Changes in the Content,Composition, and Properties of Humic Substances in Particle-Size Fractions of Soddy-Podzolic Soils under the Impact of Long-Term Drainage

Specific features of the transformation of humic substances in particle-size fractions of drained soddy-podzolic soils were studied on a field (12 ha) of the Experimental and Educational Center of Lomonosov Moscow State University in Moscow oblast. The field had a clearly pronounced microtopography. Surface-gleyed soddy-podzolic soils (Albic Stagnic Glossic Retisols (Loamic, Aric, Ochric)) of microdepressions with excessive surface moistening and nongleyed soddy-podzolic soils (Albic Glossic Retisols (Loamic, Aric, Ochric)) of elevated positions were examined. These soils were studied before the field drainage and during 25 years after drainage works in the periods differing in conditions of humification and with due account for not only drainage works but also other factors, such as topography and agrotechnology and their joint action. The specificity of transformation of humic substances in the soils and their particle-size fractions was analyzed in the basis of data on the organic carbon content, group and fractional composition of humus, the intensity of individual stages of humification (the neoformation of humic acids and the formation of humates), and the optical density of the fractions of humic acids. The results of the study of these properties in the fine soil fractions (<50 μm) made it possible to assess the response of the clay (<1 μm) and silt (1–5, 5–10, 10–50 μm) fractions to changes in the ecological situation and the role of separate particle-size fractions in the degradation of humus under adverse impacts. Overall, a clear tendency toward worsening of the humus quality was observed in both soils during the 25-year-long period, which is related to the long-term (20 years) agricultural use of the reclaimed field without application of agrochemicals. The features of humus degradation were mainly manifested in the finest (<10 μm) fractions with a general decrease in the humus content, slowing down of the formation of humic acids and humates, and considerable loss of humic acids, including their agronomically valuable fractions HA1 and HA2. The degradation of humus quality in the clay fraction was largely due to the impact of the reclamation (drainage) factor; the degradation of humus quality in the fine and medium silt fractions was mainly due to the negative changes in the agricultural background. Among negative consequences of the worsening humus quality, the lowering of soil fertility, ecological sustainability, and productivity of agrocenoses should be noted.     

The impact of different land uses in urban area on humus quality

Purpose

In urban areas, humus quantity and quality depend less on natural environmental factors than on anthropogenic ones. The aim of the study was to assess the impact of different land use types of urban soils on the properties of soil organic matter (SOM).

Materials and methods

Thirty-five sites involving four ways of soil use were examined: lawns, allotment gardens, fallows, and arable lands. The study was conducted in Pruszków Town in the Warsaw Agglomeration, Central Poland. Lawns and allotment gardens were located in the central part of the town, whereas fallows and arable lands were in the peripheral zones. Humus horizons, to a depth of 0–20 cm, were analyzed. Using Na-pyrophosphate extraction, we determined the soluble SOM compounds (PY), and the organic matter in the extraction residue, considered as humins (HM). In a separate extraction (with 0.05 M H₂SO₄), low molecular weight (LMW) humus compounds were determined. The quantity of humic acids (HA) precipitated during Na-pyrophosphate extraction was determined as well. A spectroscopic method (UV-Vis) was used to characterize HA properties. The absorption coefficients E4/E6 were calculated based on the results of absorbance measurements involving 465- and 665-nm wavelengths of UV-Vis light. Statistical analyses were performed to find similarities and differences between soils differently used in Pruszków.

Results and discussion

The dominant part of the humus in the studied soils were humins HMs. There were two times more HM in the central part of the town than that in the peripheral zones. The same observation was made for soluble humus compounds (PY). The amount of LMW fractions was similar in soils of all uses. The degree of humification was small and averaged about 30% for all soils. Fulvic acid (FA) concentrations predominated over HA concentrations in all soils. The least condensed HA occurred in the allotment gardens with an E4/E6 ratio of 5.7, whereas the most condensed HAs were present in soil on arable lands (E4/E6 ratio of 4.7).

Conclusions

The studies have shown that the type of land use affects humus properties. The main differences were found to be in the quantity of humus compounds. Soils from the central part of the town contained more stable (HM) and soluble (PY) compounds than soils in the outskirts of town. PY compounds were characterized by a simple structure. Fulvic acids (FA) dominated in all of the studied soils (low HA/FA ratio). A high E4/E6 ratio indicates low maturity of humic fractions with low molecular weight compounds.

     

Evolution of the soil humus status on the calcareous Neogene clay dumps of the Sokolov quarry complex in the Czech Republic

The development of the soil profile and the humus substance system was described for two chronosequences of soil restoration on the Neogene clay dumps. The chronosequences differed in the restoration type of vegetation: self-overgrowing or overgrowing intensified by planting tree seedlings (rehabilitation). It was found that the regeneration rates of the soil and humus profile were much higher in the case of the land rehabilitation than during the self-overgrowing of the dumps. The acceleration of the ecogenetic succession and the symbiotic nitrogen fixation in the soils of the plots with seedlings planted resulted in the accumulation of humus and nitrogen and increased the degree of organic matter humification. The enrichment of the organic matter in nitrogen and its increased input were the main reasons for the more intense humification under the rehabilitation conditions.     

有机物料对白土土壤胡敏酸结构特征的影响

【目的】研究有机物料施入对白土土壤的腐殖质含量组成和胡敏酸(HA)结构特征的影响,为明确不同腐殖质组分对土壤肥力的影响提供理论依据。【方法】供试土壤为江苏省溧阳市南渡镇"白土改良大田示范试验核心区"的南方中低产水稻土(白土)。试验设秸秆还田(ST)、施有机肥(OM)和对照(CK,不施有机物)3个处理,培肥3年。同时采集试验田周围相邻的江苏省耕地质量监测点(2007~2013年)的每年施化肥(LAF)和长期不施肥(NF)的两种处理土壤进行比对研究。分别测定土壤的基本理化性质及其腐殖质含量的组成,并提取土壤胡敏酸(HA)固体样品利用红外光谱和元素分析来进行结构表征。【结果】秸秆还田和施有机肥处理的有机碳、全氮含量明显高于对照;与对照相比,施有机物料土壤HA的E4/E6比值增加,且秸秆还田施有机肥对照。红外光谱显示,试验区域和耕地监测点的不同处理土壤HA均在1650 cm-1处(酰胺I带)和1550 cm-1处(1500~1580 cm-1酰胺II带伸缩振动)有特征吸收。施有机肥和秸秆还田处理土壤HA的2920/1720、2920/1650比值显著大于对照。在元素组成上,OM、ST处理的土壤腐殖质(HA)中C、H、N的含量比均高于CK,相对长期施化肥(LAF)和不施肥(NF)的土壤有明显提高,而氧元素的含量呈降低的趋势;OM和ST处理土壤HA的[H]/[C]和[O]/[C]原子数比均低于CK;与LAF和NF处理相比,试验区域各处理土壤腐殖质的[H]/[C]和[O]/[C]原子数比均有明显降低。【结论】有机物料施入土壤后可增加土壤有机碳含量,改善土壤理化性质,提高作物产量和品质,且施入土壤的有机物料可转化为新的腐殖质,降低土壤的腐殖化程度。土壤腐殖质(HA)的红外光谱分析说明,白土土壤HA具有明显的酰胺类化合物特征。有机物料施入后使得土壤脂族性增强,羧基量减少,芳香度降低;秸秆还田和施有机肥处理与对照相比,土壤HA的[H]/[C]和[O]/[C]比均有下降的趋势,且HA的氮素含量明显增加,这显示有机物料施入后白土土壤腐殖质发生"脱水"过程,同时也反映了白土土壤腐殖质形成的特征。     

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.     

Chemical and spectroscopic characteristics of humic acids in marshes from the Iberian Peninsula

Purpose

To characterise soil humic acids (HAs) extracted from Spanish marshes formed under different vegetation types (Spartina maritima (GSp), Juncus maritimus (GJc), Phragmites australis (GPh), and Scirpus maritimus (VSc)), soil depths (0–20, 20–40 and 40–60 cm), physiographic position (low and high marshes), wetland types (salt marshes and lagoons) and environmental conditions (Atlantic and Mediterranean coast).

Material and methods

Soil samples were collected in five Spanish marshes, three on the Galicia province and two on the Valencia province. Humic acids were extracted and their elemental composition, semiquinone-type free radical (SFR) content, FTIR and CPMAS ¹³C NMR spectra determined. Total carbon (TC), total nitrogen (TN), total sulphur (TS), CaCO₃ content, and field pH and Eh (mV) in the marsh soils sampled were also measured.

Results and discussion

The field pH and Eh values were typical of coastal areas submitted to periodic inundations and the highest TC, TN and TS contents were found in the soil of lagoon marshes as an effect of physiographic position and wetland type. The HAs, in general, were highly aliphatic and exhibited a low SFR content, which suggests a low humification degree of the SOM formed in the studied areas. This is a result of the anaerobic decomposition to which SOM is submitted and the high input of plant-derived organic matter (OM) by vegetation. However, among the studied sites low salt marsh and subsurface layer of the high salt marsh showed higher SFR content, simpler FTIR spectra, higher lignin degradation and lower O-alkyl C/alkyl C ratio than the lagoon marshes, thus suggesting the presence of a more humificated SOM in these sites.

Conclusions

From the different factors analysed, only physiographic position (low versus high salt marshes) and wetland type (marshes versus lagoons) caused variations in the HAs characteristics, because as the studied soils are under anaerobic conditions, they control the exportation of plant-derived OM and the allochthonous OM contribution in the studied areas.     

Effect of organic amendment on amount and chemical characteristics of humic acids in upland field soils

To assess the effect of continuous organic material (OM) application on soil humic acids, the amount and chemical characteristics of humic acids in various types of soils (n = 10) were compared between plots treated with farmyard manure (FYM) or rice straw compost (RSC) plus chemical fertilizer (CF) and plots treated with CF alone. The degree of humification (degree of darkening), molecular size distribution and ¹³C cross polarization/magic angle spinning nuclear magnetic resonance spectra of humic acids from CF‐treated soils showed wide variation among the soils. Humic acid content was generally larger in OM + CF soils than in corresponding CF soils, and the stable C isotopic ratio suggested partial replacement of indigenous humic acids with OM‐derived ones even where no apparent increase in humic acid content was observed. The rate of OM application and the indigenous humic acid content were related positively and negatively, respectively, to the apparent accumulation rate of humic acids among soils. The degree of humification of humic acids was generally smaller in OM + CF soils than in CF soils. Humic acids extracted from FYM and RSC exhibited chemical characteristics typical of humic acids having a smaller degree of humification, which suggested the contribution of OM‐derived humic acids to the differences between OM + CF and CF soil humic acids, such as larger average molecular sizes and smaller and larger proportions of aromatic C and O‐alkyl C, respectively, relative to total C in the OM + CF soil humic acids. Little change was observed in the chemical characteristics of humic acids when the degree of humification of indigenous humic acids was small. The effect of OM application on the chemical characteristics of humic acids was most conspicuous in soils containing humic acids having an intermediate degree of humification, possibly resulting from the combination of accelerated degradation of indigenous humic acids and the accumulation of OM‐derived humic acids.     

Special features of humus acids extraction from soils by sodium pyrophosphate solutions of different alkalinity

The regularities of extracting humus acids from soils of different types with solutions of sodium pyrophosphate at the equilibrium pH values of 5–13 were studied. The increase in the humus acids yield from the soils with the increasing alkalinity of the solution applied is directly related to the capability of acid functional groups (carboxyl and phenol hydroxyl) for dissociation at definite pH values. The regularities of the changes in the chemical nature and degree of humification of humus acids extracted from the soils related to the pH of the solution were revealed. A sodium pyrophosphate solution (pH 10) was suggested for extracting the humus acids most active in the given soil.     

淮南煤矿复垦区土壤腐殖质特征及其与重金属的关系

选择淮南典型煤矿复垦区不同土地利用方式下（菜地、玉米—小麦地、林地和荒地）的土壤作为研究对象,运用单因素方差分析和内梅罗综合污染指数调查了其腐殖质组成特征与重金属污染状况并探究两者间关系,为修复矿区复垦土壤提供依据。结果表明:土壤腐殖质含量、腐殖化程度和稳定性依菜地 > 玉米—小麦地 > 林地 > 荒地的次序从最佳向最差过渡。不同土地利用方式下土壤胡敏素（HM）的组成不同,HM各组分有机碳含量为HMr > HMi > HMc;且施用有机肥土壤较不施肥土壤中HM各组分的含量明显增加。复垦区土壤中Cu和Cd含量均高于土壤背景值,Zn含量低于土壤背景值,土壤处于轻度污染状态。施用有机肥提高复垦土壤肥力的同时,需控制有机肥中重金属含量,以降低土壤重金属污染风险。     

Paramagnetic Properties of Humic Substances in Taiga and Tundra Soils of the European Northeast of Russia

The study of paramagnetic activity of humic substances in taiga and tundra soils of the Komi Republic and the assessment of the influence of soil hydromorphism on concentrations of free radicals in the structure of humic acids (HAs) and fulvic acids (FAs) have been performed. The concentration of free radicals in HA specimens was up to 11 times higher than that in FA specimens due to a higher content of aromatic and other condensed structures in HA molecules. This fact attests to the high capacity of HAs to polymerization and complexation reactions with participation of radicals. The average value of g-factor is higher for FA specimens than for HA specimens, which attests to a greater electron density shift of unpaired electron to oxygen atom in the structure of FAs because of its spin-orbital interaction with oxygen-containing functional groups, the concentrations of which are significantly higher in FAs than in HAs. An increase in the concentration of free radicals in the molecular structure of HAs is observed in taiga soils with an increase in the degree of their hydromorphism (from automorphic to semihydromorphic soils), which is related to the biohydrothermal conditions of humus formation in bog-podzolic soils with retarded biochemical processes and low degree of plant litter humification. As a result, HAs with the high content of free radicals in their structure are formed. An opposite situation is observed for HAs in tundra soils with a decrease in the content of unpaired electrons under conditions of the increased hydromorphism. The difference in the character of changes in the paramagnetic activity of HAs in taiga and tundra soils with different degrees of hydromorphism may be related to different natures of plant residues participating in humification processes. A tendency for a decrease in the paramagnetic activity in both HAs and FAs from the south to the north is observed, which may be related to a general decrease in the content of poly-conjugated systems in the structure of humic substances in tundra soils.     

31P-NMR spectra of humic acids: A comparison of four different raw humus types in Norway

Humic acids have been prepared from four Norwegian forest soils, namely crust, felty, greasy and granular raw humus. ³¹P-NMR spectra demonstrated the presence of a variety of phosphorus esters and diesters in all the humic acids investigated. Alkylphosphonic acids and/or esters were present in humic acids from crust and felty raw humus.     

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.     

Relationships between parameters of the humus status of forest and meadow soils and their altitudinal position on the main Crimean range

The influence of bioclimatic conditions related to the elevation above sea level on the quantitative and qualitative parameters of humus in mountain soils has been studied. It is shown that changes in the water and temperature conditions with the altitude do not exert significant effect on the humus content in mountain- forest soils, because the total amount of soil organic matter mainly depends on the composition and state of the vegetation cover. The humus content is the highest in meadow soils formed on mountain plateau with excessive moistening, which determines the formation of dense grass cover and the temperature regime favorable for humification. The percentage of Cha in the composition of Corg and the optical density of humic acids (HAs) are the qualitative parameters of the soil humus status changing with the altitude. The intensity of humus coloring of the soil depends on the content and optical density of HAs. A comparison of color intensity in the mountainous meadow chernozemlike soils and plain chernozems has shown its significant dependence on the hydrothermic conditions.     

Build-up of carbon fractions in technosol-biochar amended partially reclaimed mine soil grown with <Emphasis Type="Italic">Brassica juncea</Emphasis>

Purpose

Soil organic carbon (SOC) and its labile fractions are strong determinants of physical, chemical and biological properties. The objective of the present work was to evaluate the effects of organic amendments (technosol made of wastes and biochar) and Brassica juncea L. on the soil C fractions in a reclaimed mine soil.

Materials and methods

The studied soil was from a former copper mine that was subsequently partially reclaimed with vegetation and wastes. A greenhouse experiment was carried out to amend the mine soil with different proportions of technosol and biochar mixture and planting B. juncea. B. juncea plants can tolerate high levels of metals and can produce a large amount of biomass in relatively short periods of time.

Results and discussion

The results showed that with the addition of biochar and wastes, soil pH increased from 2.7 to 6.18, SOC from undetectable to 105 g kg^?1 and soil total nitrogen (TN) from undetectable to 11.4 g kg^?1. Amending with wastes and biochar also increased dissolved organic carbon (DOC) from undetectable to 5.82 g kg^?1, carbon in the free organic matter (FOM) from undetectable to 30.42 g kg^?1, FAP (carbon in fulvic acids removed with phosphoric acid) from undetectable to 24.14 g kg^?1 and also increased the humification ratio, the humification index, the polymerisation rate and the organic carbon in the humified fractions (humic acids, fulvic acids and humin). Soils amended and vegetated with B. juncea showed lower FOM values and higher humification index values than the soils amended only with biochar and wastes.

Conclusions

This study concludes that the combined addition of wastes and biochar has a greater potential for both increasing and improving organic carbon fractions in mine soils. The authors recommend the application of biochar and technosol made of wastes as a soil amendment combined with B. juncea on soils that are deficient in organic matter, since they increased all of the SOC fractions in the studied copper mine soil.

     

Comparison of humus composition of charred Susuki (Eulalia,Miscanthus sinensis) plants before and after HNO3 treatment

Ando soils (Kurobokudo), which are characterized by the accumulation of large amounts of black humus, are widely distributed in Japan, and the black color is due to the presence of A type humic acids with a high degree of humification (Kumada 1987).     

Combination reaction between humic acid and calcium ions

In the previous paper (1), liming an acid humus volcanic ash soil resulted in the formation of humic acids combined with calcium, but had no significant effect on acid brown forest soils containing humic acids of a lower degree of humification. Subsequently, the authors examined the humus composition of the soils treated with calcium acetate, and conducted some experiments on the combination reaction between humic acid and calcium ions. The results obtained are presented in this paper.     

不同植被下复垦土壤腐殖质与Cd形态的关系

[目的]揭示不同植被下土壤腐殖质与镉(Cd)形态的关系,为控制复垦土壤中Cd的活性提供理论依据。[方法]选择淮南市大通区煤矸石充填复垦区3种典型植被恢复模式下(模式A丁香+刺槐、模式B石楠+小巢菜、模式C臭椿+小巢菜)人工恢复7a的土壤,用tessier五步提取法和腐殖质修改法测定其Cd的化学形态及腐殖质组分,运用多元统计分析方法探讨复垦土壤中腐殖质与Cd的有效态间的相互作用。[结果](1)矿区复垦地C(臭椿+小巢菜)植被配置模式的土壤腐殖化程度较A,B模式高;(2)矿区复垦地C植被配置模式下Cd的可交换态含量显著低于其他2种配置模式;(3)矿区复垦区土壤中Cd的有效态与富里酸(FA)的含量显著正相关(p0.01)。[结论]通过适宜的植被模式C(臭椿+小巢菜)调节复垦土壤腐殖质的组成和性质,可以进而控制土壤镉的潜在生物有效性。     

Effects of Amendment with Composted Sludge On Soil Humic Acid Properties

The main physical and chemical properties of a composted mixture of sewage sludge and wood chips, the nonamended soil, and soils amended with two rates of the compost, in the presence or absence of barley, were determined. Humic acids (HAs) isolated from these materials were characterized by various methods including elemental analysis and Fourier Transform infrared (FTIR), fluorescence, and electron spin resonance spectroscopies. With respect to the nonamended soil HA, the compost HA was characterized by a prevalent aliphatic character, low oxygenated functional group content, high contents of S, N-containing groups and polysaccharide components, low free radical concentration, high molecular heterogeneity, and low degrees of ring polycondensation, polymerization and humification. Compost application at the low rate appeared to induce only limited modifications in the structural and chemical properties of HAs from amended soils, whereas apparent modifications of HA properties occurred where a high amendment rate was used. The absence or presence of barley cultivation appeared not to exert any measurable effect on the composition and properties of compost-amended soil HAs.     

Characterization of humic acids from tundra soils of northern Western Siberia by electron paramagnetic resonance spectroscopy

Humic acids from polar soils—cryozems (Cryosols), gleyezems (Gleysols), and peat soils (Histosols)—have been studied by electron paramagnetic resonance spectroscopy. First information was acquired on the content of free radicals in humic acids from polar soils for the northern regions of Western Siberia (Gydan Peninsula, Belyi Island). It was found that polar soils are characterized by higher contents of free radicals than other zonal soils. This is related to the lower degree of humification of organic matter and the enhanced hydromorphism under continuous permafrost conditions. The low degree of organic matter humification in the cryolithozone was confirmed by the increased content of free radicals as determined by electron paramagnetic resonance, which indicates a low biothermodynamic stability of organic matter.     

Lipid biomarkers and their environmental significance in mine soils from Eastern Europe

The present study describes signature lipid biomarkers in reclaimed mine soils (RMSs), an unreclaimed spoil and a natural soil (Vertisol) for a major coal mine basin in Eastern Europe. Alkanes, fatty acids and fatty alcohols, as well as coal biomarkers were abundant in the mine soils and the unreclaimed spoil. The alkanes distribution in the RMSs was bimodal with maxima at C₁₈ and C₂₉/C₃₁ and points at two origins for the alkanes, terrigenous plants, including soil borne and from the coal source. Fatty acid carbon preference indices (CPI_even/odd = 10.4 and 8.1 for the mine soils under pine and grass vegetation) reflect the increasing role of terrestrial vegetation in the formation of organic matter. The higher concentrations of the long-chain alkanes, fatty acids and alcohols are speculated as the reason for the severe and extreme water repellency observed with the Vertisol and the unreclaimed spoil. The presence of terrigenous steroid and triterpenoid markers in the RMSs is an indication of the ongoing soil formation processes. The analysis of lipid extracts allowed for the assessment of sensitive molecular indicators of biogenic terrigenous and coal origin and the degree of soil recovery following >20 years of spoils reclamation.