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1.
Humic and fulvic acids as indicators of soil and water pollution   总被引：1，自引：0，他引：1  
Humic substances are the major organic components of soil and sediments, but little is known on how they are affected by environmental and industrial pollution. To find out whether such effects could be recognized, a number of analytical characteristics were compared of humic and fulvic acids extracted from unpolluted and polluted soils and sediments. The main differences were that, per unit weight, polluted humic and fulvic acids contained more N, S and H but fewer CO2H groups, and were more aliphatic than unpolluted samples. Unusually high N and S contents of humic materials appear to be the most valid indicators of pollution. Humic acids are preferred to fulvic acids as indicators of pollution because the former are more readily separated and purified.  相似文献   

2.
Humic fractions, arginine ammonification and soil respiration were monitored in spring, summer and autumn 1999 in natural pasture soil and in no-tillage or reduced-tillage soil under maize. The Typic Argiudoll soils, typical of the Argentine rolling pampa, can be structurally unstable, particularly when conventionally tilled, a form of soil management affecting the humification process. The no-tillage soil had a lower content of fulvic acids than the reduced-tillage soil in spring and summer, probably because the humification process was favored by residue management in no-tillage soil, with a significant increase in the most stable fraction. Both arginine ammonification and CO2 were significantly correlated with the humic acids and humin contents. No significant correlation was found with fulvic acids,probably due to the lability and high variability of this fraction. A high correlation was found between arginine ammonification and CO2. The highest index values were generally observed in natural pasture soil, whereas no-tillage soils showed a higher index value than reduced-tillage soils throughout, confirming the hypothesis that humification is more intense in the presence of organic residues.  相似文献   

3.
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.  相似文献   

4.
Various composts contain a significant amount of humic substances including humic acid (HA) and fulvic acids (FAs). The FA fraction in soils is considered to be sensitive to agronomic and environmental factors. In this study, three fractions of humic substances, HA (MW > 1000 Da), FA (MW > 1000 Da), and FA (MW < 1000 Da) were extracted from swine manure-based compost and characterized, and then, their reactivities were correlated with heavy metals. Compositions of the three fractions of humic substances were characterized by elemental and total acidity analyses and electron spin resonance (ESR), Fourier transform infrared (FTIR), and 13C nuclear magnetic resonance with cross-polarization and magic-angle spinning spectroscopic techniques. Elemental analyses indicated that HA has higher contents of C, H, N, and S than those of FAs. However, FA (MW > 1000) and especially FA (MW < 1000) have higher contents of O than that of HA (MW > 1000). The g values of the ESR spectra of the three fractions showed that the organic free radical characteristics and the widths of the spectra and free radical concentrations of the three fractions are significantly different. The FTIR spectra indicated that HA (MW > 1000) is abundant in C=C bonds while FA (MW > 1000), especially FA (MW < 1000), are abundant in C=O bonds. In addition, 13C NMR spectra indicate that carboxyl contents of FA (MW > 1000), especially FA (MW < 1000), are higher than that of HA (MW > 1000). The sequence of the reactivity in terms of acidic functional groups was FA (MW < 1000) > FA (MW > 1000) > HA (MW > 1000). Elemental and functional group compositions of the three fractions significantly correlated with reported reactivities with heavy metals. The application of swine manure-based compost containing HA and FAs fractions to soil and associated environments may thus significantly affect the concerned reactions with organic and inorganic compounds including pollutants.  相似文献   

5.
Organic carbon sustainability in a gravelly calcareous soil is a great challenge under the humid conditions of south Florida. The beneficial effects of compost utilization on soil fertility prompted an investigation on (i) accumulation of total organic carbon and (ii) the soil organic carbon (SOC) in humin, humic acid (HA) and fulvic acid (FA) fractions in a gravelly calcareous soil amended with composts or inorganic fertilizer. In 1996 and 1998, compost from municipal solid waste (MSW) (100% MSW), Bedminster cocompost (75% MSW and 25% biosolids) and biosolids compost (100% biosolids) at 72, 82.7 and 15.5 Mg ha?1, respectively, were each incorporated in soil beds and inorganic fertilizer (6-2.6-10) NPK at 2.8 Mg ha?1. A control (no amendment) treatment was also included. Total organic carbon and various fractions of soil organic carbon were determined in two depths (0-10 and 10-22 cm) for both soil particles (< 2mm) and pebbles (> 2mm). Inorganic and organic soil amendments had decreased soil pH and increased soil electrical conductivity (EC) 19 months from initial application. Total organic carbon contents in soil particle were 4-, 3-, and 2-fold higher in MSW compost, Bedminster cocompost and biosolids compost treatments, respectively, than those in fertilizer treated or non-treated soils. MSW compost increased total organic carbon in pebbles by 4- and 3-fold in the 0-10 and 10-22 cm deep layers, respectively, more than other treatments. The soil organic carbon accumulation decreased with depth in all treatments in soil particles, but did not in pebbles. Amending soils with MSW compost significantly increased the organic carbon in humin, HA and FA fractions more than those treated with inorganic fertilizer or non-amended. MSW compost has a potential to be used as a soil amendment to increase and sustain the organic carbon in calcareous soils of south Florida.  相似文献   

6.
Abstract

Total organic P, humic and fulvic acid‐P associations and inositol phosphates in nine volcanic soils of southern Chile were determined. The concentration of organic P (Po) ranged from 654 to 1942 ppm accounting for 49% to 64% of total soil P. Phosphorus associated to humic (HA‐P) and fulvic acids (FA‐P) accounted for 51–68% and 32–49% of Po, respectively. Inositol penta‐ and hexaphosphates represented 42% to 67% of Po suggesting that significant amounts are associated with both humic and fulvic acids. Po content was significantly correlated to organic C, total soil P and HA‐P. HA‐P and FA‐P fractions obtained from the most representative soil were examined by dyalisis and gel filtration. While approximately 96% of HA‐P presented a molecular weight higher than 100,000 daltons, 53% of FA‐P had a molecular weight under 12,000 daltons. It is suggested that these more labile organic P forms would be more easily mineralized, thus increasing the available P pool.  相似文献   

7.
We investigated the effect of continuous compost application on humus composition and N fertility of soils in a field subjected to double cropping (paddy rice and barley) for 25 years. Soil samples were collected from three different plots: (a) No-NF, fertilizer containing P and K but no N; (b) F, fertilizer containing N, P, and K; and (c) F+C, fertilizer plus compost. The amounts of total humus, extracted humus, and humic and fulvic acids increased in the order No-NF<F≪F+C. The amounts of humic and fulvic acids were 2.7 and 1.7 times larger in the F+C plot than in the F plot, respectively. The degree of humification of the humic acids decreased in the order No-NF<F<F+C. The absorption curves and 13C-NMR spectra (TOSS method) of the humic acids indicated the presence of lignin-like structure, and its degree was the strongest in the F+C plot. The 13C-NMR spectra showed distinct differences in the distribution of carbon species between humic and fulvic acids. In humic acids, the content of aromatic-C, ranging from 37 to 44%, was the highest among carbon species. In fulvic acids, the content of O-alkyl-C, ranging from 45 to 51%, was the highest. The amounts of phosphate buffer-extractable N (PEON) and total N (TN) increased in the order No-NF<F<F+C. The amounts of PEON and TN were 1.2 and 1.7 times larger in the F+C plot than in the F plot, respectively. Present and previous findings indicated that continuous compost application could improve various properties of soils in a field subjected to long-term double cropping.  相似文献   

8.
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.  相似文献   

9.
Decomposition of organic matter in inundated wetland soils requires a number of interdependent microbial processes that ultimately generate CO2 and CH4. Largely as the result of anaerobic decomposition, wetland soils store globally significant amounts of organic carbon and are currently net sources of CH4 to the atmosphere. Given the importance of wetlands in the global carbon cycle, it is important to understand controls on anaerobic decomposition in order to predict feedbacks between wetland soils and global climate change. One perplexing pattern observed in many wetland soils is the high proportion of CO2 resulting from anaerobic decomposition that cannot be explained by any measured pathway of microbial respiration. Recent studies have hypothesized that humic substances, and in particular solid-phase humic substances in wetland soils, can support anaerobic microbial respiration by acting as organic electron acceptors. Humic substances may thus account for much of the currently unexplained CO2 measured during decomposition in wetland soils. Here we demonstrate that humic acids extracted from a variety of wetland soils act as either electron donors or electron acceptors and alter the ratio of CO2:CH4 produced during anaerobic laboratory incubations. Our results suggest that soil-derived humic substances may play an important, and currently unexplored, role in anaerobic decomposition in wetland soils.  相似文献   

10.
The humus state of rainfed chernozems affected by local waterlogging was studied. The total humus content in the hydromorphic chernozems increases, as well as the content of fulvic acids, whereas the content of nonhydrolyzable residue (humin) decreases. A significant increase in the portions of the third fractions of humic and fulvic acids is observed. The role of the fine silt and clay fractions in the binding of humic substances increases in the lower horizons of locally hydromorphic soils. The increase in the content of fulvic acids (fulvatization) is mainly due to their predominance in the clay fraction. The latter is specified by the significant narrowing of the Cha-to-Cfa ratio, the lower content of the nonhydrolyzable residue, and the increased content of the clay-bound (3rd fraction) fulvic and humic acids. The composition of the humus in the fine silt fraction of the studied soils is characterized by an increased amount of humic acids of the second fraction with a decrease in the relative content of fulvic acids.  相似文献   

11.
Abstract

Regeneration of a soil with a high degree of desertification was conducted by the addition of different doses of municipal solid waste organic matter (MSW). Five years after this treatment, humic substances were extracted from these soils and characterized by spectroscopy and isoelectric focusing. No significant differences between E4/E6 ratio and ?log K (Log A400 nm‐log A600 nm) were observed for humic substances extracted from treated and untreated soils. However, the isoelectric focusing (IEF) technique established differences between the humic substances from control and treated soils. The focusing pattern of the former showed a well defined band at pH 9.1 which nearly disappeared in the soils with high doses of MSW (1–2 %). However the organic matter which focused at pH 5.8 was present in all soils.  相似文献   

12.
Water extracts were obtained from four types of soils (Brown Lowland soil, Yellow soil with manure application for 6 years, non-allophanic Andosol, and allophanic Andosol), and the organic matter in the water extracts was fractionated according to the solubility in acid and adsorption onto polyvinylpyrrolidone (PVP). For the water extracts and their fractions, the amounts of organic C, total N, and anthrone-reactive C (ARC) were analyzed, and high performance size exclusion chromatography (HPSEC) was carried out. The PVP-non-adsorbed fulvic acid (FA) fraction accounted for the largest proportion of the total water-soluble organic C, ranging from 52% for the Yellow soil to 96% for the allophanic Amdosol, followed by the PVP-adsorbed FA and humic acid (HA) fractions. The water extract of the allophanic Andosol was characterized by the lack of HA fraction and a small proportion of PVP-adsorbed FA fraction. For all the water extract samples, more than 90% of the ARC was recovered in the PVP-non-adsorbed FA fraction. The proportion of ARC in the total organic C in the fraction was also highest in the PVP-non-adsorbed FA fraction. The molecular weight (MW) of the humic substances (HS) at peak maximum was estimated at 1,300 Da for the water extracts and their fractions from the Brown Lowland soil and non-allophanic Andosol samples by HPSEC using polyethylene glycols as MW standards. Manure application increased the MW of HS in the HA and PVP-adsorbed FA fractions. On the other hand, only a small amount of HS was found in the water extract of the allophanic Andosol by HPSEC.  相似文献   

13.
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14.
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.  相似文献   

15.
Incorporation of newly-immobilized N into major soil organic matter fractions during a cropping period under paddy and upland cropping systems in the tropics was investigated in Jawa paddy fields with and without fish cultivation and a Sumatra cassava field in Indonesia. 15N-labelled urea (15N urea) was applied as basal fertilizer, and the soil samples were collected after harvest. The percentage of distribution of the residual N in soil from 15N urea into the humic acids, fulvic acid fraction, and humin were 13.1–13.9, 19.0–20.5, and 53.4–54.3%, respectively, for the Jawa paddy soils, and 14.9, 27.4, and 52.4%, respectively, for the Sumatra cassava soil. These values were comparable to the reported ones for other climatic zones. The percentage of distribution of 15N urea-derived N into humic acids was larger than that of total N into the same fraction in all the soils. The distribution into the fulvic acid fraction was also larger for 15N urea-derived N than for total N in the Jawa soils. Humic and non-humic substances in the fulvic acid fraction were separated using insoluble polyvinylpyrrolidone (PVP) into the adsorbed and non-adsorbed fractions, respectively. Less than 5% of the 15N urea-derived N in fulvic acid fraction was detected in the PVP-adsorbed fraction (generic fulvic acids). The proportion of non-hydrolyzable N remained after boiling with 6 M HCl in the 15N urea-derived N was 9.4–13.5%, 17.3–26.7%, and 8.4–16.6% for the humic acids, generic fulvic acids, and humin, respectively. The significantly low resistance to acid hydrolysis suggested that the 15N urea-derived N was less stable than the total N in soil regardless of the fractions of humus.  相似文献   

16.

Purpose

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

Materials and methods

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

Results and discussion

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

Conclusions

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

17.
Electrophoresis in 10% polyacrylamide gel in the presence of denaturants and size-exclusion chromatography in Sephadex G-75 in 7 M urea were used for the comparative analysis of humic substances isolated from a typical chernozem, soddy-podzolic soil, and chestnut soil and from the easily decomposable organic matter (plant detritus) contained in these soils. After the electrophoresis, the gel with naturally colored bands of humic substances was further stained with a dye specific for proteins by immersing into a solution containing Coomassie Brilliant Blue R-250 and CuSO4. The electrophoretic and chromatographic analyses showed that humic substances from the soils and the corresponding detritus fractions significantly differed in the intensity of the natural color of the electrophoretic fractions, the molecular-weight distribution, and the color of the electrophoretic fractions colored by the protein-specific dye (which was first discovered in this study). The hypothesis of Tyurin and Aleksandrova suggesting that the transformation of humus sources (plant detritus) into humic substances proceeds in the direction from the high-molecular compounds to the low-molecular compounds was experimentally confirmed.  相似文献   

18.
不同施肥条件土壤胡敏酸级分变异及性质的研究   总被引：11，自引：3，他引：8  
王旭东  张一平 《土壤学报》1998,35(3):404-411
以１７年长期定位试验土壤为材料,在研究土壤有机质氧化稳定性基础上,采用酒精沉淀分级方法,对不同施肥处理土壤胡敏酸的级分及光学性质进行了研究,并对胡敏酸及其级分的类型进行了划分。结果表明长期施用有机（堆肥及秸秆）土壤有机质含量明显增加,有机质的氧化稳定系数降低,土壤胡敏酸组成分布中心向高浓度酒精析出的级分偏移,颗粒小的级分比例增大,土壤胡敏酸的Ｅ４,Ｅ６值减小Ｅ４／Ｅ６增大,而单施化肥则有相反趋势。  相似文献   

19.
Abstract

Humic and fulvic acids were extracted from the surface horizons of Alfisols, Vertisols, and Entisols with good and impeded natural drainage. These profiles are located in the temperate subhumid zone. The extracted humic substances were characterized by elementary and functional group analyses, IR‐spectroscopy, differential thermal analysis (DTA) and electron spin resonance spectroscopy (ESR). Some differences in the humic substances seem to be associated with differences in the natural drainage of the soils. When data from samples of the same soil order are compared, indicate that humic (HAs) and fulvic acids (FAs) extracted from soils with impeded drainage, have higher contents of carbon and spin concentration, but less total acidity and fewer carboxylic groups (COOH), than the respective humic substances extracted from well drained soils. The IR‐spectra of the HAs extracted from soils with impeded drainage showed more aliphatic groups than those of the well drained soils. No essential differences, which could be related to the drainage conditions of the studied soils, were observed in the IR‐spectra of FAs. DTA‐diagrams shows that the thermal stability of the HAs and the FAs are related to their carbon and ash contents. Iron was the dominant element in the ash of the humic acids, aluminum and silicon were the most abundant elements in the ash of the fulvic acids.  相似文献   

20.
Humic substances play a key role in the global carbon cycling and the sequestration of micropollutants in soil. The transformation of these substances by earthworms, the dominant soil macroinvertebrates of many terrestrial ecosystems, and the mechanisms involved are still obscure. We prepared two chemically identical humic model compounds that were specifically 14C-labeled either in the aromatic or the proteinaceous component, and added them to soil incubated with the geophagous earthworm species Metaphire guillelmi (anecic) and Amynthas corrugatus (endogeic). In the absence of the earthworms, both the aromatic and the proteinaceous components were mineralized at similarly low rates (5−8% after 9 days of incubation). In the presence of the earthworms, mineralization rate of the proteinaceous component was strongly stimulated (2-fold by M. guillelmi and 1.4-fold by A. corrugatus). The mineralization rate of the aromatic component was (slightly) stimulated (1.2-fold; P < 0.05) only by A. corrugatus. In all cases, the stimulated mineralization was accompanied by a transformation of radiolabeled humic acids to fulvic acids within the earthworm guts and by an incorporation of radiolabel into the earthworm tissues. Digestion of the proteinaceous component of humic acids by the earthworms was corroborated also by a decrease of extractable humic acids in fresh cast and a stimulated mineralization of soil nitrogen; in the case of M. guillelmi, the fresh cast contained sixfold more NH4+ than the non-ingested soil. Our study provides direct evidence for the selective digestion of humic components by earthworms. Considering the ubiquity of geophagous earthworms and their large biomass, the alteration of the chemical structure of humic substances by the earthworms through their selective digestion of peptidic components may have significant impacts on the stability of humic substances and the bioavailability of micropollutants in soil.  相似文献   

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