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1.
The role of lipid components in the aggregation of several humic acids isolated from different sources was investigated using surface tensiometry. A combination of aqueous alkaline and organic solvent extractions was used to isolate two humic-like fractions (HA1 and HA2) and one lipid-like fraction from each humic acid. Fraction HA1 represents approximately two-thirds of the total organic carbon of the original humic acid and under alkaline conditions is a weak surfactant that lowers the surface tension of water by only a small amount. The HA2 fraction represents up to one-third of the humic acid and significantly lowers the surface tension of water. It is also intimately associated with the lipid fraction. Unlike the original humic acid samples, HA2 does not show micelle-like aggregation over the concentration range studied. Aggregate formation is discussed as an emergent characteristic that results from the interaction of the humic acid’s components with the lipid components serving a facilitative role.  相似文献   

2.
Sources of sedimentary humic substances: vascular plant debris   总被引：1，自引：0，他引：1  
A modern Washington continental shelf sediment was fractionated densimetrically using either an organic solvent, CBrCl3, or aqueous ZnCl2. The resulting low density materials (<2.06 g/ml) account for only 1% of the sediment mass but contain 25% of the sedimentary organic carbon and 53% of the lignin. The C/N ratios (30–40) and lignin phenol yields (Λ = 8) and compositions indicate that the low density materials are essentially pure vascular plant debris which is slightly enriched in woody (versus nonwoody) tissues compared to the bulk sediment. The low density materials yield approximately one-third of their organic carbon as humic substances and contribute 23% and 14% of the total sedimentary humic and fulvic acids, respectively. Assuming that the lignin remaining in the sedimentary fraction is also contained in plant fragments that yield similar levels of humic substances, then 50% and 30% of the total humic and fulvic acids, respectively, arise directly from plant debris.Base-extraction of fresh and naturally degraded vascular plant materials reveals that significant levels of humic and fulvic acids are obtained using classical extraction techniques. Approximately 1–2% of the carbon from fresh woods and 10–25% from leaves and bark were isolated as humic acids and 2–4 times those levels as fulvic acids. A highly degraded hardwood yielded up to 44% of its carbon as humic and fulvic acids. The humic acids from fresh plants are generally enriched in lignin components relative to carbohydrates and recognizable biochemicals account for up to 50% of the total carbon. Humic and fulvic acids extracted directly from sedimentary plant debris could be responsible for a major fraction of the biochemical component of humic substances.  相似文献   

3.
《Applied Geochemistry》2006,21(7):1226-1239
Natural organic matter (NOM) from the Han River, Korea was fractionated into humic and non-humic fractions by absorbing onto XAD-7HP, and these fractions were analyzed using UV-absorption, and for dissolved organic C (DOC). The humic fraction (i.e. humic substances; HS) was extracted and its characteristics were compared to commercial humic materials using various spectroscopic methods such as Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (1H-NMR) and fluorescence spectroscopy. The humic fraction as organic C was 47.0% on the average, however, a rainfall event brought a higher humic fraction into Han River water. The molar ratios of H/C and O/C in the HS from Han River water (HRHS) were 1.40 and 0.76, respectively, and the ratio of aliphatic to aromatic protons in the HS (PAl/PAr ratio) was 5.8. Aromaticity and humification degree (i.e., degree of condensation) of HRHS were relatively lower than those from other humic materials, while the portion of oxygenated functional groups was relatively higher. FT-IR, 1H-NMR and fluorescence spectroscopy showed distinct differences between HRHS and the commercial humic materials. Commercial humic materials are not representative of HS extracted from Han River water. The fluorescence spectra, relatively simple measurements, were found to be most useful as fingerprints for humic materials from particular sources.  相似文献   

4.
Organic matter was isolated from the water columns and sediments of two pond systems in the south-eastern United States. Water column material was ultrafiltered to provide three fractions, i.e. <0.45 μm, but > 50,000 daltons; <50,000 daltons, but > 5000 daltons; and <5000 daltons. Sedimentary organic matter was separated into humic acid and fulvic acid fractions based on solubility criteria and the humic acid fraction was ultrafiltered to provide the same fractions as the water column isolates. All fractions were analysed for organic carbon, Al, Ca, Cu, Fe, Mg and Mn. Infra-red spectra were also measured for the sedimentary organic fractions. Organic matter isolated from the water column of the two ponds had similar organic carbon and elemental distributions, as did the organic matter isolated from the two sediments. However, significant differences in the organic carbon and elemental distributions were observed for water column and sedimentary organic matter isolated from the same pond. These studies have relevance to diagenetic alterations of organic matter and geochemical cycles of elements within lakes.  相似文献   

5.
Characteristics and distributions of humic acid (HA) and soil organic matter (SOM) in a yellow soil profile and a limestone soil profile of the southwest China Karst area were systematically investigated to reveal their evolutions in different soils of the study area. The results showed that characteristics and distribution of SOM along the two soil profiles were notably different. Total organic carbon (TOC) contents of soil samples decreased just slightly along the limestone soil profile but sharply along the yellow soil profile. TOCs of the limestone soils were significantly higher than those of the corresponding yellow soils, and C/N ratios of SOMs showed a similar variation trend to that of TOCs, indicating that SOM can be better conserved in the limestone soil than in the yellow soil. The soil humic acids were exhaustively extracted and further fractionated according to their apparent molecular weights using ultrafiltration techniques to explore underlying conservation mechanisms. The result showed that C/N ratios of HAs from different limestone soil layers were relatively stable and that large molecular HA fractions predominated the bulk HA of the top soil, indicating that HA in the limestone profile was protected while bio and chemical degradations were retarded. Combined with organic elements contents and mineral contents of two soils, we concluded that high calcium contents in limestone soils may play a key role in SOM conservation by forming complexation compounds with HAs or/and enclosing SOMs with hypergene CaCO3 precipitation.  相似文献   

6.
It is generally accepted that the compositions and properties of soil organic matter (SOM) are influenced by many factors. In order to reveal the effects of soil texture on characteristics and dynamics of SOM and its sub-fraction, humic acid (HA), along two soil profiles, a yellow soil profile and a purplish soil profile, under the same climate and vegetation conditions were determined. Results indicate that the decomposition and humification degrees of SOM and HA of the purplish soils are higher than those of the corresponding yellow soils indicated by A/O–A ratios of HAs, TOCs and HA yields of bulk soil samples, nevertheless, the development degree of the purplish soil is lower than that of the yellow soil. The variations of E4/E6 ratios of HAs along the soil profiles indicate the overall molecular sizes of HAs decreased downward along the soil profiles. A/O–A ratios of HAs decreased downward along both the soil profiles indicate that humification processes decrease downward along both the soil profiles. Leaching of SOM shows significant effects on the distribution and characteristics of HAs in the yellow soil profile but the purplish soil profile, which is consistent with the higher hydrophobicity of HAs in purplish soils, shows that the distribution characteristics of SOM along the soil profiles are a complex result of the combination of soil texture and characteristics of SOM itself. The remarkably different sand contents are concluded tentatively as one of reasons to the different distributions and dynamics of HAs along the soil profiles, however, to profoundly understand the evolution and transport of SOM along soil profiles needs more researches.  相似文献   

7.
Peptides were released from organic matter fractions of three Italian soils (humin, humic and fulvic acids), when the samples were hydrolyzed in Ba(ON)2-saturated solution at 105°C for 2 hr. The peptides obtained were separated using electrophoresis and paper chromatography. The presence of polypeptides in the soil organic matter was indicated by: (1) their hydrolysis by pronase; (2) the amino acids released by 6 N HCl hydrolysis; (3) The comparison of i.r. spectra of humic fractions before and after hydrolysis with 6 N HCl.Attempts at isolating the native proteinaceous compounds using electrophoresis in polyacrylamide gel failed; additionally, our attempts to hydrolyze proteinaceous components enzymatically in unfractionated soil organic matter, as well as in its fractions, before and after methylation, with pepsin, papain and pronase, were unsuccessful. Pronase demonstrated a weak proteolytic activity only at very low substrate-enzyme ratios (20 : 1) in humic and fulvic fractions and in whole phyrophosphate extract. Deproteinated substrates treated with pronase also released free amino acids, suggesting autodigestion.In humin, humic and fulvic fractions we found a total amino acid content of 40–45%, 12–24% or 1–85, respectively. Amino acid recovery from single fractions was about 70–80% of the total content in the unfractionated soil.  相似文献   

8.
1H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -(CH2)n - CH3 (n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.  相似文献   

9.
Cross polarization, magic-angle spinning 13C nuclear magnetic resonance spectroscopy was used to characterize humic fractions isolated from different soils. The acid fractions are more aromatic than the humin fractions, probably due to the higher polyssaccharide content of humins. However, fulvic acid fractions are more aromatic than the corresponding humic acid and humin fractions. These results can be interpreted in terms of the isolation procedure, because the high affinity of Polyclar AT for phenols results in higher aromaticities as compared with other isolation methods (e.g. charcoal).  相似文献   

10.
Humic acids and fulvic acids were extracted from six paleosols in Southern Italy. Humic acids (HAs) constituted between 96.5 and 99.2% of the total extracts; the remaining materials consisted of fulvic acids (FAs). Radiocarbon ages of the HAs ranged from about 6,000 to close to 29,000 years B.P., δ13C values averaged ?25.6 ± 0.3‰ The HAs were characterized by chemical (elemental and functional group analyses) and spectroscopic (IR, ESR, 13CNMR, E4/E6 ratios) methods. FAs were characterized by chemical methods, E4/E6 ratios and IR spectra.The chemical and spectroscopic analyses showed practically no differences in the chemical structure and composition of the six HAs and FAs, so that age appeared to have little effect on these parameters. The paleosols were found to be closed systems with low polysaccharide and protein contents, thus providing unfavorable substrates for microbial activity. The preservation of the humic materials in the paleosols may have been due to low biological activity and/or to retention by amorphous minerals. The HAs did not appear to be affected by temperatures higher than 170–200°C over the 23,000 year period which we observed.  相似文献   

11.
An understanding of the processes that lead to long-term stabilization of organic matter in soils is essential to the effective implementation of strategies designed to mitigate CO2 loss from the soil carbon reservoir in temperate climatic zones. Decomposition studies indicate that montmorillonite, a smectite that often forms with interlayers rich in Ca2+, greatly retards the microbial mineralization of soil organic matter. We performed a series of atomistic simulations designed to identify favorable molecular-scale organo-mineral interactions within nanoscale, hydrated complexes consisting of a humic substance and Ca-montmorillonite. Both protonated and Ca-saturated forms of the model humic molecule, representing acidic and circumneutral solution conditions, respectively, were studied within the hydrated interlayer region of a rigid-atom model of Ca-montmorillonite. The protonated humic substance formed direct hydrophobic and hydrogen bonding (H-bonding) interactions with the clay mineral. A few polar organic groups adsorbed via water bridging interactions. The Ca-saturated humic substance adsorbed via numerous cation bridges, less numerous water bridges, and indirect H-bonding interactions mediated by water molecules. Application of molecular modeling techniques to this complex organo-mineral system thus allowed identification of interactions favorable to carbon sequestration under both acidic and circumneutral conditions.  相似文献   

12.
Lipids, fulvic acid, humic acid and kerogen were isolated from a lacustrine sediment in which the organic matter is probably derived predominantly from phytoplankton (Lake Haruna, Japan). An alkaline KMnO4 oxidation study of the organic matter showed that distributions of polymethylene chain lengths in the lipids, humic acid and kerogen fractions are almost the same. The polymethylene chains in the sediment are dominant in the kerogen, lipids and humic acid, their relative abundance estimated by the oxidation being: kerogen (42% of the total amounts of polymethylene chains estimated) > lipids (38%) > humic acid (19%) > fulvic acid (1%). It was concluded that algal lipids may have been incorporated into the kerogen and humic acid fractions after the death of the algae and during, after, their deposition.  相似文献   

13.
The use of ultrasonic vibrations (1 hr) on the extraction of humic acids (HA) from a brown soil has been compared with the extraction by mechanical stirring (24 hr) with two extractants: 0.5 N and 0.1 M Na4P2O7, followed by extraction with 0.5 N NaOH. In the pyrophosphate extraction, ultrasonic and mechanical treatments produced the same yield of HA. Further extraction with NaOH and mechanical stirring gave higher yields.The elemental composition of HA changed remarkably with both ultrasonic and mechanical systems. The HA extracted with ultrasonic treatment showed a higher ash content and a lower content of COOH and phenolic OH groups. These HA's showed higher optical density at 260 and 450 nm when pyrophosphate-extracted, and lower optical density when NaOH-extracted. Moreover the ultrasonic-treated HA in both extractants showed a lower E400/E600 ratio.Infrared examination confirmed the difference in chemical characteristics of extracted HA. The HA distribution in the different classes of nominal molecular weights by Sephadex gel filtration was influenced by both ultrasonic and mechanical systems, specially for molecular weights between 5000 and 150,000. It has been noted that the differences due to both systems are less marked than those caused by ssing different extractants.  相似文献   

14.
A rigorous mathematical expression for the dependence of colligative properties on acid dissociation of water soluble humic substances is presented. New data for number average molecular weights of a river derived humic material and its gel permeation Chromatographic fractions are compared with M?n values obtained by a reevaluation of previously published experimental observations on soil and water fulvic acids. The results reveal a remarkable similarity of fulvic acids from widely different sources with respect to number-average molecular weight.  相似文献   

15.
Humic substances were isolated from ocean, estuarine water and fresh water using a two column array of XAD-8 and XAD-4 resins in series. The extracted fulvic acids and XAD-4 fraction from different origins were characterized using UV–vis., molecular fluorescence, Fourier transform infrared (FTIR) spectroscopy and cross polarization magic angle spinning (CPMAS)-13C nuclear magnetic resonance (NMR) spectroscopy. The isolation procedure allowed us to obtain the necessary amount of sample for characterization, even in the case of open ocean water, which has a very low amount of dissolved organic carbon (DOC). Humic substances from the open ocean showed the lowest chromophore and fluorophore contents and showed relatively greater fluorescence at lower wavelengths than those from fresh water. FTIR and 13C NMR spectra highlighted the idea that humic substances from a marine environment have a more branched aliphatic structure and less aromatic structure than those highly influenced by terrestrial sources. The spectra also suggest that the open ocean humic substances have a higher content of olefinic carbons than aromatic- or alkyl-substituted carbons.  相似文献   

16.
The phosphorus content of marine humic acids (HA) is in the range of 0.1–0.2%. The C/P ratios of the HA are 300 to 400. Marine fulvic acids (FA) contain 0.4–0.8% P and have C/P ratios of 80 to 100. High molecular weight organic matter dissolved in pore waters (DOM) contains 0.5% P and has C/P of 90. The data suggest that during the formation sequence: Plankton → DOM → FA → HA → Kerogen, phosphorus is lost, mainly in the FA → HA (and possibly also in the HA → Kerogen) step. Diagenesis of sedimentary humic acids is accompanied by loss of phosphorus (as well as of nitrogen) to form HA with C/P ratios of 1000.Soil humic substances resemble marine humates in P content (0.3%) and soil FA's are about three to fivefold enriched in P relative to HA. C/P ratios are lower in soil HA (ca. 200) as compared with marine HA. Humic acids from diagenetic products such as peat and lignite are highly depleted in P. Rough calculations indicate that humate bound P may account for 20–50% of the organic phosphorus reservoir in sediments. The chemical speciation of this P is unknown, but lack of correlation with ash, Fe, Ca or Al content (in marine humates, at least) indicates that it is organically bound.  相似文献   

17.
The interactions of humic substances from Esthwaite Water with hydrous iron oxides (α-FeOOH, α-Fe2O3, amorphous Fe-gel) have been examined by measuring adsorption isotherms and by microelectrophoresis. In Na+-Cl?-HCO3?at I = 0.002 M (medium I) the extent of adsorption decreases with increasing pH. The results are consistent with a mechanism involving ligand exchange of humic anionic groups with H2O and OH?of surface Fe-OH2+and Fe-OH groups respectively, with an increasing degree of protonation of the adsorbed humics as the adsorption density increases at constant pH.At pH 7 in a medium containing Mg2+, Ca2+ and SO42?, at their Esthwaite Water concentrations and at I= 0.002 M (medium II) the adsorption capacity of goethite (α-FeOOH) is approximately twice that in medium I. Electrophoresis experiments show that the extra capacity is associated with coadsorption of Mg2+ and/or Ca2+ ions.When the iron oxides are added to samples of Esthwaite Water itself they become negatively charged and plots of electrophoretic mobility against pH for the natural water are identical to those in medium II plus humics.  相似文献   

18.
Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5–116 hr) and temperatures (150°–410°C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid <1%. Whereas n-alkanes produced from lipid show a CPI > 1.0, those produced by thermal alteration of kerogen display a CPI < 1.0. The volatiles produced by heating the lipid and humic acid fractions were largely CO2 and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C2–C4 hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.  相似文献   

19.
Humic substances (HS) were isolated from Penwhirn Reservoir (PR) and Esthwaite Water (EW) and their removal from solution by centrifugation was studied as a function of pH, humic concentration and molecular weight, and CaCl2 concentration. Large amounts (up to 50%) of PR HS could be removed but only small amounts (? 3%) of EW HS. At pH ? 5 removal of PR HS by Ca2+ can be explained satisfactorily in terms of decreases in humic solubilities induced by complexation with the cation. However, removal induced by protonation of the PR HS is unusual in that it decreases with increasing humic concentration.The results suggest that PR HS comprise a range of molecules differing in solubility, with the high-molecular-weight (40,000) components being the least soluble. The EW HS consist of molecules of weight-average molecular weight 5000 and resemble similarly sized PR HS in that they remain unaggregated in solution even when highly complexed with Ca2+.  相似文献   

20.
Vanillyl, syringyl and cinnamyl phenols occur as CuO oxidation products of humic, fulvic and base-insoluble residual fractions from soils, peat and nearshore marine sediments. However, none of these lignin-derived phenols were released by CuO oxidation of deepsea sediment or its base-extractable organic fractions. Lignin analysis indicated that peat and coastal marine sediments contained significantly higher levels of recognizable vascular plant carbon (20–50%) than soils and offshore marine sediments (0–10%).Although accounting for less than 20% of the total sedimentary (bulk) lignin, lignin components of humic acid fractions compositionally and quantitatively resembled the corresponding bulk samples and baseinsoluble residues. Recognizable lignin, presumably present as intact phenylpropanoid units, accounted for up to 5% of the carbon in peat and coastal humic acids but less than 1% in soil humic acids. Fulvic acid fractions uniformly yielded less lignin-derived phenols in mixtures that were depleted in syringyl and cinnamyl phenols relative to the corresponding humic acid fractions.Within the vanillyl and syringyl families the relative distribution of acidic and aldehydic phenols is a sensitive measure of the degree of oxidative alteration of the lignin component The high acid/aldehyde ratios and the low phenol yields of soils and their humic fractions compared to peat and coastal sediments indicate extensive degradation of the lignin source material. Likewise, the progressively higher acid/aldehyde ratios and lower phenol yields along the sequence: plant tissues (plant debris)-humic acids-fulvic acids suggest that this pattern represents the diagenetic sequence for the aerobic degradation of lignin biopolymers.  相似文献   

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