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1.
Covalent and non-covalent interaction of proteinaceous materials in soils and sediments has been suggested as an important mechanism for immobilizing nitrogen in numerous types of environments. In a previous study (Hsu P.-H., Hatcher, P.G., 2005. New evidence for covalent coupling of peptides to humic acids based on 2D NMR spectroscopy: A means for preservation. Geochimica et Cosmochimica Acta 69, 4521–4533), we provided molecular evidence for covalent, as well as non-covalent, bonding between 15N-labeled peptides and humic acid molecules using the 2D HSQC (heteronuclear single quantum coherence) NMR technique. In this report, we examine the influence of aromaticity and aliphaticity of peptides and humic materials on these covalent and non-covalent interactions. We use 2D NMR techniques to evaluate bonding interactions of 15N labeled peptides, having different aromatic and aliphatic properties, with three humic acids that vary in degree of aromaticity. The peptide containing primarily aromatic amino acid residues is observed to form covalent and non-covalent bonds with mainly aromatic-rich humic acids. The peptide composed of aliphatic amino acid residues shows, on the other hand, only bonding interactions with aliphatic-rich humic acids. These observations provide the first direct molecular evidence that aliphatic functional groups are involved in bonding with proteinaceous materials. The process may play an important role in sequestration of proteinaceous materials in sedimentary systems such as marine systems where the humic materials are mainly aliphatic in nature.  相似文献   

2.
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   

3.
13C and 1H NMR spectra were obtained for humic acids isolated from marine sediments. NMR shows great promise in identifying structural components of humic acids as some new and interesting structural features are identified. Aliphatic structures were found to constitute a much larger fraction of humic acids than previously thought, and they appeared to be highly branched. Although the aromatic content of terrestrial humic acid was found to be lower than expected, the aromaticity appears to be a specific discriminator of terrestrial/aquatic source types. A humic acid isolated from an anoxic algal sapropel was found to be composed predominantly of polyuronic acids and different than other aquatic sedimentary humic substances.  相似文献   

4.
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   

5.
Electron paramagnetic spectra of humic acid and various fractions of fulvic acid from a deep peat soil were studied and related to some of the metals present. In fulvic acid, VO2+ occurred in complexed form. The Mn2+ components all had a high degree of ionicity. In the humic acid fraction Cu2+ was present as a copper porphyrin-type complex.  相似文献   

6.
Complexes formed by the addition of vanadyl salts to a peat humic acid have been studied by EPR spectroscopy. The spectra show that the vanadium is in an environment with approximately axial symmetry. The g-values and 51V hyperfine coupling constants indicate that the vanadium remains in the vanadyl state and is complexed possibly either by oxygen donor groups or by mixed oxygennitrogen donor groups in the humic acid. Identical spectra were obtained when the vanadium was added to the humic acid as the metavanadate ion, thus showing that reduction of vanadium from oxidation state (V) to (IV) occurs.  相似文献   

7.
13C NMR spectra of solid humic substances in Holocene sediments have been obtained using cross polarization with magic-angle sample spinning techniques. The results demonstrate that this technique holds great promise for structural characterizations of complex macromolecular substances such as humin and humic acids. Quantifiable distinctions can be made between structural features of aquatic and terrestrial humic substances. The aliphatic carbons of the humic substances are dominant components suggestive of input from lipid-like materials. An interesting resemblance is also noted between terrestrial humic acid and humin spectra.  相似文献   

8.
Cross-linking of humic substances with organic bridging groups is thought to contribute to the humification of soil organic matter. Model cross-linked humic substances were prepared by cross-linking Amherst soil humic acid by a diepoxide and a polycarboxylic acid, applying procedures established for cross-linking of polymers and textile fabrics. Products of the cross-linking reactions were analyzed by FTIR and 13C CPMAS NMR. Physicochemical properties of the products were determined by solubility experiments and thermal analysis. The incorporation of the cross-linker into the matrix of the humic acid by covalent linkages was confirmed by both the disappearance of bands of the reactive functional groups of the cross-linker in the FTIR spectrum and the increase of signals related to the incorporation of the cross-linker into the matrix of the humic acid in the FTIR and 13C CPMAS NMR spectra. The formation of covalent ester and ether linkages by the cross-linking reaction was indicated. Water solubilities at pH 6.2 of the cross-linked samples as determined by UV/Vis spectrometry were reduced compared to controls. Fewer water molecule bridges were formed in the cross-linked samples, which was attributed to a lower number of available functional groups and increased distances between humic acid strands caused by the cross-linking molecules. Reduced reactivities of humic acid strands in the cross-linked samples further indicated successful cross-linking. The reactions investigated in this study can be regarded as models for reactions occurring in natural soils to test the significance of cross-linking reactions in the humification process of soil organic matter and the physico-chemical properties and ecological function of organic matter in geosolids.  相似文献   

9.
Authors' reply     
In our original work we have correctly quoted Wilson and Goh. Some comments of these authors on 13C NMR spectra recording and the importance of aromatic structures in humic substances are discussed.  相似文献   

10.
The main objective of this study is to investigate the possibility of powdered eggshell used as an adsorbent material for removal of humic acid from peat water. The influences of contact time, dose of eggshells, pH, and temperature were the factors considered in the removal processes of humic acid from peat water. In addition, adsorption isotherms of humic acid onto the powdered eggshell were also evaluated with the Langmuir and Freundlich approximations. Our results showed that the equilibrium of the process was eventually established after 60 min of the contact time, and also found that using 5 g of the powdered eggshell nearly 95 % of humic acid has been successfully removed from the peat water. The removal of humic acid gave better result when it was conducted at low pH, and it was almost unaffected the temperatures variation. The data was well fitted to Freundlich isotherm with the correlation coefficient of not <0.999, and could uptake the humic acid about 126.58 mg/g at pH 4.01, estimated from the Langmuir model. The kinetic experimental data proportionally correlated with the pseudo-second-order kinetic model with a rate constant in the range of 0.016–0.112 g mg?1 min?1, while intra-particle-diffusion were the main rate determining step in the humic acid removal process. The powdered eggshell investigated in this study, thus, exhibited as a high potential adsorbent for the removal of humic acid from peat water.  相似文献   

11.
Humic substances present a geochemically and environmentally important, yet poorly characterized, component of dissolved organic matter. In the past they have generally been described as macromolecular polymers containing many different functional groups. Recently, it has been suggested, partly on the basis of new experimental data, that such materials are rather supramolecular in nature, consisting of smaller molecular units held together by noncovalent forces such as van der Waals forces and H-bonds. A perplexing difficulty in characterizing humic acids has always been that data expected to be informative, such as their Visible-UV spectra, were sadly lacking in structure. This has usually been explained using models in which ensembles of molecules are present characterized by either long-range charge-charge interactions or random short-range donor-acceptor interactions.Structural components resembling hydroquinone:quinone donor-acceptor complexes have been postulated to explain the near-IR and visible spectra of humic acids (Del Vecchio R., and Blough N.V. (2004) On the origin of the optical properties of humic substances. Environ. Sci. 38, 3885-3891). We have calculated structures, energetics and Visible-UV spectra for several different quinone and hydroquinone monomers and for donor-acceptor complexes formed between hydroquinone, H2Q, the donor, and quinone, Q, the acceptor. Most of the Visible-UV spectral calculations are carried out using time-dependent density functional theory. For the monomers the calculated energies are in good agreement with experiment. We confirm that the absorption spectra of the D:A complexes have maxima at much lower energy than their monomeric components. These absorption energies are influenced by substituents on the aromatic rings, but are also sensitive functions of the distances between the aromatic rings. The importance of D:A complexes in generating a spectrum like that of natural humic acids is consistent with the model of Del Vecchio and Blough (2004). However, our calculations of reaction free energies indicate that the donor-acceptor interactions do not arise from free D:A complexes, but rather from forced or random close approach of D and A rings.  相似文献   

12.
To obtain information on the contribution of aromatic fragments to the chemical structure of humic substances, we carried out a study on the [1H]NMR and [13C]NMR spectra of humic and fulvic acids and their oxidative degradation products extracted from an Andosol soil.[1H]NMR spectra of all organic fractions present considerable adsorption between 7.4 and 8.8 ppm, due to the presence of aromatic protons.The percentages of aromatic protons in respect to the total amount of protons are as follows: FA 20%, HA 19%, degraded FA < 12%, degraded HA 14%. The values indicate that the contribution of aromatic structures to the humic substances is significant, also considering that they are highly substituted.The degraded fractions contain smaller amounts of aromatic protons, because degradation causes the opening of the aromatic rings. Thus results obtained from the degradation do not seem to be reliable for defining the importance of aromatic structures in humic substances.Also the [13C]NMR spectra show signals in the aromatic region which derive from unsubstituted carbon atoms, while signals originating from tertiary carbon atoms merge with the noise. We believe that, at present, [1H]NMR spectroscopy is more suited for studying the role played by aromatic compounds in organic soil fractions.  相似文献   

13.
《Applied Geochemistry》2005,20(3):537-544
Thermal analyses (TG–DTA), elemental composition and isotope analyses (13C and 15N) were performed on humic acids (HA) from peats, leonardites and lignites, in order to investigate their structure and the changes taking place during the humification process. Thermal analyses showed structural differences between HA samples in relation to their coalification rank. In particular the lignite HA were characterized by a more stable chemical composition at high temperatures.The δ13C and δ15N values can provide information on the biogeochemical processes involved in HA formation. In particular, peat HA were linked to anoxic environments that enable plant residues to persist in their structure. In contrast, leonardite and lignite HA formation seems to be governed by different biogeochemical processes from those responsible for peat diagenesis. However, the isotopic analyses did not provide any distinction between leonardite and lignite HA. On the basis of the data presented in this study, it may be concluded that TG–DTA and isotope ratio measurements are powerful tools for investigating the formation pathway of humic substances from coals.  相似文献   

14.
《Organic Geochemistry》1987,11(2):65-71
ESR measurements of stepwise-pyrolyzed melanoidins and humic substances (at various temperatures, mesh size, and pH values) furnished the following information: the melanoidin structure stabilizes the long-living free radicals in a manner similar to humic substances; the g and Ng values of melanoidins are similar to those of the humic substances, the cleavage of CC and CX (X = heteroatom) bonds increases the Ng value. Thermogravimetric curves, weight loss by stepwise pyrolysis, and 13C-CP/MAS NMR were found to be in good correlation with ESR data regarding the structural features of melanoidins and humic substances.  相似文献   

15.
《Organic Geochemistry》1987,11(2):91-101
Nuclear magnetic resonance (NMR) techniques have been applied to the structural characterization of humic substances isolated from an organic-rich sediment in Loch Thurnaig, northwest Scotland. Both the sedimentary humic acid (SHA) and sedimentary fulvic acid (SFA) fractions from Loch Thurnaig contained substantial quantities of carboxylic and alkyl carbon with a small contribution (26 and 22% respectively) of aromatic/olefinic carbon atoms. The latter structures were shown by dipolar dephasing 13C NMR to be largely non-protonated. Differences in the alkyl structures of the two fractions were noted, with the SHA containing a larger amount of branched chain aliphatic material. As branched chain compounds are more resistant to microbial degradation than straight chain compounds, this may indicate that SHA is the older, more refractory fraction of the sedimentary organic matter, although it is possible that the results reflect different algal precursor material. The fraction of aromatic carbon was higher in the SHA than in the SFA as is generally found for humic and fulvic acids isolated from the same source. The low aromaticities and highly branched aliphatic structures show that the sedimentary humic substances from the loch resemble dissolved marine humic substances rather than their terrestrial counterparts.  相似文献   

16.
A peat deposit from the East European Russian Arctic, spanning nearly 10 000 years, was investigated to study soil organic matter degradation using analyses of bulk elemental and stable isotopic compositions and plant macrofossil remains. The peat accumulated initially in a wet fen that was transformed into a peat plateau bog following aggradation of permafrost in the late Holocene (～2500 cal a BP). Total organic carbon and total nitrogen (N) concentrations are higher in the fen peat than in the moss‐dominated bog peat layers. Layers in the sequence that have lower concentrations of total hydrogen (H) are associated with degraded vascular plant residues. C/N and H/C atomic ratios indicate better preservation of organic matter in peat material dominated by bryophytes as opposed to vascular plants. The presence of permafrost in the peat plateau stage and water‐saturated conditions at the bottom of the fen stage appear to lead to better preservation of organic plant material. δ15N values suggest N isotopic fractionation was driven primarily by microbial decomposition whereas differences in δ13C values appear to reflect mainly changes in plant assemblages. Positive shifts in both δ15N and δ13C values coincide with a local change to drier conditions as a result of the onset of permafrost and frost heave of the peat surface. This pattern suggests that permafrost aggradation not only resulted in changes in vegetation but also aerated the underlying fen peat, which enhanced microbial denitrification, causing the observed 15N‐enrichment. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

17.
《Organic Geochemistry》1987,11(3):139-149
Molecular Mass (MM) distributions in humic acids from peat and two lignites have been investigated by high performance size-exclusion chromatography (SEC) after methylation and found to be in the range approximately 300 to more than 5000, with number average NM(Mn) near 800. Values of Mn determined by SEC were in good agreement with those from vapour pressure osmotery. High field13C NMR spectra of the methylated humic acids are extremely well resolved, and indicate that the samples are significantly different, despite their similar elemental compositions and MM distributions.  相似文献   

18.
Detailed structural information on two humic acids extracted from two sinking particulate matter samples at a water depth of 20 m in the Saguenay Fjord (F-20-HA) and the St. Lawrence Estuary (E-20-HA) (Canada), was obtained by advanced solid-state NMR. Spectral-editing analyses provided numerous structural details rarely reported in geochemical studies. The NMR data account almost quantitatively for the elemental compositions. The two humic acids were found to be quite similar, consisting of four main structural components: peptides (ca. 39 ± 3% vs. 34 ± 3% of all C for E-20-HA and F-20-HA, respectively); aliphatic chains, 14-20 carbons long (ca. 25 ± 5% vs. 17 ± 5% of all C); aromatic structures (ca. 17 ± 2% vs. 26 ± 2% of all C); and sugar rings (14 ± 2% vs. 15 ± 2% of all C). Peptides were identified by 13C{14N} SPIDER NMR, which selects signals of carbons bonded to nitrogen, and by dipolar DEPT, which selects CH-group signals, in particular the NCH band of peptides. The SPIDER spectra also indicate that heterocycles constitute a significant fraction of the aromatic structures. The aliphatic (CH2)n chains, which are highly mobile, contain at least one double bond per two chains and end in methyl groups. 1H spin diffusion NMR experiments showed that these mobile aliphatic chains are in close (<10 nm) proximity to the other structural components. A major bacterial contribution to these two samples could explain why the samples, which have different dominant organic matter sources (terrestrial vs. marine), are similar to each other as well as to degraded algae and particles from other waters. The NMR data suggest structures containing mobile lipids in close proximity to peptides and carbohydrates (e.g., peptidoglycan) as found in bacterial cell walls. Measured yields of muramic acid and d-amino acids confirmed the presence of bacterial cell wall components in the studied samples.  相似文献   

19.
《Applied Geochemistry》2000,15(2):133-139
The sorption of Yb3+, UO2+2, Zn2+, I− and SeO2−3 onto Al2O3, Fe2O3 and SiO2 were determined by a batch technique in the presence and absence of fulvic acids. The effects of fulvic acid on sorption were compared. The existing general consensus, that humic substances tend to enhance metal cation sorption at low pH, reduce metal cation sorption at high pH and reduce inorganic anion sorption between pH values 3 to 10, was generally shown to be true. However, in this work many exceptions to the general consensus were found. The study indicated that the effect of humic substances on sorption of inorganic cations or anions depends not only on pH, but also on the nature of the oxide, the nature of humic substance, fractionation of the humic substance by sorption, the relative strength of complexes of both soluble and sorbed humic substances, the extent of surface coverage by humic substance, the initial concentration of humic substance and the inorganic electrolyte composition.  相似文献   

20.
Freshwater humic substances from Lake Celyn, Gwynedd, N. Wales have been investigated by 13C-NMR spectroscopy. Carboxyl, aromatic, o-alkyl and alkyl resonances can be recognised. Varying pulse delay from 0.43 s to 2.5 sec has little effect on the magnitude of the signal ascribed to aromatic carbon, but there is a small nuclear Overhauser effect (1.45 at a pulse delay of 0.8 sec).The results show-that 24% of the Lake Celyn humic acid carbon is carboxyl and 40% is aromatic. The high proportion of aromatic carbon suggests the Lake Celyn humic acid is largely formed from terrestrial humic substances from the surrounding peaty watershed.  相似文献   

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