合形态研究

 运用野外调查与实验分析相结合的方法,对不同生长发育阶段红松人工林（林龄25、45、58、68 a）和红松混交林（林龄60a）根际与非根际土壤有机质含碳量、腐殖质组成与结合形态进行了研究。结果表明:不同年龄阶段红松人工纯林、红松混交林土壤有机质含碳量、腐殖质各组分含碳量随土层深度的加深而降低,并且根际土壤高于非根际土壤。就土壤腐殖质组成而言,除林龄58a红松人工林根际土壤和45a红松人工林非根际土壤外,其他林型土壤胡敏酸含碳量均高于富里酸含碳量;胡敏酸与富里酸比值（HA/FA）在1.00～2.45之间;土壤重组腐殖质、松结态腐殖质、稳结态腐殖质含碳量大小顺序为林龄58>68>25>45a;红松混交林除紧结态腐殖质外,其他腐殖质各组分含碳量均高于红松人工林。     

Systems of solutions,minerals, and humic substances in soils

The equilibrium composition of solutions, minerals, and humic substances of the humus-clay plasma from the humus horizon of a leached chernozem was calculated using the method of computerized physicochemical simulation based on Gibbs’ principle of minimum free energy in the equilibrium state of the system. It was shown that the plasma from the humus horizons of chernozems and soddy-deeply podzolic soil mainly consists of oxides, hydroxides, humic substances, kaolinite, and 2: 1 illite-smectite minerals. The stoichiometry of the humic substances corresponds to calcium-saturated humus acids with appreciable contents of iron and aluminum. The crystallochemical composition of the 2: 1 layered minerals classifies them among ferruginated mixed-layered illite-montmorillonites. Simulation at an increased concentration of carbon dioxide indicated the degradation of the humus-clay plasma in a leached chernozem under extensive soil use, which can be restored by application of potassium at rates 1-to ?1.5-fold its removal.     

Distribution of Zinc,Manganese, Copper,Cobalt, and Nickel in Andosols Profiles

The distribution of zinc, manganese, copper, cobalt, and nickel in Andosols was investigated. Sixty nine soil samples were collected from different horizons of an Andosols profile in Miyakonojo Basin in south Kyushu, Japan, The total contents of heavy metals were determined by digestion and four extraction solutions, 1 M NH₄Ac (ammonium acetate) pH 4.5, 0.1 M HCl, 0.01 M EDTA (ethylenediaminetetraacetic acid) pH 6.5, and 0.005 M DTPA (diethylenetri-aminepentaacetic acid) pH 7.3 were used to determine the contents of available Zn, Mn, Cu, Co, and Ni in Andosols in relation to the organic carbon content. The results of the extraction analysis showed that by the use of 0.1 M H Cl high value of extracted heavy metals in the upper layers of the humus horizons were obtained while EDTA extraction yielded a large amount of the above mentioned metals in the high humus horizons. The extractable heavy metals contents were high and these metals closely related to the organic carbon content mostly in the humus horizons in the profile. Where, biocycling process may play an important role in the concentration of heavy metals. Based on the study, it was found that the total content of Zn increased towards the C horizons or pumice layers in the soil profile. Such a trend was also found in the case of the Mn content. While the Cu content in the humus horizons was much higher in the upper part of each humus horizon. According to this study the distribution of heavy metals, Cu (organic matter complexes) in the Andosols profile was more stable than that of Zn (organic matter complexes) in soils. It was shown that Zn in the surface humus horizon was enriched but that some amount was leached under buried conditions. The same phenomenon was also observed in the distribution of Mn in the profile. The movement of Co and Ni in the soil profile was limited, as evidenced by the sharp reduction in the concentrations of these two metals in buried soils.

Hence, it is concluded that the distribution of Zn, Mn, Cu, Co, and Ni was considerably higher in the humus horizons of the Andosols profiles.     

Mycological complexes in Holocene and Late Pleistocene paleohorizons and in fragments of paleosols

Fragments of buried Late Pleistocene (30000-year-old) and Early Holocene (10000-year-old) paleosols contained viable complexes of microscopic fungi. The mycobiota of these paleosols represents a pool of fungal spores that is lower in number and species diversity as compared to that in the recent humus horizons and higher than that in the inclosing layers. The central part of the paleosol profiles is greatly enriched in microscopic fungi. In the intact humus horizons of the Late Holocene (1000–1200 years) paleosols, actively functioning fungal complexes are present. These horizons are characterized by their higher level of CO₂ emission. The buried horizons, as compared to the recent mineral ones, contain a greater fungal biomass (by several times) and have a higher species diversity of microscopic fungi (including fungi that are not isolated from the recent horizons). Nonsporulating forms are also present there as sterile mycelium. The seasonal dynamics of the species composition and biomass of the fungal complexes were more prominent and differed from those inherent to the surface soil horizons. In the buried humus horizons, the dynamics of the fungal biomass were mainly due to the changes in the content of spores. The data on the composition of the fungal complexes in the buried soils confirm (due to the presence of stenotopic species) the results of paleobotanic analyses of the past phytocenoses or do not contradict them.     

Characteristics of organic matter in soil surface horizons derived from calcareous and metamorphic rocks and different vegetation types from the Mediterranean high-mountains in SE Spain

A study was carried out on some basic characteristics of the organic matter in the surface horizons of soils from the two different geological (calcareous and acid metamorphic rocks) and ecological systems under a Mediterranean climate in Southeast Spain. The results show some noticeable differences in soil organic matter composition. This is likely due to typical Mediterranean climate and well adapted vegetation. There is a tendency towards a greater stability for the soil humus formed under slightly alkaline soil in comparison to the slightly acidic environment. The samples taken from the latter environment have a higher content in free organic matter, a lower content in total extractable humin and a greater relative proportion of aliphatic chains and lignin in the humic acids. The results also suggest some differences caused by the type of vegetation (forest and scrubland ecosystems) in the soil humus chemistry, with a more obvious negative effect under reforestations with species of Pinus in an acidic soil environment (a higher content in free organic matter, lesser presence of fungal-derived perylenequinonic pigments in the humic acids, and a higher content in little evolved forms of nitrogen and lignin in the humic acids). In general the organic matter under scrubland and Quercus vegetation is more decomposed and the humus is more evolved than under Pinus vegetation.     

土壤有机矿质复合体研究 Ⅶ．土壤结合态腐殖质的形成特点及其结合特征

本文系统剖析了熊毅－傅积平改进区分的土壤结合态腐殖质的形成特点，胡，富组成及其结合特征。结果表明：（１）用０．１ｍｏｌ／ＬＮａＯＨ及０．１ｍｏｌ／ＬＮａＯＨ＋０．１ｍｏｌ／ＬＮａ４Ｐ２Ｏ７混合液连续浸提的松结态（Ｈ１）和稳结态（Ｈ２）腐殖质所占的比例随土壤ｐＨ升高分别呈减少和增加趋势。统计分析显示Ｈ１与游离态铁，铝呈极显著的正相关，与交换性钙呈极显著负相关，Ｈ２则与交换性钙呈极显著正相关，而与游离     

集约经营对山核桃林地土壤腐殖质组分碳含量的影响

[目的]研究并探讨土壤腐殖质各组分碳含量的变化规律,为山核桃林地土壤管理提供理论依据。[方法]采集并分析山核桃林经营历史为5,10,15,20a的土壤样品的土壤腐殖质各组分碳含量,并与天然混交林(0a)进行比较。[结果]与天然山核桃—阔叶混交林(0a)相比,随着经营历史的延长,林地土壤腐殖质各组分碳含量的变化主要发生在表层(0—10cm),胡敏酸碳、富里酸碳和胡敏素碳含量均下降。与0a相比,集约经营5a后胡敏酸碳、富里酸碳和胡敏素碳含量分别下降了42.8%,23.9%和21.2%,而集约经营20a后,分别下降了45.3%,39.0%,32.3%。集约经营20a后,亚表层(10—30cm)土壤胡敏素碳含量上升了94.2%。[结论]集约经营降低了山核桃林地土壤表层和亚表层的胡敏酸碳和富里酸碳含量,同时也降低了表层土壤胡敏素碳含量,而提高了亚表层土壤胡敏素碳含量。     

Chemical Characterization of Sewage Sludges in Chile and Their Potential Utilization as Amendment to Reclaim Soils for Forestation Purposes

Soils open for forestation in Chile are characterized by their very low organic carbon content; therefore, new forest plantations, needed to restore soil ecological equilibria, are scarcely developed. Stabilized sewage sludge contain organic compounds which have been demonstrated can serve as good soil amendments. To evaluate their actual uses in Chile it is necessary to characterize the carbon (C)-distribution pattern of such sludges in order to foresee their potential contribution for soil reclamation and plant growth, acting both as a source of stable C-reservoir and as readily available C-source.

The molecular weight (m.w.) distribution and carbon balance in Chilean sewage sludges are quite similar to soil humus and some woody by-products, as sawdust and bark dust. Total C varies from 30 to 35%, N from 5 to 9%, and P from 10,000 to 12,000 ppm. No significant content was found for heavy metals.

The C-balance indicates that around 70% of total-C is under stabilized forms as humine and humic macromolecule structures. The sewage sludge can be considered as good amendments for forest soils, especially in areas heavily eroded and depleted of natural humus. Their soluble-C fractions (13% of total-C) will serve as good energy starter source to strengthen indigenous soil microbial ecology, while their high m.w. fractions (humic acid-like and humine-like macromolecules) will serve both as good humus reservoir and as microelement frame in soils treated with such sewage sludges.     

不同培肥方式黑土腐殖质形态特征研究

针对吉林省黑土区存在的土壤有机质下降、耕地质量退化等问题,利用公主岭国家黑土肥力与肥料效益监测基地连续20年的长期定位试验,采用核磁共振波谱分析法(NMR)、红外光谱分析法(IR)等现代分析方法,研究了不同培肥途径耕层土壤腐殖质的组成、形态结构及动态变化趋势。结果表明:不同培肥途径对耕层土壤腐殖质特征影响明显。施用玉米秸秆处理(S+NPK)和施用有机肥+轮作处理(M+NPK+R)均显著增加了土壤胡敏酸中脂肪族结构成分,单施有机肥处理(M+NPK)显著增加了土壤胡敏酸中羟基含量,S+NPK处理游离羧基含量显著增多。S+NPK、M+NPK及M+NPK+R处理,土壤富啡酸的甲基、亚甲基和次甲基结构成分显著增多,游离羧基含量也显著增多。单施化肥处理,浸提的富啡酸中无机碳酸盐和硅酸盐成分明显增多,化肥长期施用导致土壤中游离富啡酸数量显著减少,土壤的耗竭式利用,导致土壤中铁、铜结合态或络合态的富啡酸增加。不同培肥方式对黑土胡敏酸和富啡酸的元素组成影响有较大的差异,但均可引发胡敏酸C含量降低,N含量增加,富啡酸C、N、H含量增加,O含量降低,可通过不同的培肥方式对土壤腐殖质的元素组成进行调节。     

Radiocarbon ages of humic substances in chernozems

Data on radiocarbon ages of different fractions of humus (humic acids, fulvic acids, and humin) in the profiles of chernozems are analyzed. A chronoecological grouping of humus in modern and buried (fossil) soils is suggested. An increase in the radiocarbon age of humic substances down the soil profile has a stepwise character. It is shown that the ¹⁴C content in chernozems decreases down the soil profile more somewhat slower than the ¹²C content. The dependence of a decrease in the humus content of buried soils on the age of burying is traced for a time span of 800 ka.     

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.