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1.
The aim of this work is to study the structural changes involved in humification processes. Total humic extracts (THE) obtained from five composted materials of diverse origin (solid wastes of wineries, solid mill olive wastes, domestic wastes, ovine manures plus straw, and a mixture of animal manures), and their corresponding initial raw fresh organic mixtures were studied using 13C nuclear magnetic resonance (NMR) using the cross-polarization magic angle spinning technique (CPMAS), 1H NMR, Fourier transform infrared spectroscopy (FTIR) and high pressure size exclusion chromatography (HPSEC). One group of three humic acids extracted from soils, and a second group consisting of two reference humic acids and two reference fulvic acids (1S104H, 1R103H, 1R101F and 1R107F) obtained from the International Humic Substances Society were also characterized using these techniques, in order to compare the features of reference humic and fulvic acids with those of composted materials. Likewise, the results were compared with those obtained in previous studies, in which UV–Visible and fluorescence spectroscopies were employed to characterize the humification degree of the molecular systems.The results obtained by 13C CPMAS NMR, 1H NMR and FTIR indicate that, in general, humification seems to be associated with an increase in the aromatic character of the systems, with the presence of phenol groups as principal substituents and a reduction in oxygen containing functional groups, principally carboxylic or carbonylic groups, as well as the development of molecular fractions with larger size. These results also support the suitability of UV–Visible and fluorescence spectroscopies in the assessment of the humification course of humic extracts in composting processes.  相似文献   

2.
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   

3.
Organic matter from an arable soil derived from base rich parent material was extracted by alkali and fractionated on the basis of solubility in 0.1 N HCl, hot water and hot 6 N HCl and by selective adsorption on charcoal. The distribution of associated metals was determined and Cu had the largest proportion, 15%, associated with the organic matter. Moderate proportions of the total Al, Co, Ni, and V (3–8%) but only small amounts (?1%) of the Mn, Fe, Ti, Cr, Ba and Sr were extracted from the soil by alkali. The Fe and Ti were concentrated mainly in the humic fraction whereas Mn and V were both found largely in the fulvic acid.Electron paramagnetic resonance spectra of the various fractions were examined and attempts made to relate the spectra to the forms of some of the metals present. In the humic acid fraction Cu was present partly as a copper porphyrin-type complex but in the fulvic acid it was in some other complexed form. VO2+ occurred in complexed forms in the fulvic acid which were more covalent than VO2+ humic acid complexes, whereas the Mn2+ components of the humic and fulvic acids all had a high degree of ionicity.  相似文献   

4.
在长时间尺度上研究土壤中腐殖物质的组成和腐殖化特征对于正确评价土壤有机质的稳定性具有重要意义。文中对洛川黄土/古土壤剖面S8以上的17个黄土和古土壤样品中的胡敏酸（HA）、富里酸（FA）和胡敏素（HM）进行定量研究,并对HA和FA的E465、E665值等进行了测定。结合该课题组对矿物组成、总有机碳（TOC）及其各组分含...  相似文献   

5.
Aqueous solutions of increasing pH (7.0, 10.6 and 12.6) were used to extract exhaustively the organic matter (OM) from a pelo-stagnogley (heavy clay) soil in long term cultivation. OM yield was 1.7 times greater when the extracts were processed using an XAD-8 and XAD-4 resin-in-tandem procedure than that from the procedure of the International Humic Substances Society (IHSS). The substantial difference can be attributed to the amount retained by the XAD-4 resin, which is lost in the IHSS process. Elemental, δ13C, δ15N, cation exchange capacity, neutral sugars, amino acids and solid state CPMAS 13C NMR analyses indicated significant, but rational similarities and differences between the various fractions isolated. There was strong NMR evidence for material derived from lignin in all the humic and fulvic acid isolates. The signals were attenuated in the more transformed/oxidized fractions isolated at lower pH. Novel humic acid fractions enriched in carbohydrate/peptide functionalities were isolated from the more hydrophobic extracts at pH 10.6 and 12.6. Isolates from XAD-4, of microbial origin, were enriched in neutral sugars but not in amino acids, and had minimal aromaticity. Components isolated from the cultivated soil were broadly similar to those from a comparable soil in long term grassland. The compositions of fractions isolated from the drainage water were similar to those extracted from the soil but had higher carboxyl content. The amount and composition of the various organic fractions in grassland and the continuously cropped soil are discussed in terms of their potential to contribute to carbon sequestration by soil under similar management regimes.  相似文献   

6.
The role of organic ligands in metal complexing in natural waters has received little attention because of uncertainties regarding both the abundance and nature of dissolved organic carbon compounds. Recent data show that the bulk of dissolved organic matter in natural waters consists of highly oxidized and chemically and biologically stable polymeric compounds closely resembling soil humic substances. Average molar concentrations of these aquatic humics in major U.S. rivers range from 5 × 10?6to 3 × 10?5 moles 1?1. Fractional elution of soil organic matter by meteoric waters may be considered to be the main process contributing to the presence of humic matter in rivers. The aquatic humic polymers participate in complex formation through ionizable functional groups with a range of differential acidities. The stabilities of metal-humic complexes in natural waters are higher than those of the corresponding inorganic metal complexes. Quantitative evaluation of the metal-organic interactions can be approached by applying variable equilibrium functions which take into account the differential physico-chemical characteristics of the active complexing sites on the polymer molecule. Assuming an average humic concentration of 10 mg 1?1, complexation of trace metals can be significant even in the presence of excess concentrations of major cations.  相似文献   

7.
《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   

8.
In the Upper Cretaceous sequence of the Negev (southern Israel) the organic matter in phosphorites and cherts differs from that associated with oil shales in its higher content of humic substances and lower kerogen content, and in its more intensive microbial alteration. The n-alkane distribution pattern of the oil shales, phosphorites and cherts indicates that marine biota, probably algae, are the main organic precursors of their organic matter. In some of the oil shales, however, some contribution of terrestrial organic matter is also evident. Similar high phytane/pristane ratios indicate that the organic matter in the oil shales as well as in the phosphorites and cherts accumulated under reducing conditions. The main differences in the organic matter composition are attributed to early diagenetic processes rather than to different biotic precursors or to late modifications due to temperature-induced maturation. The depositional model suggested for the sequence involves upwelling conditions at the boundary between the deep Tethys and the shallow shelf, which induced high organic productivity deep into the inner shelf. Bottom water circulation enabled intensive microbial alteration of the organic matter, followed by a winnowing process leading to phosphorite formation. Since humification is considered an oxygen-consuming reaction, these processes favoured the formation of oxygen-enriched humic substances and the oxidation of humic substances already present. These humic substances are relatively resistant to further alteration and their conversion into kerogen is thus retarded. Subsequently, syndepositional tectonic activity resulted in the introduction of less saline water, restriction of bottom-water circulation and the establishment of a density stratification in the water body. Consequently, aeration of the bottom layer and the sediments was inhibited, microbial alteration was reduced and later winnowing processes were prevented. Such conditions favoured the formation of kerogen directly, rather than through humic substances, and also favoured the preservation of most of the organic matter in the form of oil shale deposits instead of phosphorites.  相似文献   

9.
129I is one of the three major radiation risk contributors to the public as a consequence of past nuclear processing activities at Department of Energy (DOE) facilities. Elevated levels of 129I are present in the surface soils of F-Area of Savannah River Site, which used to be an isotope separation facility for the production of nuclear weapons components. The 129I in soils is thought to be bound predominantly to soil organic matter (SOM). Measurements of stable 127I and radioactive 129I in humic acids (HAs) and fulvic acids (FAs) obtained by five successive alkaline, two glycerol and one citric acid-alkaline extraction, demonstrated that these extractable humic substances (HS) together account for 54-56% and 46% of the total 127I and 129I in the soil, respectively. The remainder was likely bound to residual SOM. The iodine content (μg-I/g-C) generally decreased with each subsequent extract, while 129I/127I increased concurrently. The coincident variations in chemical compositions, aromaticity (estimated by UV spectroscopy), functional groups (e.g., aliphatic), degree of humification, relative migration in the hydrophobic interaction column, and molecular weight indicated that: (1) iodine in different HAs was bound to a small-size aromatic subunit (∼10 kDa); (2) the large-size subunit (∼90 kDa), which likely linked the small-size unit through some weak chemical forces (hydrogen bonds, hydrophobic or electrostatic interactions), determined the relative mobility of iodine bound to organic matter; (3) from the strong correlation between iodine content and aromaticity in the HAs, we suggested that iodine incorporation into the SOM via covalent aromatic C-I bond is the key mechanism controlling iodine behavior in this system. However, this relationship is not universal for all fractions of organic matter as evidenced from the different slopes of this relationship at the two sampling sites, as well as from the different relationships for HAs and FAs, respectively. These differences in iodination are due to different SOM molecular sizes, compositions, and availability of preferred iodination sites. 129I in the soil downstream from the contaminated site and near a wetland abruptly dropped below our detection limit (0.5 pCi-129I/g-soil), which suggests that the high SOM in the plume soil around the 129I-contaminated F-Area might be a natural barrier to scavenge radioiodine released from the nuclear waste repository by forming organo-iodine compounds. Soil resuspension experiments showed that mobile 129I was mostly associated with a low average molecular weight amphiphilic organic carrier (13.5-15 kDa). SOM clearly behaves as a sink for iodine at the Savannah River Site F-Area. However, this work demonstrates that a small fraction of the SOM can also behave as a source, namely that a small fraction that may be readily dispersible under some environmental conditions and presumably release iodine in the organic-colloidal form. This radioiodinated organo-colloid likely can get into the groundwater through infiltration or surface runoff where it might migrate further into the wetlands. Results from this study provide the geochemical basis for future 129I migration controls, remediation, and/or land-groundwater management strategies.  相似文献   

10.
Two organic rich sediments, an oxic muddy sand and a silty mud containing sulphate reducing and methane producing metabolic zones, were sampled from Loch Duich, a fjord type estuary in the N.W. coast of Scotland. Dissolved organic carbon (DOC), as measured by dry combustion and UV absorption, remained constant (8.3–15.8 mg C/l) with depth in the oxic pore waters at a concentration at least twice that of the overlying seawater. DOC in the anoxic pore waters increased linearly with depth from 13.6 at the surface to 55.9–70.5 mg C/l at 80cm. Most of the DOC was present in the high molecular weight (HMW) fraction as separated by ultrafiltration; the low molecular weight (LMW) fraction remained constant (10.0 mg C/l) in both oxic and anoxic pore waters. Spectroscopic data showed the ‘humic’ fraction of the HMW dissolved organic matter was mainly fulvic acid, a small proportion (approx 1%) of humic acid, and a third fraction, possibly melanoidins, which increased relative to fulvic acid with depth. These data confirm the pathway of humification (NissenBaum et al, 1971; nissenbaum and Kaplan, 1972) where HMW organic matter accumulates in pore waters as condensation products of LMW organic substances.  相似文献   

11.
Characterization of humic substances is challenging due to their structural complexity and heterogeneity. Solid state nuclear magnetic resonance (NMR) is regarded as one of the best tools for elucidating structures of humic substances. The primary solid state NMR technique that has been used so far is the routine 13C cross polarization-magic angle spinning (CP-MAS) technique. Although this technique has markedly advanced our understanding of humic substances, the full potential of NMR for characterizing humic substances has yet to be realized. Recent technical developments and applications of advanced solid state NMR have revealed the promise to provide deeper insights into structures of humic substances. In this paper, we summarized and demonstrated the systematic solid state NMR protocol for characterization of humic substances using a humic acid as an example. This protocol included (1) identification of specific functional groups using spectral editing techniques, occasionally assisted by 1H13C two-dimensional heteronuclear correlation (2D HETCOR) NMR, (2) quantification of specific functional groups based on direct polarization-magic angle spinning (DP-MAS) and DP-MAS with recoupled dipolar dephasing, combined with spectral editing techniques, (3) determination of connectivities and proximities of specific functional groups by 1H13C 2D HETCOR or 2D HETCOR combined with spectral editing techniques, and (4) examination of domains and heterogeneities by 1H13C 2D HETCOR with 1H spin diffusion. We used a soil humic acid as an example to demonstrate how this protocol was applied to the characterization of humic substances step by step. Afterwards, based on typical 13C NMR spectra of humic substances we described how we could combine different NMR techniques to identify specific functional groups band by band from downfield to upfield. Finally, we briefly mentioned the potential new NMR techniques that could be developed to enrich the current systematic protocol. This systematic protocol is not only applicable to humic substances but also to other natural organic matter samples.  相似文献   

12.
Chemical interactions between 2-aminobenzothiazole (ABT) and a soil humic acid (HA) extracted from a gleyic planosol were investigated by solid-state 13C CP/MAS NMR spectroscopy. Reactions of the HA with ABT 13C-labelled at the C-2 position were performed in aqueous solution under noncatalysed and enzyme-catalysed conditions. Without enzymic catalysis the amount of ABT-2-13C taken up by soil HA in an oxygen atmosphere was about twice the uptake under argon. In the presence of the oxidative enzyme laccase and air, about three times as much ABT was bound to HA as compared to the uptake in a control experiment with inactivated laccase. The results suggest that oxidation reactions of the humic acid significantly enhance the extent of binding between ABT and HA. The 13C NMR spectra of the HA–ABT adducts indicated that in both noncatalysed and enzyme-catalysed reactions ABT may be bound to humic acid by noncovalent as well as covalent bonds.  相似文献   

13.
Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai−, derived from DOC at sample pH and the concentration of organic anion, Ax− at the equivalence point were calculated using car☐yl contents from isolated and purified humic material from soil solutions. Subtracting Ax− from Ai− yields the contribution of humic substances to the buffering capacity (Aequiv.−). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado.  相似文献   

14.
The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS 15N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by 15N NMR. Liquid state 15N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection (1H–15N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.  相似文献   

15.
CPMAS 13C NMR spectra of two estuarine sedimentary humic acids were recorded on a Bruker WP-SY 200 spectrometer. Both samples were found to contain similar aromatic and aliphatic carbon fractions. The sedimentary humic acids have unusually high methoxyl contents and more than one type of methoxyl is indicated. The high methoxyl content may be related to relatively low values for estuarine sedimentary humic acid-metal complexes. Carbohydrate contents of the humic acid samples were also found to be low.  相似文献   

16.
The effects of organic matter, humic acid and Tween-80 on decabromodiphenyl ether (BDE-209) behavior in soil columns were investigated. The BDE-209 transport was simulated in 4-cm-length soil columns whether organic matter was added or not. A high concentration of BDE-209 was washed out of the soil column in the presence of 500 mg L?1 of Tween-80 for forming and suspending contaminated soil colloids in more than 4-cm-length ones (especially in 10-cm-length ones). While the humic acid was to facilitate BDE-209 adsorption onto soil particles (like soil colloids), Tween-80 was to enhance BDE-209 movement in porous media. The significant concentration averaged from 0.2 to 0.1 μg L?1 in soil columns of length from 10 to 24 cm with Tween-80 addition by comparing the estimated marginal means (p < 0.05, SPSS). Contrasted with humic acid-binding BDE-209 in soil particles, Tween-80 could carry contaminant soil colloids into deeper layers and even affect the final effluents of 25-cm-length columns. It was visibly presented that the BDE-209 concentration in the effluents was mainly induced by Tween-80. Thus, BDE-209 was carried by soil colloids to transport and pollute longer and wider soil distance with the help of the effective promoters and stabilizers of Tween-80 and humic acid in soil matrix.  相似文献   

17.
Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.  相似文献   

18.
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   

19.
为探讨天然黏土矿物及有机质对纳米乳化油在多孔介质中迁移滞留的影响，本文选取高岭石和蒙脱石这两种黏土矿物以及有机质的典型代表腐殖酸，开展了单一矿物、有机质及有机矿质复合物对纳米乳化油的吸持批实验研究，并运用比表面积全分析、扫描电镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射(XRD)等技术手段探讨了吸持机理。实验结果表明，介质对纳米乳化油的吸持均符合Freundlich模型；单一矿物及腐殖酸对纳米乳化油的吸持能力表现为：蒙脱石>腐殖酸>高岭石，有机矿质复合样品的吸持能力表现为：蒙脱石-腐殖酸>高岭石-腐殖酸，且均大于其对应的单一样品，出现了“1+1>2”的现象，表明介质组成越复杂，对纳米乳化油的吸持滞留程度越大。进一步分析证实，纳米乳化油主要通过氢键和疏水作用吸持在矿物和腐殖酸表面，表面结构性质是高岭石和蒙脱石吸持过程中的主导因素，因此蒙脱石具有更强的吸持能力，而腐殖酸的吸持主要通过颗粒间聚集作用来实现；对于复合样品，吸持主要通过氢键、配体交换和疏水作用结合来实现。腐殖酸与矿物的复合会增加吸持位点并且增强矿物表面疏水性，从而促进吸持。腐殖酸与纳米乳化油的共吸...  相似文献   

20.
The process of the transformation of fresh organic matter (OM) into more stable and recalcitrant humic substances is still not completely clear. Understanding how OM humification evolves in northern bog environments is extremely important, especially considering that they represent one of the largest terrestrial carbon pools.Structural changes of OM occurring during the humification process have been generally evaluated by indirect measurements of the degree of humification. Several approaches have been used, often providing contrasting results probably because humification is a complex process that evolves differently according to varying pedoclimatic conditions.In the present work, the authors followed the evolution of peat OM along a 165 cm bog profile (covering the mid- to late Holocene) correlating results obtained from both organic petrological and chemical investigation. Data clearly underline a significant agreement between the two perspectives, both showing either a quite immature peat material or the presence of three distinct zones along the profile. In detail, both spectroscopic (i.e., FT-IR and three dimensional fluorescence spectra, humification indexes), and Rock-Eval pyrolysis results (low residual organic carbon content and high hydrogen and oxygen index values) showed the occurrence of a central zone (from 20-30 cm to 120 cm depth) often characterized by high heterogeneity and a low degree of humification when compared to the upper ∼20 and bottom 40 cm sections.  相似文献   

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