Origin and properties of humus in the subsoil of irrigated rice paddies

A pot experiment was conducted to estimate the amount of dissolved organic carbon (DOC) leached from the submerged plow layer of rice paddies during the cultivation period and its accumulation in the subsoil. Organic matter in the leachate was fractionated using insoluble polyvinylpyrrolidone (PVP) which can adsorb aromatic components having hydroxyl and/or carboxyl groups. Total amount of DOC leached throughout the growth period of rice plant corresponded to ca. 0.5% of total-C in the plow layer soil sample (total C, 17.8 g kg^-1) irrespective of the presence of rice plant, and the PVP-adsorbed fraction accounted for 34–43% of it. The amount of DOC in the leachate decreased by more than 50%, and that of the PVP-adsorbed and non-adsorbed fractions decreased by 79–82 and 45–47% by passing through the subsoil packed in the glass columns, respectively. The decreases were considered to be due to the adsorption to the subsoil, since a corresponding increase was observed in the total carbon content in the subsoil. Successive extraction of organic matter from the subsoil before and after the rice growth period with water, 0.25 M NaNSON and 0.1 m Na₄P₂O₇ (pH 7.0) solutions showed that the amount of organic carbon adsorbed on PVP mainly increased in the Na₄P₂O₇ (pH 7.0)-extractable fractions during the rice growth period, while the amount of organic carbon non-adsorbed on PVP increased in all the fractions extracted. These results suggested that the PVP-adsorbed fractions in the leachate were adsorbed to the subsoil mainly by coordinate bonding while the PVP-non-adsorbed fractions were adsorbed by physical adsorption, weak hydrogen bonding, ion bonding, and coordinate bonding.     

Effect of the natural reforestation of an arable land on the organic matter composition in soddy-podzolic soils

The dynamics of the organic matter composition in soddy-podzolic soils during the natural reforestation of an arable land in the southern taiga zone have been discussed. It has been shown that the contents of the total and labile carbon in the old plow horizon increase with the age of the fallow in the chronosequence of soils established in the Parfen’evo district of Kostroma oblast. The parameters characterizing the labile soil organic matter include the contents of the carbon extractable by mild chemical extractants (distilled water, 0.1 M K₂SO₄ solution, 0.1 M neutral Na₄P₂O₇ solution), the microbial biomass, and the light fraction. The granulo-densimetric fractionation has shown that the contents of carbon in the light and organomineral fractions of the soil vary in the course of the postagrogenic succession. The content of the clay-fraction carbon increases and its portion in the total carbon of the soil decreases at the transition from the plowland to the forest. The reforestation of agrosoddy-podzolic soils enhances the physical protection of the soil organic matter due to the increase in the portion of microaggregate carbon.     

SIZE FRACTIONATION, DISSOLUTION ANALYSIS, AND INFRA-RED SPECTROSCOPY OF HUMUS COMPLEXES IN ANDO SOILS

Eight samples of Ando soil A₁ and buried A₁ horizons of different ages were fractionated into clay-, silt-, and sand-size separates, and the yields and carbon contents of these separates were determined. The clay-size separates were subjected to two series of successive extractions, 1) 0.1 M Na₄ P₂ O₇/2% Na₂ CO₃/0.5 M NaOH and 2) dithionite-citrate/2% Na₂ CO₃/0.5 M NaOH; and to difference infra-red spectroscopy for identification of the extracted constituents. The result indicated that humus evolves from forms with a very low complexing ability for Al and Fe into forms that complex Al and Fe in the A₁ horizon, and that humus further interacts with allophane-like constituents, allophane and imogolite in the buried A₁ horizon. These reactions between humus and inorganic constituents result in formation of silt- and sand-size aggregates which are stable to sonic wave treatment, but are broken down into finer particles upon boiling with H₂ O₂.     

A comparison of the effectiveness of various extractants for determining humus quality in a calcareous soil

Abstract

Humic substances from an Argentinian chesnut (Mollisol) soil were extracted with Na‐Dowex A‐1 resin, 0.1 N NaOH and 0.1 M Na₄P₂O₇ without decalcification and with 0.1 N NaOH after decalcification. Humic to fulvic (Ch/Cf) acid and E₄/E₆ ratios of the extracts were determined and compared.

A simpler and more rapid procedure than the classical ones for extracting and characterizing soil humus is proposed. The procedure is based on the use of a chelating resin as extractant and on the direct determination of analytical properties of humus in aliquots of the extract.     

CHANGES IN MOLECULAR WEIGHT DISTRIBUTION OF SOIL ORGANIC MATTER DURING SOIL DEVELOPMENT

Ten different topsoils representing members of three soil chronosequences were pre-treated with 0.1 M HC1 and extracted with neutral 0.1 M Na₄P₂O₇ followed by 0.5 M NaOH. Extracts were purified and fractionated into five different nominal molecular weight fractions using gel filtration. With increasing soil development, the proportion of large molecules (>200 000) in the organic matter decreased with an increase in the proportion of intermediate size molecules (200 000 – 10 000). This effect was more evident in the mild Na₄P₂O₇ extracts than in the subsequent NaOH extracts, and in soils of the Manawatu chronosequence than in those of the other two chronosequences and are attributed to changes in the nature and humification of soil organic matter during soil development.     

Humus composition and humification degree of humic acids of alpine meadow soils in the northeastern part of the Qinghai–Tibet Plateau

The characteristics of humus composition are important for understanding the mechanism of carbon storage in the Qinghai–Tibet Plateau. The aim of this study was to characterize the quality of soil organic matter (SOM) in this region. Soil samples from four soil profiles in fenced study sites in the alpine grassland were collected at altitudes of 4200, 4000, 3800, and 3400 m, along the southwest facing slope in the Qilian Mountains. The humus composition and humification degree of the humic acid (HA) were determined by two methods: (1) extraction with 0.5% sodium hydroxide (NaOH) followed by 0.1 M sodium pyrophosphate (Na₄P₂O₇) (OH-PP method); and (2) treating once with 0.1 M hydrochloric acid (HCl) followed by extracting with 0.5% NaOH (Cl-OH method). Physico-chemical analysis revealed higher exchangeable cation content and higher base saturation ratios could be related to slightly acidic to neutral soils, which could be regarded as calcium (Ca)-rich soils. The amounts of combined-form HAs obtained by HCl pretreatment (HA_Cl – HA_OH; ?HA_Cl) were remarkably higher than those extracted with Na₄P₂O₇ (HA_PP), indicating that the combined form of HAs is mainly Ca. In addition, the proportion of HA_PP in the total HAs extracted with both NaOH and Na₄P₂O₇ (HA_OH + HA_PP) obtained in the OH-PP method increased with soil depth and decreasing elevation, indicating that HAs associated with aluminum (Al) and iron (Fe) were distinguished in the subsoils of lower elevation. Therefore, the formation of the organo-mineral complex may contribute to stabilizing SOM in the Qinghai–Tibet Plateau. Moreover, Type A-HA with the highest degree of humification was obtained from the deeper horizons with the Cl-OH method and almost all horizons by extraction with Na₄P₂O₇ in the OH-PP method. Further studies using various spectroscopic analyses are necessary to elucidate the chemical properties of SOM in this region.     

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     

Chemical characteristics and potential source of fulvic acids leached from the plow layer of paddy soil

To understand better the chemical characteristics and source of dissolved organic matter (DOM) leached from the plow layer of rice paddies, a lysimeter study was conducted, which simulated submerged paddy topsoil during rice growth. The fulvic acid (FA) fraction in the percolation water from the lysimeter was collected by adsorption onto insoluble polyvinylpyrrolidone (PVP), and the temporal variations in its elemental composition, molecular size distribution, IR spectra, ¹³C CPMAS NMR spectra, and δ¹³C values were investigated. The proportion of the FA fraction to bulk DOM varied greatly, but the chemical characteristics of the FA fraction did not change appreciably during the experimental period. Thus, it is considered that the changes in the DOM composition in percolation water were mainly due to the differing contributions of the FA fraction. Further, to investigate the source of the FA fraction in the leachate, the chemical characteristics of the FA fraction in the leachate were compared with those extracted from the plow layer soil. A sequential extraction of the FA fraction was conducted using a sequence of water, 0.25 M Na₂SO₄, 0.1 M Na₄P₂O₇ (pH 7.0), 0.1 M Na₄P₂O₇ (pH 10.5), and NaBH₄+0.1 M Na₄P₂O₇ (pH 10.5). It was found that the water- and 0.25 M Na₂SO₄-extractable fractions, which were most mobile, were not the only source of the FA fraction in the leachate. The small molecular size sub-fraction of the NaBH₄+0.1 M Na₄P₂O₇ (pH 10.5)-extractable FAs, most of which are probably bound mainly to iron oxides, are considered to be another source of the FA fraction leached from the plow layer of paddy fields.     

A rapid method for the determination of fixed ammonium in soil

Abstract

Five different procedures for the oxidation of organic carbon were compared in order to determine the most suitable method for use as a pretreatment before the determination of fixed NH₄‐N in soils. Three of the procedures involved a method based on the use of a solution containing 0.1M Na₄P₂O₇, 0.1M NaCl, and 6% H₂O₂, applied for three different periods of time, 10 days, 20 days, and whatever number of days are required until frothing no longer occurs. This third period of time is designated as NF (no frothing). The remaining two procedures involved a method based on the use of a 3M NaOCl solution applied for two different periods of time, 3‐cycles and 5‐cycles.

Two of the procedures, the NF treatment with H₂O₂+NaCl+Na₄P₂O₇ and the 5‐cycle treatment with NaOCl, were found to give the must efficient removal of organic C. The amount of residual N in the soil after the NF treatment was highly correlated with the amount of residual N in the soil after the 5‐cycle treatment. It is concluded that the 5‐cycle treatment is as effective as the NF treatment for the oxidation of organic C in the soil before carrying out the determination of fixed NH₄‐N. The 5‐cycle treatment has the advantage of being a faster and simpler analytical procedure than the NF treatment.     

Effects of heavy metal accumulation in apple orchard soils on microbial biomass and microbial activities

Abstract

The effects of heavy metals (Cu, Pb, and As) accumulated in apple orchard surface soils on the microbial biomass, dehydrogenase activity, and soil respiration were investigated. The largest concentrations of total Cu, Pb, and As found in the soils used were 1,010, 926, and 166 mg kg^?1 soil, respectively. The amounts of microbial biomass C and N, expressed on a soil organic C and soil total N basis, respectively, were each negatively correlated with the amounts of total, 0.1 M HCI-extractable, and 0.1 M CaCl₂-extractable Cu as logarithmic functions, the correlation coefficient being lowest for the 0.1 M CaCl₂extractable Cu. Nevertheless, they were not correlated with the soil pH which was controlling the solubility of Cu in 0.1 M CaCl₂. The dehydrogenase activity expressed per unit of soil organic C was also negatively correlated with the amounts of total, 0.1 M HCI-extractable Cu, and 0.1 M CaCl₂-extractable Cu as logarithmic functions. However, the correlation coefficient was highest for the 0.1 M CaCl₂-extractable Cu. Although the soil respiration per unit of soil total organic C did not show any significant correlations with the total concentrations of heavy metals, it showed negative significant correlations with the amount of 0.1 M HCI-extractable Cu, and to a greater extent, with the amount of 0.1 M CaCl₂-extractable Cu. Both the dehydrogenase activity and respiration per unit of soil total organic C increased significantly with increasing soil pH. These results suggested that in apple orchard soils with heavy metal accumulation the microbial biomass was adversely affected by the slightly soluble Cu, whereas the microbial activities by the readily soluble Cu whose amount depended on the soil pH. The respiration per unit of microbial biomass C showed a positive significant correlation with the logarithmic concentration of total Cu. Furthermore, the contribution of fungi to substrate-induced respiration increased with increasing total Cu content in the soils.     

Electrofocusing: A new method for characterization of soil humic matter

Electrofocusing in polyacrylamide gel was carried out on humic substances extracted by 0.1 n NaOH, 0.1m Na₄P₂O₇, and by the method of Burns, El Sayed and McLaren (1972) from the upper and lower organic horizons of an alpine podsol. The electrophoretic patterns were characteristic of both humus origin and extractions procedure. The best resolution of the isoelectric bands for the humus were obtained by the Burns-McLaren procedure. The ionic component does not have much influence on the distribution of humus constituents within the electrophoretic pattern, but the presence of phosphate appears to be essential to obtain good separations.     

Fractionation of selenium and detection of selenomethionine in a soil extract

Abstract

A procedure is described to fractionate, identify and quantify organic selenium compounds at μg/kg levels in soil extracts. The fractionation is based first on the different solubility of humates and fulvates at low pH, followed by adsorption chromatography with XAD‐8 resin. The latter uses a pH gradient to elute the acidic and basic hydrophobic fulvates as well as hydrophilic fulvates. The neutral hydrophobic fulvates were retained on the column and determined by difference from the total extractable selenium. A 0.1MNaOH/0.1 M Na₄P₂O₇solution extracted 33% of the total soil selenium. In the soil studied, organic selenium was 20% of total extractable selenium. One of the hydrophilic fulvates has been identified as selenomethionine by gas chromatography‐mass spectrometry. The quantity of organic selenium and the presence of selenomethionine suggests that organoselenium compounds could be an important source of plant available selenium     

MOLECULAR SIZES AND FUNCTIONAL GROUPS OF HUMIC SUBSTANCES EXTRACTED BY 0.1M PYROPHOSPHATE FROM SOIL AGGREGATES OF DIFFERENT STABILITY1

Aggregates from non-cultivated soil and from cultivated soil enriched with mineral fertilizers or farmyard manure were separated into fractions of different diameter and stability. The humic substances extracted from each type of aggregate were subjected to gel-filtration on Sephadex. The more stable aggregates had a higher content of Na₄P₂O₇-extractable humus and free iron hydroxides, and a predominance of humic substances of apparent molecular weight >100 000, whereas the less stable aggregates were richer in compounds of low molecular weight. Structure stability was lower in the cultivated soil than in the non-cultivated, and in the soil with mineral fertilizers in comparison to that with farmyard manure. Humus of m.w. >100 000 had a COOH content twice as great and a phenolic OH content five times greater per unit of molecular weight than humus with m.w. <100 000. The former is the more suitable stabilizer of soil aggregates.     

东祁连山不同高寒草地型牧草返青期土壤碳分布特征

以东祁连山高寒草地为样点,对土壤有机质、K2SO4浸提碳和微生物量碳(氯仿熏蒸浸提法)等进行了研究.结果表明:该区土壤有机质介于82.3～207.2 g·kg-1,植被类型影响土壤有机质含量.土壤K2SO4浸提碳介于23.61～138.81 mg·kg-1,分别占土壤有机质和土壤微生物量碳的0.03%～0.06%和9.97%～18.46%;灌丛草地中,高山柳草地显著低于杜鹃草地(P<0.05);草本草地中,珠芽蓼草地、沼泽草地和嵩草草地显著高于禾草草地(P<0.05).土壤微生物量碳介于156.19～1 182.84mg·kg-1,上层显著高于下层(P<0.05),除2005年沼泽草地外草本草地与灌丛草地间差异显著(P<0.05);微生物量碳对土壤有机质的贡献率介于0.19%～0.48%,禾草草地最低(0.19%),金露梅灌丛草地最高(0.48%),除珠芽蓼草地和沼泽草地外均为上层高于下层;且除禾草草地和嵩草草地外微生物量碳与土壤有机质、全氮和速效磷间呈显著(P<0.05)或极显著正相关(P<0.01),与土壤K2SO4浸提碳在灌丛草地呈显著正相关(P<0.05),在草本草地呈极显著正相关(P<0.01),与微生物量氮、磷间呈极显著正相关(P<0.01).该结果表明微生物量碳及其对土壤有机质的贡献率在草地型闻和土层间差异明显,且与土壤有机质、K2SO4浸提碳、全氮和速效磷关系密切.     

Effect of liming on organically complexed aluminum of nonallophanic Andosols from northeastern Japan

Aluminum–humus complexes are believed to be highly stable under natural conditions in nonallophanic Andosols. However, it has been shown that the aluminum complexed with humus is easily released by acidic buffer solutions and possibly controls the aluminum solubility of these soils. Thus, it is highly probable that Al–humus complexes are easily influenced by rather simple chemical treatments. We examined the effects of liming (CaCO₃ treatment) on Al–humus complexes of A and B horizons from Andosols. It was observed that liming reduced the Al release rates from soil samples with pH 3.5 acetate buffer solution and the amounts of the KCl-extractable Al, suggesting the formation of precipitation from easily exchangeable Al. A much larger decrease with liming was also obtained for 0.1 M sodium pyrophosphate-extractable Al (decrease rates of 7–52%) and 0.5 M CuCl₂-extractable Al (decrease rates of 9–43%). These results strongly indicate that liming reduces significant amounts of organically complexed Al as well as the exchangeable Al. The increase in the cation exchange capacity of soils at pH 7 after liming further suggested that the carboxyl group of humus complexed with Al was partly liberated from the Al complexation and became to develop negative charges.     

Factors Affecting Microbial Biomass and Dehydrogenasc Activity in Apple Orchard Soils with Heavy Metal Accumulation

The size of the microbial biomass and dehydrogenase activity were measured in air-dried and rewetted apple orchard surface soils with accumulation of Cu, Pb, and As due to the application of Bordeaux mixtures and lead arsenate. The largest amounts of total Cu, Pb, and As found in the soils used were 1,108, 1,271, and 209 mg kg^-1 soil, respectively. The amounts of 0.1 M HCl-extractable heavy metals were strongly correlated with the total amounts, while those of 0.1 M CaCl₂-extractable heavy metals, except for As, increased significantly with decreasing soil pH. The amounts of microbial biomass C and N, expressed on a soil organic C and total N basis, respectively, were each negatively correlated with the amounts of total and 0.1 M HCl-extractable Cu. On the other hand, the dehydrogenase activity was not affected by the amounts of total and 0.1 M HCl-extractable heavy metals, and was negatively correlated with the amount of 0.1 M CaCl₂-extractable Cu and positively with the soil pH. Higher significant correlations were observed when the dehydrogenase activity was calculated per unit of soil organic C. Thus the microbial biomass was adversely affected by the slightly soluble fractions of Cu accumulated in apple orchard soils, whereas the dehydrogenase activity was affected by the water-soluble and exchangeable Cu of which amount depended on the soil pH. It is suggested that the microbial biomass and dehydrogenase activity expressed on a soil organic matter basis could become useful indicators for assessing the effects of heavy metals on the size and activity of the microbial biomass in soils differing in organic matter contents.     

FTIR‐spectroscopic characterization of humic acids and humin fractions obtained by advanced NaOH,Na4P2O7, and Na2CO3 extraction procedures

Aim of our study was the development of the methodological basis for the characterization of humic fractions of a long‐term field experiment. Humic acids (HAs) were extracted from three layers of a nontilled soil using three different extractants (1 M NaOH, 0.1 M Na₄P₂O₇, 1 M Na₂CO₃), and the humin fraction was enriched. NaOH as extractant for FTIR analysis of humic substances yields higher resolved IR spectra, especially in the important regions of stretching vibrations including aromatic and aliphatic groups and in the fingerprint area including amides, aliphats, and aromats than the other extractants. The NaOH extraction has lower extraction yields as compared to Na₄P₂O₇ and Na₂CO₃ and represents a different part of the soil organic matter (SOM). This is reflected by lower C : N ratios and higher E₄ : E₆ and fulvic acid–to–humic acid ratios as compared to the other extractants. The FTIR band areas of HA fraction obtained by NaOH showed an increase of the aromatic and carbonyl groups and a decrease of amide groups with increasing soil depth. Aliphatic groups showed contradicting results: The bands of the stretching vibrations increased, and the band of the bending vibrations decreased. We assume that band interactions in the bending vibrations were responsible for that phenomenon under the assumption of an increase of aliphatic groups with increasing soil depth. The IR bands of the enriched humin fraction showed a decreasing trend in case of both aliphatic bands deriving from stretching vibrations and an increase of aromatic characteristics with depth. Our study led to the conclusion that HA fractions obtained by 1 M NaOH represent a small and dynamic fraction indicated by the measured yields in combination with values of N_t, C : N, E₄ : E₆ ratios, and ratios of fulvic acids (FA) to HA. The humin fraction has a high contribution to the total organic C and represents a more stabilized fraction of SOM which still shows changes in its aromatic and aliphatic characteristics with soil depth.     

A Hybrid Approach for PAHs and Metals Removal from Field-Contaminated Sediment Using Activated Persulfate Oxidation Coupled with Chemical-Enhanced Washing

The aim of this study was to investigate the removal of both polycyclic aromatic hydrocarbons (PAHs) and heavy metals from field-contaminated sediments by activated persulfate oxidation. Various chemicals, including hydroxypropyl-??-cyclodextrin (HPCD), S,S-ethylenediaminedisuccinic acid (EDDS), tetrasodium pyrophosphate (Na₄P₂O₇), and hydrochloric acid (HCl), were applied individually before or after activated persulfate oxidation to enhance the co-removal of both types of pollutants. It was found that the organic removal efficiency was not significantly enhanced by increasing the concentration of HPCD from 2.5 to 5.0?mM. The removal efficiency of heavy metals was not improved even at an excess amount of EDDS after activated persulfate oxidation. However, the addition of EDDS acted as the Fe²⁺ carrier for activated persulfate oxidation. In addition, no significant enhancement of heavy metal removal was observed by increasing the concentrations of Na₄P₂O₇ and HCl from 0.01 to 0.1?M after activated persulfate oxidation. However, comparing 0.1?M HCl with 0.1?M Na₄P₂O₇, HCl was shown to be more effective in promoting the removal of organic pollutants. With further adjustments on the experimental conditions, the highest removal amount of metals and PAHs was achieved by adding 2?M of HCl with 3?days mixing, followed by Fe²⁺-activated persulfate oxidation (PS/Fe²⁺ molar ratio at 4:1) for further 6?h mixing. The removal efficiency of low and high molecular weight PAHs was about 70 and 20?%, respectively, while the removal efficiency of metals was 70, 100, 40, 65, 65, 80, and 100?% for Cr, Cu, Hg, Mn, Ni, Pb, and Zn, respectively.     

Soil organic matter alteration under biochar amendment: study in the incubation experiment on the Podzol soils of the Leningrad region (Russia)

Purpose

Biochar is one of the most widely used ameliorants for soil amendment, which is known as factor which rises crop yields and levels of soil biological activity. Nowadays, it is under investigated how biochar application affects the dynamics of the humic components and whole soil organic matter (SOM) and the processes of its alteration. This investigation is aimed to evaluate the influence of biochar on the content, composition, and transformation of humic acids (HAs) as the main component of the SOM.

Materials and methods

The incubation experiment was carried out on three Podzol Antric soils, with varying amounts of initial total organic carbon. The incubation time was 90 days, using biochar gravimetric doses of 0.1 and 1.0%. The biochar was produced by fast pyrolysis of birch and aspen wood at 550 °С. Humus composition was analyzed for the organic matter fractions extracted with 0.1 M NaOH (containing HAs 1 + fulvic acids (FAs) 1) and 0.1 M Na₄P₂O₇ (containing HAs 1 + FAs 1 + HAs 2 + FAs 2). Isolated HAs were characterized for their elemental composition (C, N, H, and S) and molecular composition with the use of solid-state 13C nuclear magnetic resonance (13C-NMR) techniques.

Results and discussion

We found that 0.1% of biochar amendment does not influence SOM mineralization, but 1.0% of biochar increases the mineralization by 15–18%. This process is accompanied by changes in the composition and properties of the HS. The increased proportion of HA aromatic fragments in biochar indicates an increasing of their stability. However, in soils with high humus content and a significant amount of insoluble matter, the processes of mineralization and the growth of HAs are taking place simultaneously. The replenishment of HAs could be the outcome of both the intensification of the transformation processes (mineralization and humification) of the more sustainable insoluble matter compounds and the humification of the biochar itself.

Conclusions

The influence of biochar on humification in Podzol Antric soils was revealed on the basis of incubation experiment. Both negative and positive changes under biochar in HS system were demonstrated. The active decrease of humus total contents and also the labile HS ought to qualify as negative changes. The increase of HA chemical maturity that leads to the stability of humus in whole as well as the intensive new HA formation thought to qualify as positive changes.

     

Comparison of carbon skeletal structures in black humic acids from different soil origins

Andosols are characterized by an abundance of black humic acids (HAs) belonging to Type A with a high content of aromatic carbon (C) in particular condensed aromatic C. Black HAs are also observed in other soils, such as Chernozems and the subsoil of paddy field, and extracted after washing with an acid or using chelating agent such as sodium pyrophosphate (Na₄P₂O₇). However, contribution of condensed aromatic structures to those soil HAs are unknown. To obtain the information about C skeletal structures of black HAs in soils other than Andosols, HAs were obtained from 2 Chinese Chernozem samples, 2 subsoil samples from Japanese paddy fields (Fulvisols), and a Rendzina-like soil (Cambisols) as well as an Andosol sample (reference) by successive extraction with 0.1 M NaOH (HAs₁) and 0.1 M Na₄P₂O₇ (HAs₂), and ¹³C nuclear magnetic resonance and X-ray diffraction 11-band profile analyses were applied. In the black HAs₂ from the non-Andosol samples, the proportion of C present as aromatic C, size of C layer planes, and relative C layer plane content ranged from 52 to 59%, 0.48 to 1.92 nm (mean size, 0.76–0.91 nm), and 58 to 100 AU (arbitrary unit) mg^?1, respectively, with a positive correlation between total C layer plane content and the degree of humification. Those ranges were similar to the distribution ranges of Andosols HAs₁ reported by our previous study.